WO2019062446A1 - Flue gas treatment method - Google Patents

Flue gas treatment method Download PDF

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Publication number
WO2019062446A1
WO2019062446A1 PCT/CN2018/103022 CN2018103022W WO2019062446A1 WO 2019062446 A1 WO2019062446 A1 WO 2019062446A1 CN 2018103022 W CN2018103022 W CN 2018103022W WO 2019062446 A1 WO2019062446 A1 WO 2019062446A1
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Prior art keywords
flue gas
treating agent
nano
weight
diameter
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PCT/CN2018/103022
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French (fr)
Chinese (zh)
Inventor
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 WO2019062446A1 publication Critical patent/WO2019062446A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602

Definitions

  • the invention relates to a method for treating flue gas, in particular to a method for desulfurization and denitrification of flue gas.
  • Sulfur dioxide is the most common sulfur-containing oxide with a strong pungent odor and is one of the major pollutants in the atmosphere. Since coal and petroleum usually contain sulfur compounds, sulfur dioxide is formed during combustion; steel also contains a large amount of sulfur, and a large amount of sulfide is released into the air during steel making and iron making. When sulfur dioxide is dissolved in water, sulfurous acid is formed, which forms acid rain. If SO 2 is further oxidized in the presence of nitrogen dioxide, sulfuric acid is formed, which is extremely harmful to the environment and human health.
  • Dioxin (1,4-dioxadiene) is a monocyclic organic compound. It is a by-product that is not useful in industry. It is often found in the atmosphere, soil and water with tiny particles. The main sources of pollution are the chemical metallurgical industry, waste incineration, papermaking and the production of pesticides. Metal smelting produces a large amount of dioxins, especially the smelting of copper, aluminum and zinc, which produces a large amount of dioxins. Metal smelting is an important source of emissions of these toxic gases.
  • the main method of industrial desulfurization is lime-limestone desulfurization, the absorbent powder is slurried, and SO 2 in the flue gas is absorbed in the absorption tower.
  • Wet desulfurization produces large amounts of wastewater and requires an additional wastewater treatment system.
  • the operating cost is high, the floor space is large, the system management operation is complicated, and the wear and corrosion phenomenon is more serious.
  • by-products derived from desulfurization are piled up in large quantities because of their low quality and limited market space, causing secondary pollution to the environment.
  • the main method of denitration on the market are the selective catalytic reduction (SCR) method, under the action of the catalyst, when the presence of oxygen, introduced into the reactor in preference to ammonia reacts with NO x in the flue gas, generates Environmentally friendly N 2 and H 2 O.
  • SCR selective catalytic reduction
  • the SCR technology has high denitration efficiency and mature technology, but the operating cost is high.
  • SO 2 in the flue gas is easily oxidized to produce SO 3 , and the reaction with excess ammonia gas to form ammonium hydrogen sulfate causes corrosion to the equipment.
  • the removal of dioxins in flue gas is mainly activated carbon adsorption and flue gas quenching technology.
  • Activated carbon only transfers dioxins from flue gas to activated carbon, and does not fundamentally remove dioxins.
  • the flue gas quenching technology refers to the sudden drop of the flue gas temperature from 800 ° C to below 200 ° C to avoid the production of dioxins.
  • Chinese Patent Application No. 201220444793.2 discloses a device for suppressing the production of dioxin in incineration flue gas. The device uses a waste heat recovery method to firstly take the waste gas from the incinerator in a safe temperature range in which no dioxin is produced.
  • the high-temperature flue gas is reduced to the middle temperature section, and then the quenching and cooling is performed in the sensitive temperature region where the dioxin is generated, so that the content of dioxin in the incinerated flue gas discharged is much lower than the control index stipulated by the national standard.
  • This method causes a large amount of waste of resources, and cannot simultaneously achieve desulfurization and denitrification.
  • An object of the present invention is to provide a method for treating flue gas which can simultaneously desulfurize, denitrify, and deodorize. Further, the method of the present invention is high in efficiency, simple in operation, and low in operating cost.
  • the invention provides a method for treating flue gas, which comprises the following steps:
  • the flue gas having an oxygen content of 3 to 8 vol% is subjected to dust removal treatment to obtain flue gas after dust removal; and the dust content in the flue gas after the dust removal is 10 to 30 mg/Nm 3 ;
  • the flue gas temperature is 200 ⁇ 500 ° C
  • the flue gas flow rate is 3 ⁇ 8m / s
  • the flue gas treating agent comprises the following components based on 100 parts by weight of the flue gas treating agent: 70 to 96 parts by weight of the nano-calcium oxide, 2 to 15 parts by weight of the nano-ferric oxide, and 2 to 15 parts by weight of the nano-silica.
  • the flue gas treating agent further comprises a binder selected from the group consisting of lactic acid, carboxymethyl cellulose, polyvinyl alcohol, and starch. At least one of alumina, tianqing powder.
  • the flue gas treating agent further comprises glass fibers.
  • the flue gas treating agent is obtained by uniformly mixing the respective components to obtain a solid mixture, and uniformly mixing the solid mixture with water to obtain a semi-dry mixture.
  • the semi-dry mixture is shaped, then autoclaved and dried to obtain the flue gas treating agent; the autoclave curing temperature is 160-200 ° C, and the pressure is 0.6-1.8 MPa.
  • the flue gas treating agent is in the form of particles selected from tabular particles, spherical particles or columnar particles; the flake particles have a thickness of 5 to 10 mm and a diameter of 10 to 25 mm; the columnar particles have a diameter of 1 to 3 mm and a length of 3 to 8 mm; and the spherical particles have a diameter of 2 to 5 mm.
  • the purifying treatment is performed in a tubular fixed bed, and the flue gas treating agent is filled in a reaction tube of the tubular fixed bed, and a filling height thereof is
  • the length of the reaction tube is 80 to 90%; and the diameter of the reaction tube is greater than 8 times the diameter of the flue gas treating agent.
  • the flue gas treating agent is in a honeycomb shape; the honeycomb pores have a pore diameter of 4.5 to 7.5 mm, and the honeycomb pores have a density of 800 to 1200 particles/m 2 .
  • the flue gas treating agent is a flat module and is prepared by coating the semi-dry mixture on the surface of the sheet substrate, then passing through the wrinkles and cutting. A veneer is formed, and the veneers are assembled into a flat module.
  • the veneer has a height of 400 to 800 mm, a width of 400 to 550 mm, a thickness of 0.5 to 1.0 mm, and a spacing between adjacent two veneers of 5 to 9mm.
  • the flue gas treatment method of the present invention preferably, SO 2 concentration in the flue gas before the dust removal is 1000 ⁇ 3000mg / m 3, NO x concentration was 100 ⁇ 350mg / m 3, the concentration of dioxin body is pre-existence 5 ⁇ 25ng ⁇ TEQ/m 3 .
  • the flue gas treatment method of the invention can simultaneously realize flue gas desulfurization, denitration and deodorization, and has high efficiency, simple operation, low operation cost, wide use range, no pollutants and no secondary pollution to the environment. .
  • the flue gas treatment method of the invention has a desulfurization efficiency of over 95%, a denitration efficiency of 94% or more, and a dioxin efficiency of 91% or more.
  • the flue gas treatment method of the invention can simultaneously comprehensively treat the flue gas, thereby simultaneously removing sulfur dioxide, nitrogen oxides and dioxins in the flue gas.
  • the method includes the following dust removal step, purification treatment step, and the like.
  • the flue gas having an oxygen content of 3 to 8 vol% is subjected to dust removal treatment to obtain flue gas after dust removal; and the dust content in the flue gas after the dust removal is 10 to 30 mg/Nm 3 .
  • the oxygen content in the flue gas is 3 to 8 vol%, preferably 5 to 8 vol%.
  • the nano-ferric oxide in the flue gas treating agent can oxidize NO to NO 2 to ensure the denitration effect.
  • the flue gas treatment method of the present invention further includes the step of adjusting the oxygen content of the flue gas. Specifically, when the oxygen content in the flue gas is insufficient, an oxygen fan may be used to add air or oxygen to the flue gas to make the oxygen content in the flue gas reach the above range. It is suitable to control the oxygen content of the flue gas within the scope of the present invention.
  • the oxygen content in the flue gas is too low to ensure the denitration effect; if the oxygen content is too high, the energy consumption and cost are increased.
  • the dust removal treatment may employ a bag type dust removal method, a cyclone type dust removal method, or an electric dust removal method, and is preferably electric dust removal.
  • the dust content in the flue gas after dust removal is 10 to 30 mg/Nm 3 , preferably 10 to 20 mg/Nm 3 , and more preferably 10 to 15 mg/Nm 3 .
  • the flue gas can be smoothly passed through the pores of the flue gas treating agent, and the flue gas treating agent which is not easily clogged and severely worn is formed.
  • the SO 2 concentration in the flue gas is 1000 to 3000 mg/m 3 , and more preferably 1,500 to 2500 mg/m 3 before the dust removal treatment.
  • the NO x concentration in the flue gas is 100 ⁇ 350mg / m 3, more preferably 100 ⁇ 250mg / m 3.
  • the concentration of the dioxin prodrug (e.g., chlorophenol) in the flue gas is 5 to 25 ng ⁇ TEQ/m 3 , and more preferably 10 to 17 ng ⁇ TEQ/m 3 .
  • the water content in the flue gas is from 0.5 to 8 wt%, more preferably from 1 to 5 wt%. This can improve the removal effect.
  • TEQ represents an international toxicity equivalent with a meaning well known in the art.
  • the purifying treatment of the present invention is to treat the flue gas after the dedusting with the flue gas treating agent, thereby purifying the flue gas after the dedusting, and the purifying treatment includes desulfurization, denitration and deodorization.
  • the temperature of the purification treatment is 200 to 500 ° C, preferably 230 to 400 ° C. At this temperature, it is more favorable for the ferric oxide in the flue gas treatment agent to catalyze the oxidation of NO to NO 2 , and the calcium oxide in the flue gas treatment agent reacts with the dioxin-like precursors in the flue gas, hindering the dioxins.
  • the nano-calcium oxide active component in the flue gas treating agent can be desulfurized and denitrated.
  • the flow rate of the flue gas may be from 3 to 8 m/s, preferably from 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treating agent, and the flue gas purifying treatment can be continuously performed.
  • the flue gas treating agent of the present invention comprises the following components: 70 to 96 parts by weight of nano-calcium oxide, 2 to 15 parts by weight of nano-ferric oxide, and 2 to 15 parts by weight of nano-silica based on 100 parts by weight of the flue gas treating agent. .
  • it comprises the following components: 80 to 90 parts by weight of nano-sized calcium oxide, 5 to 10 parts by weight of nano-sized ferric oxide, and 5 to 10 parts by weight of nano-silica.
  • the flue gas treating agent is composed only of 70 to 96 parts by weight of nano-calcium oxide, 2 to 15 parts by weight of nano-ferric oxide, and 2 to 15 parts by weight of nano-silica. .
  • Nano-silica provides a certain adsorption for SO 2 and NO, which increases the possibility of adsorption of reactants on the surface of the flue gas treatment agent; nano-silica and nano-calcium oxide form gelation to improve the smoke treatment agent. Intensity; and excess nano-calcium oxide acts as a desulfurization agent and reacts with dioxin-like precursors in the flue gas to hinder the formation of dioxins; nano-ferric oxide converts NO to NO 2 .
  • the surface of the nano-calcium oxide particles and the SO 2 in the flue gas are reacted by a gas-solid phase to form calcium sulfite and calcium sulfate to achieve the purpose of removing SO 2 .
  • Catalytic iron can be efficiently when the nano oxide particles in the high-temperature (200 ⁇ 350 °C) oxidation of NO to generate NO 2, NO 2 is more conducive to the absorption of calcium oxide nanoparticles, to remove nitrogen oxides.
  • nano-silica can make the flue gas treatment agent have higher catalytic activity under a wider temperature window; at the same time, gelation between nano-silica and nano-calcium oxide can improve the smoke treatment agent. Mechanical behavior. Through the synergy between the three oxides and the high surface activity of the nanomaterials, the flue gas is simultaneously desulfurized and denitrified.
  • the flue gas treating agent further includes a binder for bonding the nano-calcium oxide, nano-ferric oxide, and nano-silica together to facilitate application.
  • the binder may be selected from at least one of lactic acid, carboxymethyl cellulose, polyvinyl alcohol, starch, alumina, and talc; preferably carboxymethyl cellulose or starch.
  • the binder has a weight of 1 to 10% by weight of the flue gas treating agent.
  • the flue gas treating agent may further include fibers such as glass fibers to improve the tensile properties of the flue gas treating agent.
  • the nano silica, the nano calcium oxide, and the nano iron oxide may have a particle diameter of 5 to 100 nm, preferably 10 to 90 nm.
  • the flue gas treating agent of the present invention can be obtained by uniformly mixing the respective components to obtain a solid mixture, uniformly mixing the solid mixture with water to obtain a semi-dry mixture, and molding the semi-dry mixture, followed by steaming. Pressurizing and drying to obtain the flue gas treating agent.
  • the autoclave curing temperature is 160 to 200 ° C, and the pressure is 0.6 to 1.8 MPa.
  • the treatment temperature is 180 to 190 ° C and the pressure is 0.8 to 1.5 MPa.
  • the drying temperature is 100 to 120 °C.
  • the flue gas treating agent of the present invention may be in the form of pellets, honeycombs or flat sheets; preferably in the form of a honeycomb or a flat plate. This is convenient for improving the desulfurization and denitration effect.
  • the flue gas treating agent is in the form of particles. It may be at least one of tabular grains, spherical particles or columnar particles.
  • the tabular grains have a thickness of 5 to 10 mm and a diameter of 10 to 25 mm.
  • the tabular grains may be prepared using a rotary tablet press or a single punch tablet machine.
  • the columnar particles have a diameter ranging from 1 to 3 mm and a length of from 3 to 8 mm; preferably, the columnar particles have a diameter ranging from 1 to 2 mm and a length of from 2 to 5 mm; more preferably, the diameter of the columnar particles is 1.5mm, length is 3mm.
  • the columnar particles may be prepared into a strip shape by a single screw extruder, a twin screw extruder or a hydraulic extruder, and then cut into columnar particles of a certain length.
  • the spherical particles have a diameter ranging from 2 to 5 mm.
  • the spherical particles may be first prepared into a strip shape by a single screw extruder, a twin screw extruder or a hydraulic extruder, cut to a diameter equal to the length, and then processed by a shaping granulator.
  • the purification treatment may be carried out in a tubular fixed bed in which the flue gas treating agent is filled in a reaction tube of the tubular fixed bed, and the filling height is 80 of the length of the reaction tube. ⁇ 90%; and the diameter of the reaction tube is greater than 8 times the diameter of the flue gas treating agent.
  • the reaction tube diameter of the tubular fixed bed may be 15 to 150 mm, and the diameter of the reaction tube is greater than 8 times the diameter of the granular flue gas treatment agent.
  • the heat exchange medium of the tubular fixed bed may be selected from a heat transfer oil, a molten salt or a flue gas to ensure a heating temperature of 200 to 500 ° C.
  • the heat exchange medium is more preferably a molten salt.
  • the flow rate of the flue gas in the tubular fixed bed may be 3 to 8 m/s, preferably 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treating agent, and the ash accumulation in the reaction tube is less.
  • the flue gas treating agent is in the form of a honeycomb.
  • the pore diameter of the honeycomb hole may be 4.5 to 7.5 mm, more preferably 5 to 6.5 mm, still more preferably 5.11 to 6.35 mm.
  • the density of the honeycomb cells may be 800 to 1200 / m 2 , preferably 900 to 1100 / m 2 .
  • the flue gas treating agent has a length of 700 to 1500 mm.
  • the honeycomb flue gas treating agent is placed in the flue gas passage and then subjected to purification treatment.
  • the diameter of the honeycomb flue gas treating agent matches the diameter of the flue gas passage.
  • the flue gas treating agent has a length of 1000 mm, a cross section of 150 x 150 mm, and the number of honeycomb holes is 22.
  • the flow rate of the flue gas through the honeycomb flue gas treating agent is 3 to 8 m/s, and more preferably 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treatment agent to ensure that the flue gas purification treatment is continuously performed.
  • the flue gas treating agent is in the form of a flat plate.
  • the semi-dry mixture was coated on the surface of the sheet-like substrate, and then pleated and cut into a veneer, which was assembled into a flat-shaped flue gas treating agent.
  • the height of the veneer may be 400 to 800 mm, more preferably 500 to 700 mm; the width of the veneer may be 400 to 550 mm, more preferably 420 to 500 mm, still more preferably 430 to 470 mm; and the thickness of the veneer may be 0.5 to 1.0.
  • Mm is more preferably 0.6 to 0.8 mm.
  • the veneer has a height of 600 mm, a width of about 450 mm, and a thickness of 0.7 mm.
  • the spacing between adjacent veneers may be 5 to 9 mm, preferably 6 to 8 mm.
  • the flat flue gas treating agent is placed in the flue gas passage and then subjected to purification treatment.
  • the flow rate of the flue gas through the flat flue gas treating agent module is 3 to 8 m/s, more preferably 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treatment agent to ensure that the flue gas purification treatment is continuously performed.
  • the embodiments of the present invention are further illustrated by the following examples, but are not intended to limit the invention.
  • the average particle diameter of the nano-calcium oxide, the nano-ferric oxide and the nano-silica was 25 nm.
  • nano-calcium oxide 80 parts by weight of nano-calcium oxide, 10 parts by weight of nano-ferric oxide and 10 parts by weight of nano-silica are uniformly mixed to obtain a solid mixture, which is uniformly mixed with water to obtain a semi-dry mixture, which is added into a hydraulic extruder.
  • Columnar particles having a diameter of 1.5 mm and a length of 3 mm were dried to obtain a flue gas desulfurization denitration agent.
  • nano-calcium oxide 90 parts by weight of nano-calcium oxide, 5 parts by weight of nano-ferric oxide and 5 parts by weight of nano-silica are uniformly mixed to obtain a solid mixture, which is uniformly mixed with water to obtain a semi-dry mixture, which is added to a rotary tableting machine.
  • the flaky particles having a thickness of 8 mm and a diameter of 10 mm were dried to obtain a flue gas desulfurization denitration agent.
  • nano-calcium oxide 90 parts by weight of nano-calcium oxide, 5 parts by weight of nano-ferric oxide and 5 parts by weight of nano-silica are uniformly mixed to obtain a solid mixture, which is uniformly mixed with water to obtain a semi-dry mixture, which is added to a twin-screw extruder and extruded.
  • the columnar particles having a diameter of 2 mm and a length of 2 mm were cut and dried to obtain a flue gas desulfurization denitration agent.
  • the semi-dry mixture of Preparation Example 2 was pressure-coated on the surface of the sheet substrate (thin stainless steel mesh panel), then pleated, cut, and made into a veneer, and a plurality of the veneers were assembled into a flat flue gas.
  • the desulfurization and denitration agent has a height of 600 mm, a width of 450 mm, a thickness of 0.7 mm, and a spacing between adjacent veneers of 7 mm.
  • the semi-dry mixture of Preparation Example 1 was pressed into a honeycomb shape to obtain a honeycomb flue gas desulfurization denitration agent having a pore diameter of 6 mm, a density of 1000 / m 2 and a length of 800 mm.
  • the flue gas is dedusted by an electric precipitator, and the dust content in the flue gas after dedusting is 10 mg/Nm 3 ;
  • the flue gas is dedusted by an electric precipitator, and the dust content in the flue gas after dedusting is 12 mg/Nm 3 ;
  • the honeycomb flue gas treating agent of Preparation Example 5 is placed in a flue, and the flue gas after dust removal passes through the honeycomb flue gas treating agent at a flow rate of 4 m/s for purification treatment, and the desulfurization efficiency is 95.2%.
  • the efficiency is 94.3%, the efficiency of de-dioxin is 91%, and the purified flue gas meets the discharge standard.
  • the flue gas is dedusted by an electric precipitator, and the dust content in the flue gas after dedusting is 14 mg/Nm 3 ;

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Abstract

A flue gas treatment method, comprising the following steps: (1) performing dedusting processing on flue gas having an oxygen content of 3-8 vol% to obtain dedusted flue gas, the dust content of the dedusted flue gas being 10-30 mg/Nm3; and (2) enabling the dedusted flue gas to contact a flue gas treating agent to perform purification processing on the dedusted flue gas, the purification processing comprising desulfurization, denitration, and de-dioxin. The temperature of the flue gas is 200-500°C, and the flow rate of the flue gas is 3-8 m/s. Based on 100 parts by weight of the flue gas processing agent, the flue gas processing agent comprises the following components: 70-96 parts by weight of nano calcium oxide, 2-15 parts by weight of nano ferric oxide, and 2-15 parts by weight of nano silicon dioxide.

Description

烟气治理方法Flue gas treatment method 技术领域Technical field
本发明涉及一种烟气治理方法，尤其涉及一种烟气脱硫脱硝脱二噁英的方法。The invention relates to a method for treating flue gas, in particular to a method for desulfurization and denitrification of flue gas.
背景技术Background technique
二氧化硫是最常见的含硫氧化物，有强烈刺激性气味，是大气主要污染物之一。由于煤和石油通常都含有硫化合物，因此燃烧时会生成二氧化硫；钢铁中也含有大量的硫，在炼钢、炼铁过程中会产生大量的硫化物释放到空气中。当二氧化硫溶于水中，会形成亚硫酸，进而形成酸雨。若在二氧化氮的存在下，SO 2进一步氧化，便会生成硫酸，对环境和人类健康造成极大的危害。 Sulfur dioxide is the most common sulfur-containing oxide with a strong pungent odor and is one of the major pollutants in the atmosphere. Since coal and petroleum usually contain sulfur compounds, sulfur dioxide is formed during combustion; steel also contains a large amount of sulfur, and a large amount of sulfide is released into the air during steel making and iron making. When sulfur dioxide is dissolved in water, sulfurous acid is formed, which forms acid rain. If SO 2 is further oxidized in the presence of nitrogen dioxide, sulfuric acid is formed, which is extremely harmful to the environment and human health.
钢铁和煤炭中也含有大量的氮，在高温燃烧条件下，则生成NO x，NO x主要以NO的形式存在，最初排放的NO x中NO约占95％。NO在大气中极易与空气中的氧发生反应，生成NO 2。在温度较大或有云雾存在时，NO 2进一步与水分子作用形成硝酸，硝酸也是形成酸雨重要成分。在有催化剂存在时，再加上合适的气象条件，NO 2转变成硝酸的速度加快，特别是当NO 2与SO 2同时存在时，可以相互催化，形成硝酸的速度更快。 Steel and Coal also contains a large amount of nitrogen, at a high temperature combustion condition, to generate NO x, NO x mainly in the form of NO, emissions of NO x in the first NO accounts for about 95%. NO reacts easily with oxygen in the air in the atmosphere to form NO 2 . When the temperature is high or there is cloud, NO 2 further reacts with water molecules to form nitric acid, which is also an important component of acid rain. In the presence of a catalyst, coupled with suitable meteorological conditions, the rate at which NO 2 is converted to nitric acid is increased, especially when NO 2 and SO 2 are present together, which can catalyze each other and form nitric acid at a faster rate.
二噁英(1,4-二氧杂环己二烯)是一个单环有机化合物。它是一种在工业上没有用处的副产物，常以微小的颗粒存在于大气、土壤和水中，主要的污染源是化工冶金工业、垃圾焚烧、造纸以及生产杀虫剂等产业。金属冶炼会产生大量的二噁英，特别是紫铜、铝和锌的冶炼会产生大量的二噁英。金属冶炼是排放这些有毒气体的重要来源。Dioxin (1,4-dioxadiene) is a monocyclic organic compound. It is a by-product that is not useful in industry. It is often found in the atmosphere, soil and water with tiny particles. The main sources of pollution are the chemical metallurgical industry, waste incineration, papermaking and the production of pesticides. Metal smelting produces a large amount of dioxins, especially the smelting of copper, aluminum and zinc, which produces a large amount of dioxins. Metal smelting is an important source of emissions of these toxic gases.
随着人们环保意识的增强和国家对金属冶炼排放气体的严厉监 察，发展脱硫脱硝脱二噁英技术变得尤为重要。目前国内外普遍采用的方法只能单一地脱硫、脱硝、脱二噁英，或者同时脱硫、脱硝，而不能同时将三种物质脱除。With the enhancement of people's awareness of environmental protection and the state's strict monitoring of metal smelting and emission gases, it has become more important to develop desulfurization and denitrification and dioxin technology. At present, the methods commonly used at home and abroad can only desulfurize, denitrate, de-dioxin, or simultaneously desulfurize and denitrify, but not simultaneously remove three substances.
目前，工业上脱硫的主要方法有石灰-石灰石脱硫，将吸收剂粉制成浆液，在吸收塔中将烟气中的SO 2吸收。湿法脱硫会产生大量的废水，需要增加废水处理系统。运行费用高，占地面积大，系统管理操作复杂，磨损腐蚀现象比较严重。而且脱硫产生的副产品因为品质不高，市场空间有限而被大量堆放，对环境造成二次污染。 At present, the main method of industrial desulfurization is lime-limestone desulfurization, the absorbent powder is slurried, and SO 2 in the flue gas is absorbed in the absorption tower. Wet desulfurization produces large amounts of wastewater and requires an additional wastewater treatment system. The operating cost is high, the floor space is large, the system management operation is complicated, and the wear and corrosion phenomenon is more serious. Moreover, by-products derived from desulfurization are piled up in large quantities because of their low quality and limited market space, causing secondary pollution to the environment.
目前，市场上脱硝的主要方法是选择性催化还原(SCR)方法，在催化剂的作用下，在有氧气存在时，通入反应器中的氨气优先于烟气中的NO x反应，生成对环境无污染的N 2和H 2O。SCR技术脱硝效率很高，且技术比较成熟，但是，运行成本较高。而且由于催化剂的存在，烟气中的SO 2容易被氧化产生SO 3，并且与过量的氨气反应生成硫酸氢铵对设备造成腐蚀。 Currently, the main method of denitration on the market are the selective catalytic reduction (SCR) method, under the action of the catalyst, when the presence of oxygen, introduced into the reactor in preference to ammonia reacts with NO x in the flue gas, generates Environmentally friendly N 2 and H 2 O. The SCR technology has high denitration efficiency and mature technology, but the operating cost is high. Moreover, due to the presence of the catalyst, SO 2 in the flue gas is easily oxidized to produce SO 3 , and the reaction with excess ammonia gas to form ammonium hydrogen sulfate causes corrosion to the equipment.
目前针对烟气中二噁英的脱除主要是活性炭吸附和烟气骤冷技术。活性炭只是将二噁英从烟气中转移到活性炭中，不能从根本上将二噁英脱除。烟气骤冷技术是指将烟气温度从800℃骤降到200℃以下，避免二噁英的产生。例如，申请号为201220444793.2的中国专利申请公开了一种抑制焚烧烟气中产生二噁英的装置，该装置在不产生二噁英的安全温度区间范围，采用余热回收方式先将来自焚烧炉的高温烟气降至中温段，然后在生成二恶英的敏感温度区域实施急冷降温，保证排放的焚烧烟气中二噁英的含量大大低于国家标准规定的控制指标。该方法造成大量资源浪费，且不能同时实现脱硫脱硝。At present, the removal of dioxins in flue gas is mainly activated carbon adsorption and flue gas quenching technology. Activated carbon only transfers dioxins from flue gas to activated carbon, and does not fundamentally remove dioxins. The flue gas quenching technology refers to the sudden drop of the flue gas temperature from 800 ° C to below 200 ° C to avoid the production of dioxins. For example, Chinese Patent Application No. 201220444793.2 discloses a device for suppressing the production of dioxin in incineration flue gas. The device uses a waste heat recovery method to firstly take the waste gas from the incinerator in a safe temperature range in which no dioxin is produced. The high-temperature flue gas is reduced to the middle temperature section, and then the quenching and cooling is performed in the sensitive temperature region where the dioxin is generated, so that the content of dioxin in the incinerated flue gas discharged is much lower than the control index stipulated by the national standard. This method causes a large amount of waste of resources, and cannot simultaneously achieve desulfurization and denitrification.
因此，需要一种能够同时脱硫、脱硝、脱二噁英的烟气治理方法。Therefore, there is a need for a flue gas treatment method capable of simultaneously desulfurizing, denitrifying, and deodorizing.
发明内容Summary of the invention
本发明的目的在于提供一种烟气治理方法，其可以同时脱硫、脱 硝、脱二噁英。进一步地，本发明的方法效率高，操作简单，运行费用低。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for treating flue gas which can simultaneously desulfurize, denitrify, and deodorize. Further, the method of the present invention is high in efficiency, simple in operation, and low in operating cost.
本发明提供一种烟气治理方法，其包括如下步骤：The invention provides a method for treating flue gas, which comprises the following steps:
(1)将含氧量为3～8vol％的烟气进行除尘处理，得到除尘后的烟气；所述除尘后的烟气中含尘量为10～30mg/Nm 3； (1) The flue gas having an oxygen content of 3 to 8 vol% is subjected to dust removal treatment to obtain flue gas after dust removal; and the dust content in the flue gas after the dust removal is 10 to 30 mg/Nm 3 ;
(2)将所述除尘后的烟气与烟气处理剂接触，从而对除尘后的烟气进行净化处理，所述的净化处理包括脱硫、脱硝和脱二噁英；烟气温度为200～500℃，烟气流速为3～8m/s；(2) contacting the dust-removed flue gas with the flue gas treating agent to purify the flue gas after dedusting, the purifying treatment including desulfurization, denitration and de-dioxin; the flue gas temperature is 200~ 500 ° C, the flue gas flow rate is 3 ~ 8m / s;
其中，基于100重量份烟气处理剂，烟气处理剂包含如下组分：纳米氧化钙70～96重量份、纳米三氧化二铁2～15重量份和纳米二氧化硅2～15重量份。Wherein, the flue gas treating agent comprises the following components based on 100 parts by weight of the flue gas treating agent: 70 to 96 parts by weight of the nano-calcium oxide, 2 to 15 parts by weight of the nano-ferric oxide, and 2 to 15 parts by weight of the nano-silica.
根据本发明的烟气治理方法，优选地，步骤(1)中，所述烟气处理剂还包括粘合剂，所述粘结剂选自乳酸、羧甲基纤维素、聚乙烯醇、淀粉、氧化铝、田青粉中的至少一种。According to the flue gas treatment method of the present invention, preferably, in the step (1), the flue gas treating agent further comprises a binder selected from the group consisting of lactic acid, carboxymethyl cellulose, polyvinyl alcohol, and starch. At least one of alumina, tianqing powder.
根据本发明的烟气治理方法，优选地，步骤(1)中，所述烟气处理剂还包括玻璃纤维。According to the flue gas treating method of the present invention, preferably, in the step (1), the flue gas treating agent further comprises glass fibers.
根据本发明的烟气治理方法，优选地，所述的烟气处理剂通过如下方法制得：将各个组分混合均匀，得到固体混合物，将所述固体混合物与水混合均匀得到半干混合物，将所述半干混合物成型、再经蒸压养护和烘干，得到所述烟气处理剂；所述蒸压养护的温度为160～200℃，压力为0.6～1.8MPa。According to the flue gas treatment method of the present invention, preferably, the flue gas treating agent is obtained by uniformly mixing the respective components to obtain a solid mixture, and uniformly mixing the solid mixture with water to obtain a semi-dry mixture. The semi-dry mixture is shaped, then autoclaved and dried to obtain the flue gas treating agent; the autoclave curing temperature is 160-200 ° C, and the pressure is 0.6-1.8 MPa.
根据本发明的烟气治理方法，优选地，所述烟气处理剂为颗粒状，其选自片状颗粒、球状颗粒或柱状颗粒；所述片状颗粒的厚度为5～10mm，且直径为10～25mm；所述柱状颗粒的直径为1～3mm，且长度为3～8mm；所述球状颗粒的直径为2～5mm。According to the flue gas treatment method of the present invention, preferably, the flue gas treating agent is in the form of particles selected from tabular particles, spherical particles or columnar particles; the flake particles have a thickness of 5 to 10 mm and a diameter of 10 to 25 mm; the columnar particles have a diameter of 1 to 3 mm and a length of 3 to 8 mm; and the spherical particles have a diameter of 2 to 5 mm.
根据本发明的烟气治理方法，优选地，所述净化处理在列管式固 定床中进行，所述烟气处理剂填充在所述列管式固定床的反应管内，其填充高度为所述反应管的长度的80～90％；且所述反应管的直径大于所述烟气处理剂的直径的8倍。According to the flue gas treatment method of the present invention, preferably, the purifying treatment is performed in a tubular fixed bed, and the flue gas treating agent is filled in a reaction tube of the tubular fixed bed, and a filling height thereof is The length of the reaction tube is 80 to 90%; and the diameter of the reaction tube is greater than 8 times the diameter of the flue gas treating agent.
根据本发明的烟气治理方法，优选地，所述烟气处理剂为蜂窝状；蜂窝孔的孔径为4.5～7.5mm，蜂窝孔的密度为800～1200个/m 2。 According to the flue gas treatment method of the present invention, preferably, the flue gas treating agent is in a honeycomb shape; the honeycomb pores have a pore diameter of 4.5 to 7.5 mm, and the honeycomb pores have a density of 800 to 1200 particles/m 2 .
根据本发明的烟气治理方法，优选地，所述烟气处理剂为平板状模块，并通过如下方法制备：将所述半干混合物涂覆在片状基材表面上，然后经过褶皱和裁剪制成单板，将所述单板组装成平板状模块。According to the flue gas treatment method of the present invention, preferably, the flue gas treating agent is a flat module and is prepared by coating the semi-dry mixture on the surface of the sheet substrate, then passing through the wrinkles and cutting. A veneer is formed, and the veneers are assembled into a flat module.
根据本发明的烟气治理方法，优选地，所述单板的高度为400～800mm，宽度为400～550mm，厚度为0.5～1.0mm，且相邻两个单板之间的间距为5～9mm。According to the method for treating flue gas of the present invention, preferably, the veneer has a height of 400 to 800 mm, a width of 400 to 550 mm, a thickness of 0.5 to 1.0 mm, and a spacing between adjacent two veneers of 5 to 9mm.
根据本发明的烟气治理方法，优选地，除尘处理之前的烟气的SO 2浓度为1000～3000mg/m 3，NO x浓度为100～350mg/m 3，二噁英前生体的浓度为5～25ng·TEQ/m 3。 The flue gas treatment method of the present invention, preferably, SO 2 concentration in the flue gas before the dust removal is 1000 ~ 3000mg / m 3, NO x concentration was 100 ~ 350mg / m 3, the concentration of dioxin body is pre-existence 5 ~25ng·TEQ/m 3 .
本发明的烟气治理方法能够同时实现烟气的脱硫、脱硝和脱二噁英，且效率高，操作简单，运行费用低，使用范围广，而且不会产生污染物，不对环境造成二次污染。本发明的烟气治理方法的脱硫效率达95％以上，脱硝效率94％以上，脱二噁英效率91％以上。The flue gas treatment method of the invention can simultaneously realize flue gas desulfurization, denitration and deodorization, and has high efficiency, simple operation, low operation cost, wide use range, no pollutants and no secondary pollution to the environment. . The flue gas treatment method of the invention has a desulfurization efficiency of over 95%, a denitration efficiency of 94% or more, and a dioxin efficiency of 91% or more.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。The present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited thereto.
本发明的烟气治理方法可以同时对烟气进行综合治理，从而同时脱除烟气中的二氧化硫、氮氧化物和二噁英等。该方法包括如下除尘步骤、净化处理步骤等。The flue gas treatment method of the invention can simultaneously comprehensively treat the flue gas, thereby simultaneously removing sulfur dioxide, nitrogen oxides and dioxins in the flue gas. The method includes the following dust removal step, purification treatment step, and the like.
<除尘步骤><Dust removal step>
本发明的除尘步骤为将含氧量为3～8vol％的烟气进行除尘处理，得到除尘后的烟气；所述除尘后的烟气中含尘量为10～30mg/Nm 3。 In the dust removing step of the present invention, the flue gas having an oxygen content of 3 to 8 vol% is subjected to dust removal treatment to obtain flue gas after dust removal; and the dust content in the flue gas after the dust removal is 10 to 30 mg/Nm 3 .
在本发明中，烟气中的含氧量为3～8vol％，优选为5～8vol％。当烟气中含氧量为上述范围时，能够使烟气处理剂中的纳米三氧化二铁将NO氧化为NO 2，从而保证脱硝效果。本发明的烟气治理方法还包括调节烟气的含氧量的步骤。具体地，当烟气中含氧量不足时，可以采用氧化风机向烟气中加入空气或氧气，来使烟气中含氧量达到上述范围。烟气的含氧量控制在本发明的范围内是合适的，烟气中含氧量过低，不能保证脱硝效果；含氧量过高，则增加能耗和成本。 In the present invention, the oxygen content in the flue gas is 3 to 8 vol%, preferably 5 to 8 vol%. When the oxygen content in the flue gas is in the above range, the nano-ferric oxide in the flue gas treating agent can oxidize NO to NO 2 to ensure the denitration effect. The flue gas treatment method of the present invention further includes the step of adjusting the oxygen content of the flue gas. Specifically, when the oxygen content in the flue gas is insufficient, an oxygen fan may be used to add air or oxygen to the flue gas to make the oxygen content in the flue gas reach the above range. It is suitable to control the oxygen content of the flue gas within the scope of the present invention. The oxygen content in the flue gas is too low to ensure the denitration effect; if the oxygen content is too high, the energy consumption and cost are increased.
除尘处理可以采用布袋式除尘、旋流式除尘或者电除尘的方法，且优选为电除尘。经过除尘工序，可以脱除烟气中较大及微小的颗粒。除尘后的烟气中含尘量为10～30mg/Nm 3，优选为10～20mg/Nm 3，更优选为10～15mg/Nm 3。当脱尘后的烟气中的含尘量为上述范围时，能够保证烟气顺利通过烟气处理剂的孔道，而不易发生堵塞和严重磨损成型的烟气处理剂。 The dust removal treatment may employ a bag type dust removal method, a cyclone type dust removal method, or an electric dust removal method, and is preferably electric dust removal. After the dust removal process, large and tiny particles in the flue gas can be removed. The dust content in the flue gas after dust removal is 10 to 30 mg/Nm 3 , preferably 10 to 20 mg/Nm 3 , and more preferably 10 to 15 mg/Nm 3 . When the dust content in the flue gas after the dust removal is in the above range, the flue gas can be smoothly passed through the pores of the flue gas treating agent, and the flue gas treating agent which is not easily clogged and severely worn is formed.
在除尘处理之前，烟气中SO 2浓度为1000～3000mg/m 3，更优选为1500～2500mg/m 3。所述烟气中NO x浓度为100～350mg/m 3，更优选为100～250mg/m 3。所述烟气中二噁英前生体(例如氯酚)的浓度为5～25ng·TEQ/m 3，更优选为10～17ng·TEQ/m 3。所述烟气中含水量为0.5～8wt％，更优选为1～5wt％。这样可以改善脱除效果。TEQ表示国际毒性当量，具有本领域熟知的含义。 The SO 2 concentration in the flue gas is 1000 to 3000 mg/m 3 , and more preferably 1,500 to 2500 mg/m 3 before the dust removal treatment. The NO x concentration in the flue gas is 100 ~ 350mg / m 3, more preferably 100 ~ 250mg / m 3. The concentration of the dioxin prodrug (e.g., chlorophenol) in the flue gas is 5 to 25 ng·TEQ/m 3 , and more preferably 10 to 17 ng·TEQ/m 3 . The water content in the flue gas is from 0.5 to 8 wt%, more preferably from 1 to 5 wt%. This can improve the removal effect. TEQ represents an international toxicity equivalent with a meaning well known in the art.
<净化处理步骤><purification processing step>
本发明的净化处理为将所述除尘后的烟气与烟气处理剂接触，从而对除尘后的烟气进行净化处理，所述的净化处理包括脱硫、脱硝和 脱二噁英。净化处理的温度为200～500℃，优选为230～400℃。在此温度下，更有利于烟气处理剂中的三氧化二铁催化NO氧化为NO 2，烟气处理剂中的氧化钙与烟气中二噁英类前生体反应，阻碍二噁英的生成，同时烟气处理剂中纳米氧化钙活性成分可以脱硫脱硝。烟气的流速可以为3～8m/s，优选为4～6m/s。采用这样的流速，烟气能够顺利流过烟气处理剂，能够保证烟气净化处理能够连续进行。 The purifying treatment of the present invention is to treat the flue gas after the dedusting with the flue gas treating agent, thereby purifying the flue gas after the dedusting, and the purifying treatment includes desulfurization, denitration and deodorization. The temperature of the purification treatment is 200 to 500 ° C, preferably 230 to 400 ° C. At this temperature, it is more favorable for the ferric oxide in the flue gas treatment agent to catalyze the oxidation of NO to NO 2 , and the calcium oxide in the flue gas treatment agent reacts with the dioxin-like precursors in the flue gas, hindering the dioxins. The nano-calcium oxide active component in the flue gas treating agent can be desulfurized and denitrated. The flow rate of the flue gas may be from 3 to 8 m/s, preferably from 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treating agent, and the flue gas purifying treatment can be continuously performed.
基于100重量份烟气处理剂，本发明的烟气处理剂包含如下组分：纳米氧化钙70～96重量份、纳米三氧化二铁2～15重量份和纳米二氧化硅2～15重量份。优选地，其包含如下组分：纳米氧化钙80～90重量份、纳米三氧化二铁5～10重量份和纳米二氧化硅5～10重量份。根据本发明的一个实施方式，所述烟气处理剂仅由如下组分组成：纳米氧化钙70～96重量份、纳米三氧化二铁2～15重量份和纳米二氧化硅2～15重量份。纳米二氧化硅为SO 2和NO提供一定的吸附性，提高了反应物在烟气处理剂表面吸附的可能性；纳米二氧化硅和纳米氧化钙生成胶凝作用从而提高了烟气处理剂的强度；而过量的纳米氧化钙作为脱硫脱销剂，并与烟气中二噁英类前生体反应，阻碍二噁英的生成；纳米三氧化二铁则将NO催化转化为NO 2。 The flue gas treating agent of the present invention comprises the following components: 70 to 96 parts by weight of nano-calcium oxide, 2 to 15 parts by weight of nano-ferric oxide, and 2 to 15 parts by weight of nano-silica based on 100 parts by weight of the flue gas treating agent. . Preferably, it comprises the following components: 80 to 90 parts by weight of nano-sized calcium oxide, 5 to 10 parts by weight of nano-sized ferric oxide, and 5 to 10 parts by weight of nano-silica. According to an embodiment of the present invention, the flue gas treating agent is composed only of 70 to 96 parts by weight of nano-calcium oxide, 2 to 15 parts by weight of nano-ferric oxide, and 2 to 15 parts by weight of nano-silica. . Nano-silica provides a certain adsorption for SO 2 and NO, which increases the possibility of adsorption of reactants on the surface of the flue gas treatment agent; nano-silica and nano-calcium oxide form gelation to improve the smoke treatment agent. Intensity; and excess nano-calcium oxide acts as a desulfurization agent and reacts with dioxin-like precursors in the flue gas to hinder the formation of dioxins; nano-ferric oxide converts NO to NO 2 .
本发明中，纳米氧化钙粒子表面与烟气中的SO 2通过气-固相反应生成亚硫酸钙和硫酸钙，达到去除SO 2的目的。纳米三氧化二铁粒子处于中高温(200～350℃)时能够有效催化氧化NO从而生成NO 2，NO 2更有利于被纳米氧化钙吸收，从而除去氮氧化物。纳米二氧化硅作为添加剂，能够使烟气处理剂在较宽的温度窗口下具有较高的催化活性；同时纳米二氧化硅和纳米氧化钙之间形成胶凝作用，能够提高烟气处理剂的机械性能。通过三种氧化物之间的协同作用，并利用纳米材料表面活性高特点，从而对烟气进行同时脱硫脱硝脱二噁英。 In the present invention, the surface of the nano-calcium oxide particles and the SO 2 in the flue gas are reacted by a gas-solid phase to form calcium sulfite and calcium sulfate to achieve the purpose of removing SO 2 . Catalytic iron can be efficiently when the nano oxide particles in the high-temperature (200 ~ 350 ℃) oxidation of NO to generate NO 2, NO 2 is more conducive to the absorption of calcium oxide nanoparticles, to remove nitrogen oxides. As an additive, nano-silica can make the flue gas treatment agent have higher catalytic activity under a wider temperature window; at the same time, gelation between nano-silica and nano-calcium oxide can improve the smoke treatment agent. Mechanical behavior. Through the synergy between the three oxides and the high surface activity of the nanomaterials, the flue gas is simultaneously desulfurized and denitrified.
根据本发明的另一个实施方式，所述烟气处理剂还包括粘结剂， 其用于将所述纳米氧化钙、纳米三氧化二铁和纳米二氧化硅粘结在一起，从而便于应用。所述粘结剂可以选自乳酸、羧甲基纤维素、聚乙烯醇、淀粉、氧化铝、田青粉中的至少一种；优选为羧甲基纤维素或淀粉。本发明中，所述粘结剂的重量占所述烟气处理剂的1～10wt％。烟气处理剂还可以包括纤维，例如玻璃纤维，从而改善烟气处理剂的抗拉伸性能。According to another embodiment of the present invention, the flue gas treating agent further includes a binder for bonding the nano-calcium oxide, nano-ferric oxide, and nano-silica together to facilitate application. The binder may be selected from at least one of lactic acid, carboxymethyl cellulose, polyvinyl alcohol, starch, alumina, and talc; preferably carboxymethyl cellulose or starch. In the present invention, the binder has a weight of 1 to 10% by weight of the flue gas treating agent. The flue gas treating agent may further include fibers such as glass fibers to improve the tensile properties of the flue gas treating agent.
在本发明中，纳米二氧化硅、纳米氧化钙和纳米三氧化二铁的粒径可以为5～100nm，优选为10～90nm。In the present invention, the nano silica, the nano calcium oxide, and the nano iron oxide may have a particle diameter of 5 to 100 nm, preferably 10 to 90 nm.
本发明的烟气处理剂可以通过如下方法制得：将各个组分混合均匀，得到固体混合物，将所述固体混合物与水混合均匀得到半干混合物，将所述半干混合物成型、再经蒸压养护和烘干，得到所述烟气处理剂。蒸压养护的温度为160～200℃，压力为0.6～1.8MPa。优选地，处理温度为180～190℃，压力为0.8～1.5MPa。烘干的温度为100～120℃。经过上述处理，可以改善脱硫脱硝和脱二噁英效果。The flue gas treating agent of the present invention can be obtained by uniformly mixing the respective components to obtain a solid mixture, uniformly mixing the solid mixture with water to obtain a semi-dry mixture, and molding the semi-dry mixture, followed by steaming. Pressurizing and drying to obtain the flue gas treating agent. The autoclave curing temperature is 160 to 200 ° C, and the pressure is 0.6 to 1.8 MPa. Preferably, the treatment temperature is 180 to 190 ° C and the pressure is 0.8 to 1.5 MPa. The drying temperature is 100 to 120 °C. After the above treatment, the effects of desulfurization, denitrification and deodorization can be improved.
本发明的烟气处理剂可以为颗粒状、蜂窝状或平板状；优选为蜂窝状或平板状。这样便于改善脱硫脱硝效果。The flue gas treating agent of the present invention may be in the form of pellets, honeycombs or flat sheets; preferably in the form of a honeycomb or a flat plate. This is convenient for improving the desulfurization and denitration effect.
根据本发明的一个实施方式，烟气处理剂为颗粒状。其可以为片状颗粒、球状颗粒或柱状颗粒中的至少一种。所述片状颗粒的厚度为5～10mm，直径为10～25mm。所述片状颗粒可以采用旋转式压片机或者单冲压片机制备。所述柱状颗粒的直径范围为1～3mm，长度为3～8mm；优选地，所述柱状颗粒的直径范围为1～2mm，长度为2～5mm；更优选地，所述柱状颗粒的直径为1.5mm，长度为3mm。所述柱状颗粒可以采用单螺杆挤条机、双螺杆挤条机或者液压型挤条机制备制成长条状，然后切割成一定长度的柱状颗粒。所述球状颗粒的直径范围为2～5mm。所述球状颗粒可以首先采用单螺杆挤条机、双螺杆挤条机或者液压型挤条机制备制成长条状，切割至直径与长度基本 相等，然后再经整形造粒机加工制成。According to an embodiment of the invention, the flue gas treating agent is in the form of particles. It may be at least one of tabular grains, spherical particles or columnar particles. The tabular grains have a thickness of 5 to 10 mm and a diameter of 10 to 25 mm. The tabular grains may be prepared using a rotary tablet press or a single punch tablet machine. The columnar particles have a diameter ranging from 1 to 3 mm and a length of from 3 to 8 mm; preferably, the columnar particles have a diameter ranging from 1 to 2 mm and a length of from 2 to 5 mm; more preferably, the diameter of the columnar particles is 1.5mm, length is 3mm. The columnar particles may be prepared into a strip shape by a single screw extruder, a twin screw extruder or a hydraulic extruder, and then cut into columnar particles of a certain length. The spherical particles have a diameter ranging from 2 to 5 mm. The spherical particles may be first prepared into a strip shape by a single screw extruder, a twin screw extruder or a hydraulic extruder, cut to a diameter equal to the length, and then processed by a shaping granulator.
在本发明中，所述净化处理可以在列管式固定床中进行，所述烟气处理剂填充在所述列管式固定床的反应管内，其填充高度为所述反应管的长度的80～90％；且所述反应管的直径大于所述烟气处理剂的直径的8倍。列管式固定床的反应管管径可以为15～150mm，且所述反应管直径大于所述颗粒状烟气处理剂直径的8倍。采用这样的设置，烟气与所述颗粒状烟气处理剂具有较大的接触面积，从而有利于烟气的脱硫脱硝。列管式固定床的换热介质可以选自导热油、熔盐或烟道气，以保证加热温度达到200～500℃。所述换热介质更优选为熔盐。烟气在所述列管式固定床中的流速可以为3～8m/s，优选为4～6m/s。采用这样的流速，烟气能够顺利流过烟气处理剂，且反应管内积灰较少。In the present invention, the purification treatment may be carried out in a tubular fixed bed in which the flue gas treating agent is filled in a reaction tube of the tubular fixed bed, and the filling height is 80 of the length of the reaction tube. ～90%; and the diameter of the reaction tube is greater than 8 times the diameter of the flue gas treating agent. The reaction tube diameter of the tubular fixed bed may be 15 to 150 mm, and the diameter of the reaction tube is greater than 8 times the diameter of the granular flue gas treatment agent. With such an arrangement, the flue gas has a large contact area with the granular flue gas treating agent, thereby facilitating desulfurization and denitrification of the flue gas. The heat exchange medium of the tubular fixed bed may be selected from a heat transfer oil, a molten salt or a flue gas to ensure a heating temperature of 200 to 500 ° C. The heat exchange medium is more preferably a molten salt. The flow rate of the flue gas in the tubular fixed bed may be 3 to 8 m/s, preferably 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treating agent, and the ash accumulation in the reaction tube is less.
根据本发明的另一个实施方式，烟气处理剂为蜂窝状。蜂窝孔的孔径可以为4.5～7.5mm，更优选为5～6.5mm，再优选为5.11～6.35mm。蜂窝孔的密度可以为800～1200个/m 2，优选为900～1100个/m 2。所述烟气处理剂的长度为700～1500mm。将蜂窝状烟气处理剂置于烟气通道中，然后进行净化处理。 According to another embodiment of the invention, the flue gas treating agent is in the form of a honeycomb. The pore diameter of the honeycomb hole may be 4.5 to 7.5 mm, more preferably 5 to 6.5 mm, still more preferably 5.11 to 6.35 mm. The density of the honeycomb cells may be 800 to 1200 / m 2 , preferably 900 to 1100 / m 2 . The flue gas treating agent has a length of 700 to 1500 mm. The honeycomb flue gas treating agent is placed in the flue gas passage and then subjected to purification treatment.
在本发明中，蜂窝状烟气处理剂的直径与所述烟气通道的直径相匹配。例如，烟气处理剂的长度为1000mm，截面为150×150mm，蜂窝孔的数量为22个。烟气经过所述蜂窝状烟气处理剂的流速为3～8m/s，更优选为4～6m/s。采用这样的流速，烟气能够顺利流过烟气处理剂，保证烟气净化处理连续进行。In the present invention, the diameter of the honeycomb flue gas treating agent matches the diameter of the flue gas passage. For example, the flue gas treating agent has a length of 1000 mm, a cross section of 150 x 150 mm, and the number of honeycomb holes is 22. The flow rate of the flue gas through the honeycomb flue gas treating agent is 3 to 8 m/s, and more preferably 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treatment agent to ensure that the flue gas purification treatment is continuously performed.
根据本发明的再一个实施方式，烟气处理剂为平板状。将半干混合物涂覆在片状基材表面上，然后经过褶皱和裁剪制成单板，将所述单板组装成平板状烟气处理剂。单板的高度可以为400～800mm，更优选为500～700mm；单板的宽度可以为400～550mm，更优选为420～ 500mm，再优选为430～470mm；单板的厚度可以为0.5～1.0mm，更优选为0.6～0.8mm。根据本发明的一个实施方式，所述单板的高度为600mm，宽度为450mm左右，厚度0.7mm。相邻单板之间的间距可以为5～9mm，优选为6～8mm。将平板状烟气处理剂置于烟气通道中，然后进行净化处理。According to still another embodiment of the present invention, the flue gas treating agent is in the form of a flat plate. The semi-dry mixture was coated on the surface of the sheet-like substrate, and then pleated and cut into a veneer, which was assembled into a flat-shaped flue gas treating agent. The height of the veneer may be 400 to 800 mm, more preferably 500 to 700 mm; the width of the veneer may be 400 to 550 mm, more preferably 420 to 500 mm, still more preferably 430 to 470 mm; and the thickness of the veneer may be 0.5 to 1.0. Mm is more preferably 0.6 to 0.8 mm. According to an embodiment of the invention, the veneer has a height of 600 mm, a width of about 450 mm, and a thickness of 0.7 mm. The spacing between adjacent veneers may be 5 to 9 mm, preferably 6 to 8 mm. The flat flue gas treating agent is placed in the flue gas passage and then subjected to purification treatment.
在本发明中，烟气经过平板状烟气处理剂模块的流速为3～8m/s，更优选为4～6m/s。采用这样的流速，烟气能够顺利流过烟气处理剂，保证烟气净化处理连续进行。In the present invention, the flow rate of the flue gas through the flat flue gas treating agent module is 3 to 8 m/s, more preferably 4 to 6 m/s. With such a flow rate, the flue gas can smoothly flow through the flue gas treatment agent to ensure that the flue gas purification treatment is continuously performed.
以下通过实施例来进一步说明本发明的实施方法，但并不构成对本发明的限制。以下实施例中，纳米氧化钙、纳米三氧化二铁和纳米二氧化硅的平均粒径均为25nm。The embodiments of the present invention are further illustrated by the following examples, but are not intended to limit the invention. In the following examples, the average particle diameter of the nano-calcium oxide, the nano-ferric oxide and the nano-silica was 25 nm.
制备例1Preparation Example 1
将纳米氧化钙为80重量份、纳米三氧化二铁10重量份和纳米二氧化硅10重量份混合均匀，得到固体混合物，加水混合均匀，得到半干混合物，加入液压型挤条机，制成直径为1.5mm、长度为3mm的柱状颗粒，干燥，得到烟气脱硫脱硝剂。80 parts by weight of nano-calcium oxide, 10 parts by weight of nano-ferric oxide and 10 parts by weight of nano-silica are uniformly mixed to obtain a solid mixture, which is uniformly mixed with water to obtain a semi-dry mixture, which is added into a hydraulic extruder. Columnar particles having a diameter of 1.5 mm and a length of 3 mm were dried to obtain a flue gas desulfurization denitration agent.
制备例2Preparation Example 2
将纳米氧化钙为90重量份、纳米三氧化二铁5重量份和纳米二氧化硅5重量份混合均匀，得到固体混合物，加水混合均匀，得到半干混合物，加入旋转式压片机，制成厚度为8mm、直径为10mm的片状颗粒，干燥，得到烟气脱硫脱硝剂。90 parts by weight of nano-calcium oxide, 5 parts by weight of nano-ferric oxide and 5 parts by weight of nano-silica are uniformly mixed to obtain a solid mixture, which is uniformly mixed with water to obtain a semi-dry mixture, which is added to a rotary tableting machine. The flaky particles having a thickness of 8 mm and a diameter of 10 mm were dried to obtain a flue gas desulfurization denitration agent.
制备例3Preparation Example 3
将纳米氧化钙为90重量份、纳米三氧化二铁5重量份和纳米二氧化硅5重量份混合均匀，得到固体混合物，加水混合均匀，得到半干混合物，加入双螺杆挤条机，挤出，切割成直径2mm、长度2mm的柱状颗粒，干燥，得到烟气脱硫脱硝剂。90 parts by weight of nano-calcium oxide, 5 parts by weight of nano-ferric oxide and 5 parts by weight of nano-silica are uniformly mixed to obtain a solid mixture, which is uniformly mixed with water to obtain a semi-dry mixture, which is added to a twin-screw extruder and extruded. The columnar particles having a diameter of 2 mm and a length of 2 mm were cut and dried to obtain a flue gas desulfurization denitration agent.
制备例4Preparation Example 4
将制备例2的半干混合物加压涂覆在片状基材表面(薄型不锈钢筛网板)上，然后褶皱、裁剪，制成单板，将多张所述单板组装成平板状烟气脱硫脱硝剂，其中单板的高度为600mm，宽度为450mm，厚度为0.7mm，相邻单板之间的间距为7mm。The semi-dry mixture of Preparation Example 2 was pressure-coated on the surface of the sheet substrate (thin stainless steel mesh panel), then pleated, cut, and made into a veneer, and a plurality of the veneers were assembled into a flat flue gas. The desulfurization and denitration agent has a height of 600 mm, a width of 450 mm, a thickness of 0.7 mm, and a spacing between adjacent veneers of 7 mm.
制备例5Preparation Example 5
将制备例1的半干混合物压制成蜂窝状，得到蜂窝状烟气脱硫脱硝剂，蜂窝孔的孔径为6mm，密度为1000个/m 2，长度为800mm。 The semi-dry mixture of Preparation Example 1 was pressed into a honeycomb shape to obtain a honeycomb flue gas desulfurization denitration agent having a pore diameter of 6 mm, a density of 1000 / m 2 and a length of 800 mm.
实施例1Example 1
(1)将含氧量为3vol％、含水量为1wt％、SO 2浓度为1500mg/m 3、NO x浓度为100mg/m 3、二噁英前生体的浓度为10ng·TEQ/m 3的烟气采用电除尘器进行除尘，除尘后的烟气中含尘量为10mg/Nm 3； (1) The oxygen content of 3vol%, a water content of 1wt%, SO 2 concentration of 1500mg / m 3, NO x concentration of 100mg / m 3, the concentration of dioxin body is pre-existence 10ng · TEQ / m 3 of The flue gas is dedusted by an electric precipitator, and the dust content in the flue gas after dedusting is 10 mg/Nm 3 ;
(2)将制备例1的颗粒填充至列管式固定床的反应管内，反应管的直径为135mm，换热介质为熔盐，片状颗粒在反应管内的填充高度为反应管长度的90％；所述除尘后的烟气通过该列管式固定床，流速为5m/s，反应管内温度为200℃，进行净化处理，脱硫效率为95.6％，脱硝效率为96.2％，脱二噁英效率为92％，净化后的烟气符合排放标准。(2) The particles of Preparation Example 1 were filled into a reaction tube of a fixed-tube tubular fixed bed, the diameter of the reaction tube was 135 mm, the heat exchange medium was a molten salt, and the filling height of the tabular particles in the reaction tube was 90% of the length of the reaction tube. The dust after the dust removal passes through the tubular fixed bed, the flow rate is 5 m/s, the temperature inside the reaction tube is 200 ° C, and the purification treatment is performed, the desulfurization efficiency is 95.6%, the denitration efficiency is 96.2%, and the efficiency of de-dioxin is removed. At 92%, the purified flue gas meets emission standards.
实施例2Example 2
(1)将含氧量为4vol％、含水量为3wt％、SO 2浓度为2000mg/m 3、NO x浓度为200mg/m 3、二噁英前生体的浓度为15ng·TEQ/m 3的烟气采用电除尘器进行除尘，除尘后的烟气中含尘量为12mg/Nm 3； (1) The oxygen content of 4vol%, a moisture content of 3wt%, SO 2 concentration of 2000mg / m 3, NO x concentration of 200mg / m 3, the concentration of dioxin body is pre-existence 15ng · TEQ / m 3 of The flue gas is dedusted by an electric precipitator, and the dust content in the flue gas after dedusting is 12 mg/Nm 3 ;
(2)将制备例5的蜂窝状烟气处理剂放置于烟道中，除尘后的烟气通过该蜂窝状烟气处理剂，流速为4m/s，进行净化处理，脱硫效率为95.2％，脱硝效率为94.3％，脱二噁英效率为91％，净化后的烟气符合排放标准。(2) The honeycomb flue gas treating agent of Preparation Example 5 is placed in a flue, and the flue gas after dust removal passes through the honeycomb flue gas treating agent at a flow rate of 4 m/s for purification treatment, and the desulfurization efficiency is 95.2%. The efficiency is 94.3%, the efficiency of de-dioxin is 91%, and the purified flue gas meets the discharge standard.
实施例3Example 3
(1)将含氧量为6vol％、含水量为5wt％、SO 2浓度为2500mg/m 3、NO x浓度为250mg/m 3、二噁英前生体的浓度为17ng·TEQ/m 3的烟气采用电除尘器进行除尘，除尘后的烟气中含尘量为14mg/Nm 3； (1) The oxygen content of 6vol%, a moisture content of 5wt%, SO 2 concentration of 2500mg / m 3, NO x concentration of 250mg / m 3, the concentration of dioxin body is pre-existence 17ng · TEQ / m 3 of The flue gas is dedusted by an electric precipitator, and the dust content in the flue gas after dedusting is 14 mg/Nm 3 ;
(2)将制备例5的烟气处理剂放置于烟道中，除尘后的烟气通过该烟气处理剂，流速为6m/s，进行净化处理，脱硫效率为96.8％，脱硝效率为95.7％，脱二噁英效率为90.8％，净化后的烟气符合排放标准。(2) The flue gas treating agent of Preparation Example 5 was placed in the flue, and the flue gas after the dedusting was passed through the flue gas treating agent at a flow rate of 6 m/s for purification treatment, the desulfurization efficiency was 96.8%, and the denitration efficiency was 95.7%. The efficiency of dioxin removal is 90.8%, and the purified flue gas meets the discharge standard.
本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。The present invention is not limited to the above-described embodiments, and any variations, modifications, and alterations that may be conceived by those skilled in the art are intended to fall within the scope of the present invention without departing from the spirit of the invention.

Claims (10)

  1. 一种烟气治理方法，其特征在于，所述烟气治理方法包括如下步骤：A method for treating flue gas, characterized in that the method for treating flue gas comprises the following steps:
    (1)将含氧量为3～8vol％的烟气进行除尘处理，得到除尘后的烟气；所述除尘后的烟气中含尘量为10～30mg/Nm 3； (1) The flue gas having an oxygen content of 3 to 8 vol% is subjected to dust removal treatment to obtain flue gas after dust removal; and the dust content in the flue gas after the dust removal is 10 to 30 mg/Nm 3 ;
    (2)将所述除尘后的烟气与烟气处理剂接触，从而对除尘后的烟气进行净化处理，所述的净化处理包括脱硫、脱硝和脱二噁英；烟气温度为200～500℃，烟气流速为3～8m/s；(2) contacting the dust-removed flue gas with the flue gas treating agent to purify the flue gas after dedusting, the purifying treatment including desulfurization, denitration and de-dioxin; the flue gas temperature is 200~ 500 ° C, the flue gas flow rate is 3 ~ 8m / s;
    其中，基于100重量份烟气处理剂，烟气处理剂包含如下组分：纳米氧化钙70～96重量份、纳米三氧化二铁2～15重量份和纳米二氧化硅2～15重量份。Wherein, the flue gas treating agent comprises the following components based on 100 parts by weight of the flue gas treating agent: 70 to 96 parts by weight of the nano-calcium oxide, 2 to 15 parts by weight of the nano-ferric oxide, and 2 to 15 parts by weight of the nano-silica.
  2. 根据权利要求1所述的烟气治理方法，其特征在于，步骤(1)中，所述烟气处理剂还包括粘合剂，所述粘结剂选自乳酸、羧甲基纤维素、聚乙烯醇、淀粉、氧化铝、田青粉中的至少一种。The method for controlling flue gas according to claim 1, wherein in the step (1), the flue gas treating agent further comprises a binder selected from the group consisting of lactic acid, carboxymethyl cellulose, and poly At least one of vinyl alcohol, starch, alumina, and talc.
  3. 根据权利要求2所述的烟气治理方法，其特征在于，步骤(1)中，所述烟气处理剂还包括玻璃纤维。The method for controlling flue gas according to claim 2, wherein in the step (1), the flue gas treating agent further comprises glass fibers.
  4. 根据权利要求1～3任一项所述的烟气治理方法，其特征在于，所述的烟气处理剂通过如下方法制得：将各个组分混合均匀，得到固体混合物，将所述固体混合物与水混合均匀得到半干混合物，将所述半干混合物成型、再经蒸压养护和烘干，得到所述烟气处理剂；所述蒸压养护的温度为160～200℃，压力为0.6～1.8MPa。The flue gas treating method according to any one of claims 1 to 3, wherein the flue gas treating agent is obtained by uniformly mixing the respective components to obtain a solid mixture, and the solid mixture is obtained. Mixing with water to obtain a semi-dry mixture, forming the semi-dry mixture, and then autoclaving and drying to obtain the flue gas treating agent; the autoclave curing temperature is 160-200 ° C, and the pressure is 0.6. ~1.8MPa.
  5. 根据权利要求4所述的烟气治理方法，其特征在于，所述烟气处理剂为颗粒状，其选自片状颗粒、球状颗粒或柱状颗粒；所述片状颗粒的厚度为5～10mm，且直径为10～25mm；所述柱状颗粒的直径为1～3mm，且长度为3～8mm；所述球状颗粒的直径为2～5mm。The method for treating flue gas according to claim 4, wherein the flue gas treating agent is in the form of particles, which are selected from the group consisting of tabular particles, spherical particles or columnar particles; and the flake particles have a thickness of 5 to 10 mm. And the diameter is 10 to 25 mm; the columnar particles have a diameter of 1 to 3 mm and a length of 3 to 8 mm; and the spherical particles have a diameter of 2 to 5 mm.
  6. 根据权利要求4的烟气治理方法，其特征在于，所述净化处理 在列管式固定床中进行，所述烟气处理剂填充在所述列管式固定床的反应管内，其填充高度为所述反应管的长度的80～90％；且所述反应管的直径大于所述烟气处理剂的直径的8倍。A method of treating flue gas according to claim 4, wherein said purifying treatment is carried out in a tubular fixed bed, said flue gas treating agent being filled in said reaction tube of said tubular fixed bed, and having a filling height of The reaction tube has a length of 80 to 90%; and the diameter of the reaction tube is greater than 8 times the diameter of the flue gas treating agent.
  7. 根据权利要求4的烟气治理方法，其特征在于，所述烟气处理剂为蜂窝状；蜂窝孔的孔径为4.5～7.5mm，蜂窝孔的密度为800～1200个/m 2。 The method for controlling flue gas according to claim 4, wherein the flue gas treating agent is in a honeycomb shape; the honeycomb pores have a pore diameter of 4.5 to 7.5 mm, and the honeycomb pores have a density of 800 to 1,200 / m 2 .
  8. 根据权利要求4的烟气治理方法，其特征在于，所述烟气处理剂为平板状模块，并通过如下方法制备：将所述半干混合物涂覆在片状基材表面上，然后经过褶皱和裁剪制成单板，将所述单板组装成平板状模块。A method of treating flue gas according to claim 4, wherein said flue gas treating agent is a flat module and is prepared by coating said semi-dry mixture on a surface of a sheet-like substrate and then passing through a wrinkle And cutting into a single board, and assembling the single board into a flat module.
  9. 根据权利要求8所述的烟气治理方法，其特征在于，所述单板的高度为400～800mm，宽度为400～550mm，厚度为0.5～1.0mm，且相邻两个单板之间的间距为5～9mm。The method for treating flue gas according to claim 8, wherein the veneer has a height of 400 to 800 mm, a width of 400 to 550 mm, a thickness of 0.5 to 1.0 mm, and between adjacent two veneers. The spacing is 5 to 9 mm.
  10. 根据权利要求1～3任一项所述的烟气治理方法，其特征在于，除尘处理之前的烟气的SO 2浓度为1000～3000mg/m 3，NO x浓度为100～350mg/m 3，二噁英前生体的浓度为5～25ng·TEQ/m 3。 The flue gas treatment method according to any one of claims 1 to 3, characterized in that, SO 2 concentration in the flue gas before the dust removal is 1000 ~ 3000mg / m 3, NO x concentration was 100 ~ 350mg / m 3, The concentration of the dioxin progenitor is 5 to 25 ng·TEQ/m 3 .
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CN107511070A (en) * 2017-09-30 2017-12-26 中晶蓝实业有限公司 Smoke treating method
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