WO2019062455A1 - Flue gas desulfurization and denitration agent, preparation method therefor and applications thereof - Google Patents

Flue gas desulfurization and denitration agent, preparation method therefor and applications thereof Download PDF

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Publication number
WO2019062455A1
WO2019062455A1 PCT/CN2018/103040 CN2018103040W WO2019062455A1 WO 2019062455 A1 WO2019062455 A1 WO 2019062455A1 CN 2018103040 W CN2018103040 W CN 2018103040W WO 2019062455 A1 WO2019062455 A1 WO 2019062455A1
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flue gas
weight
parts
gas desulfurization
carbide slag
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PCT/CN2018/103040
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French (fr)
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 WO2019062455A1 publication Critical patent/WO2019062455A1/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
    • B01D53/46—Removing components of defined structure
    • B01D53/60—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
    • B01D53/81—Solid phase processes
    • 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
    • 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
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to a flue gas desulfurization and denitration agent, a preparation method and application thereof, in particular to a flue gas desulfurization and denitration agent based on calcium carbide slag, a preparation method and application thereof.
  • SO 2 and NO X are the major pollutants.
  • the emission content is clearly defined. Since both of them exist in the flue gas at the same time, the method of separately removing will bring about a problem of a large number of equipments, a large area, complicated operation, and large investment in the early stage.
  • SO 2 and NO X are acidic oxides while removing entirely feasible, currently there are some exemplary industrial and commercial operation means.
  • the current integration methods of flue gas desulfurization and denitrification are mainly divided into three types: wet desulfurization and denitrification, dry desulfurization and denitrification, and semi-dry desulfurization and denitrification.
  • wet removal effect is good, but the waste liquid pollution is serious
  • the dry removal effect is good, but the operation cost is high
  • the semi-dry method has the advantages of the dry method and the wet method, but there are also unstable operations. problem.
  • most of the formulations are prepared by mixing various pure effective components, thereby causing high cost of the desulfurization and denitration agent. How to use industrial waste to produce desulfurization and denitrification agents has become a hot research topic.
  • Carbide slag is industrial waste generated in the process of reacting calcium carbide with water to form acetylene gas.
  • the main component of the calcium carbide slag is Ca(OH) 2 , and also contains various impurities such as sulfides, cyanides, oxides of iron magnesium aluminum, and the like.
  • the Ca(OH) 2 dissolution rate in the carbide slag is greater than CaCO 3 , so it can be used for flue gas desulfurization.
  • CN101642674B discloses a wet flue gas desulfurization process for calcium carbide slag pretreatment, which uses a calcium carbide slag slurry as a desulfurizing agent to carry out a wet desulfurization treatment on a flue gas, a catalyst is added to the calcium carbide slag slurry, and air is blasted for oxidation reaction.
  • the calcium carbide slurry after the oxidation reaction is further used as a desulfurizing agent for the flue gas wet desulfurization treatment.
  • CN101816891A discloses an ozone method wet flue gas desulfurization process for pretreatment of calcium carbide slag, wherein the calcium slag is used as a desulfurizing agent to perform wet desulfurization of the flue gas, and in the process of calcium carbide slag slag, a mixture of ozone and oxygen is introduced.
  • the oxidation reaction, the oxidized calcium carbide slurry is used as a desulfurizing agent for flue gas desulfurization.
  • the above processes all use the calcium carbide slag alone as a desulfurizing agent, and do not consider it as a denitration agent. At the same time, the above processes are all wet desulfurization processes, and it is easy to produce a large amount of industrial waste liquid.
  • the effective component content of desulfurization and denitrification from calcium carbide slag is 25-30% by weight. If a single calcium carbide slag is used for desulfurization and denitration, a large amount of calcium carbide slag is required for the unit removal amount under the premise of satisfying the high desulfurization and denitration efficiency. This results in a large equipment and high operating costs.
  • An object of the present invention is to provide a flue gas desulfurization and denitration agent, which may be the flue gas while the removal of SO 2 and NO X. According to a further object of the present invention, the amount of calcium carbide slag required for unit removal is significantly reduced on the premise of satisfying higher desulfurization and denitration efficiency.
  • Another object of the present invention is to provide a method for preparing a flue gas desulfurization and denitration agent, which is simple in preparation process.
  • a further object of the present invention is to provide a flue gas desulfurization applications denitration agent which can effectively remove flue gas SO 2 and NO X, and may reduce the amount of carbide slag removal unit amount.
  • the invention provides a flue gas desulfurization denitration agent, which comprises the following components:
  • the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 , WO 3 , K 2 O, dinuclear cobalt phthalocyanine iron (II) or CaSiO 3 ;
  • the flue gas desulfurization denitration agent does not contain calcium oxide.
  • the flue gas desulfurization denitration agent according to the present invention preferably comprises the following components:
  • the catalyst is 2 to 3 parts by weight.
  • the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 .
  • the calcium carbide slag is a finished product having a particle size of less than 200 mesh obtained by grinding a calcium carbide slag product produced by a dry acetylene process; and the magnesium oxide is a powder having a particle size of less than 100 mesh.
  • the body has an active magnesium oxide content of more than 70% by weight.
  • the active magnesium oxide content in the magnesium oxide is from 80% by weight to 85% by weight.
  • the flue gas desulfurization denitration agent of the present invention is composed of the following components:
  • the flue gas desulfurization denitration agent of the present invention preferably, is in the form of a dry powder.
  • the invention also provides a preparation method of the above flue gas desulfurization denitration agent, comprising the steps of mixing calcium carbide slag, magnesium oxide and a catalyst.
  • the invention also provides the use of the above flue gas desulfurization denitration agent for dry flue gas desulfurization and denitrification.
  • the dry flue gas desulfurization and denitration is carried out in a flue gas desulfurization and denitration device including a flue gas inlet and a flue gas outlet, and the flue gas flow rate of the flue gas inlet is 1000000 to 12.5 million m 3 /h,
  • the temperature is 110-130 ° C
  • the sulfur dioxide concentration is 350 mg/m 3 or more
  • the nitrogen oxide concentration is 350 mg/m 3 or more
  • the flue gas flow rate of the flue gas outlet is 800,000 to 900,000 m 3 /h
  • the temperature is 50 to 70 ° C
  • the sulfur dioxide concentration is 35 mg/m 3 or less
  • the nitrogen oxide concentration is 70 mg/m 3 or less.
  • the invention realizes the secondary utilization of calcium carbide slag, and achieves the purpose of treating waste by waste.
  • Desulfurization agent of the present invention can simultaneously denitration of flue gas SO 2 and NO X removal.
  • the amount of calcium carbide slag required for the unit removal amount is remarkably reduced on the premise of satisfying the high desulfurization and denitration efficiency.
  • the desulfurization and denitration agent is low in cost and simple in preparation method.
  • the flue gas desulfurization denitration agent of the invention is a flue gas treatment agent, and has the functions of desulfurization and denitration.
  • the flue gas desulfurization and denitration agent of the invention mainly comprises calcium carbide slag, magnesium oxide as an auxiliary material, and a suitable catalyst is added. This can make the function of the calcium carbide slag fully exerted, has both desulfurization and denitration functions, and can reduce the amount of calcium carbide slag under the unit removal amount.
  • the flue gas desulfurization denitration agent of the present invention does not contain calcium oxide.
  • the amount of calcium carbide slag used in the unit removal amount represents the weight of the carbide slag required to remove the same amount of flue gas.
  • the present inventors have found that calcium oxide does not significantly reduce the amount of calcium carbide slag per unit removal.
  • the flue gas desulfurization denitration agent of the present invention comprises the following components: calcium carbide slag, magnesium oxide and a catalyst.
  • the calcium carbide slag is used in an amount of 70 to 93 parts by weight, preferably 80 to 92 parts by weight, more preferably 83 to 86 parts by weight.
  • the magnesium oxide is used in an amount of 5 to 25 parts by weight, preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight.
  • the catalyst is used in an amount of 1 to 5 parts by weight, preferably 2 to 3 parts by weight, more preferably 2 to 2.5 parts by weight.
  • the carbide slag is industrial waste, thereby achieving the purpose of waste disposal.
  • the calcium carbide slag of the present invention is preferably a finished product having a particle size of less than 200 mesh obtained by grinding the calcium carbide slag product produced by the dry acetylene process.
  • the carbide slag may have a particle size of less than 200 mesh, preferably less than 300 mesh, more preferably less than 350 mesh.
  • the use of the above calcium carbide slag is beneficial to improve the desulfurization and denitration effect.
  • the magnesium oxide may be a powder having a particle size of less than 100 mesh, preferably a powder having a particle size of less than 200 mesh.
  • the active magnesium oxide content may be more than 70% by weight, preferably 70% by weight to 85% by weight, more preferably 80% by weight to 85% by weight. The use of the above magnesium oxide is beneficial to improve the desulfurization and denitration effect.
  • the catalyst may be selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 , WO 3 , K 2 O, dinuclear cobalt phthalocyanine iron (II) or CaSiO 3 .
  • the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 . More preferably, the catalyst is TiO 2 , Al(OH) 3 or V 2 O 5 . According to an embodiment of the invention, the catalyst is Al(OH) 3 or V 2 O 5 . V 2 O 5 is most preferred.
  • the flue gas desulfurization denitration agent is composed of 92 parts by weight of calcium carbide slag, 5 parts by weight of magnesium oxide and 3 parts by weight of titanium dioxide.
  • the flue gas desulfurization denitration agent comprises 87.6 parts by weight of calcium carbide slag, 10 parts by weight of magnesium oxide and 2.4 parts by weight of aluminum hydroxide.
  • the flue gas desulfurization denitration agent is composed of 83 parts by weight of calcium carbide slag, 15 parts by weight of magnesium oxide, and 2 parts by weight of vanadium pentoxide.
  • the flue gas desulfurization denitration agent may be in the form of a dry powder.
  • the dry powder of the desulfurization and denitrification agent and the pre-dusting flue gas are thoroughly mixed in the flue gas pipeline, and then enter the absorption tower for desulfurization and denitration treatment, and the flue gas after desulfurization and denitration is discharged by the chimney.
  • the flue gas desulfurization denitration agent of the present invention can be produced by a conventional method.
  • calcium carbide slag, magnesium oxide and a catalyst are uniformly mixed to obtain a product.
  • the preparation method of the present invention further comprises the step of treating the calcium carbide slag: the calcium carbide slag product is subjected to a drying, crushing and sieving step to obtain a carbide slag having a particle size of less than 200 mesh.
  • the flue gas desulfurization denitration agent of the invention is used for dry flue gas desulfurization and denitrification.
  • the dry powder of the desulfurization and denitrification agent and the pre-dusting flue gas are thoroughly mixed in the flue gas pipeline, and then enter the absorption tower for desulfurization and denitration treatment, and the flue gas after the desulfurization and denitration is discharged by the chimney.
  • the dry flue gas desulfurization and denitration of the present invention is carried out in a flue gas desulfurization and denitration apparatus including a flue gas inlet and a flue gas outlet.
  • the flue gas inlet has a flue gas flow rate of 1,000,000 to 12.5 million m 3 /h, a temperature of 110 to 130 ° C, a sulfur dioxide concentration of 350 mg/m 3 or more, and a nitrogen oxide concentration of 350 mg/m 3 or more.
  • the flue gas inlet has a flue gas flow rate of 150,000 to 110,000 m 3 /h, a temperature of 120 to 130 ° C, a sulfur dioxide concentration of 500 mg/m 3 or more, and a nitrogen oxide concentration of 400 mg/m 3 or more.
  • the flue gas flow rate of the flue gas outlet is 800,000 to 900,000 m 3 /h, the temperature is 50 to 70 ° C, the sulfur dioxide concentration is 35 mg/m 3 or less, and the nitrogen oxide concentration is 70 mg/m 3 or less.
  • the flue gas outlet has a flue gas flow rate of 850,000 to 900,000 m 3 /h, a temperature of 55 to 65 ° C, a sulfur dioxide concentration of 28 mg/m 3 or less, and a nitrogen oxide concentration of 65 mg/m 3 or less. In this way, it is more advantageous to reduce the amount of calcium carbide slag under the unit removal amount.
  • the desulfurizing agent of this comparative example consisted of 100 parts by weight of carbide slag. After desulfurization and denitrification using the desulfurizer, the flue gas data at the outlet is detected as shown in the following table.
  • the desulfurization agent has a desulfurization efficiency of 95% by weight and a denitration efficiency of only 65 wt%.
  • the desulfurizing agent of the present comparative composition was composed of 5 parts by weight of calcium oxide, 3 parts by weight of a catalyst, and 92 parts by weight of calcium carbide slag.
  • the catalyst is TiO 2
  • the calcium carbide slag is a finished product having a particle size of less than 200 mesh obtained by grinding the calcium carbide slag product produced by the dry acetylene process.
  • the flue gas data at the outlet is detected as shown in the following table.
  • the desulfurization agent has a desulfurization efficiency of 95% by weight and a denitration efficiency of only 70% by weight.
  • the amount of calcium carbide slag per unit removal amount was equivalent.
  • the desulfurization denitration agent of this example consisted of 5 parts by weight of magnesium oxide, 3 parts by weight of a catalyst, and 92 parts by weight of calcium carbide slag.
  • Magnesium oxide has an active magnesium oxide of more than 70% by weight and a particle size of less than 100 mesh.
  • the catalyst is TiO 2
  • the calcium carbide slag is a finished product of a calcium carbide slag product produced by a dry acetylene process having a particle size of less than 200 mesh.
  • the calcium carbide slag, the magnesium oxide and the catalyst are uniformly mixed to obtain a desulfurization and denitration agent A1.
  • the flue gas data at the outlet is detected as shown in the following table.
  • the desulfurization denitration agent has a desulfurization efficiency of 95 wt% and a denitration efficiency of 85 wt%. Compared with Comparative Examples 1, 2, the amount of calcium carbide slag removed per unit was reduced by 30%.
  • the desulfurization denitration agent of this example consisted of 10 parts by weight of magnesium oxide, 2.4 parts by weight of a catalyst, and 87.6 parts by weight of calcium carbide slag.
  • Magnesium oxide has an active magnesium oxide of more than 75 wt% and a particle size of less than 100 mesh.
  • the catalyst is Al(OH) 3
  • the calcium carbide slag is a finished product of a calcium carbide slag product produced by a dry acetylene process having a particle size of less than 200 mesh.
  • the calcium carbide slag, the magnesium oxide and the catalyst are uniformly mixed to obtain a desulfurization and denitration agent A2.
  • the flue gas data at the outlet is detected as shown in the following table.
  • the desulfurization denitration agent has a desulfurization efficiency of 96 wt% and a denitration efficiency of 86 wt%. Compared with Comparative Examples 1, 2, the amount of calcium carbide slag removed per unit was reduced by 35%.
  • the desulfurization denitration agent of this example consisted of 15 parts by weight of magnesium oxide, 2 parts by weight of a catalyst, and 83 parts by weight of calcium carbide slag.
  • Magnesium oxide has an active magnesium oxide of more than 80% by weight and a particle size of less than 100 mesh.
  • the catalyst is V 2 O 5
  • the calcium carbide slag is a finished product of a calcium carbide slag product produced by a dry acetylene process having a particle size of less than 200 mesh.
  • the calcium carbide slag, the magnesium oxide and the catalyst are uniformly mixed to obtain a desulfurization and denitration agent A3.
  • the flue gas data at the outlet is detected as shown in the following table.
  • the desulfurization denitration agent A3 has a desulfurization efficiency of 98 wt% and a denitration efficiency of 90 wt%. Compared with Comparative Examples 1, 2, the amount of calcium carbide slag removed per unit was reduced by 37%.

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Abstract

A flue gas desulfurization and denitration agent, a preparation method therefor and applications thereof. The flue gas desulfurization and denitration agent comprises the following components: 70 to 93 parts carbide slag, 5 to 25 parts magnesium oxide, and 1 to 5 parts of a catalyst by weight, the catalyst is one or more selected from TiO2, Al(OH)3, V2O5,WO3, K2O, binuclear ferrocobalt phthalocyanine (II) or CaSiO3, and the flue gas desulfurization and denitration agent not containing calcium oxide. The flue gas desulfurization and denitration agent can remove SO2 and NOX from flue gas simultaneously. By means of the flue gas desulfurization and denitration agent, under the premise of satisfying high desulfurization and denitration efficiency, the carbide slag dosage needed by unit removal can be significantly reduced

Description

烟气脱硫脱硝剂及其制备方法和应用Flue gas desulfurization and denitration agent, preparation method and application thereof 技术领域Technical field
本发明涉及一种烟气脱硫脱硝剂及其制备方法和应用，尤其是一种基于电石渣的烟气脱硫脱硝剂及其制备方法和应用。The invention relates to a flue gas desulfurization and denitration agent, a preparation method and application thereof, in particular to a flue gas desulfurization and denitration agent based on calcium carbide slag, a preparation method and application thereof.
背景技术Background technique
从大气污染来说，SO 2和NO X是主要污染物。在国家实施颁布的《大气污染物综合排放标准GB16297-1996》等系列标准和法规中，均对其排放含量进行了明确限定。由于其二者同时存在于烟气中，若采取分别脱除的方法将带来设备繁多、占地面积大、操作复杂、前期投资大的问题。SO 2和NO X都是酸性氧化物，同时脱除完全可行，目前也存在一些工业示范和商业运行装置。当前烟气脱硫脱硝一体化的方法主要分为湿法脱硫脱硝、干法脱硫脱硝和半干法脱硫脱硝三种。总的来说，湿法脱除效果好，但废液污染严重；干法脱除效果好，但操作费用高；半干法兼具干法与湿法的优点，但也存在操作不稳定的问题。在配制一体化脱硫脱硝剂的过程中，多数配方采用各种纯净的有效组分进行混合配制的方法，由此造成脱硫脱硝剂成本较高。如何利用工业废料生产脱硫脱硝剂成为目前的研究热点。 For pollution from the atmosphere, SO 2 and NO X are the major pollutants. In the series of standards and regulations such as the “Integrated Emission Standard for Air Pollutants GB16297-1996” promulgated by the state, the emission content is clearly defined. Since both of them exist in the flue gas at the same time, the method of separately removing will bring about a problem of a large number of equipments, a large area, complicated operation, and large investment in the early stage. SO 2 and NO X are acidic oxides while removing entirely feasible, currently there are some exemplary industrial and commercial operation means. The current integration methods of flue gas desulfurization and denitrification are mainly divided into three types: wet desulfurization and denitrification, dry desulfurization and denitrification, and semi-dry desulfurization and denitrification. In general, the wet removal effect is good, but the waste liquid pollution is serious; the dry removal effect is good, but the operation cost is high; the semi-dry method has the advantages of the dry method and the wet method, but there are also unstable operations. problem. In the process of formulating the integrated desulfurization and denitration agent, most of the formulations are prepared by mixing various pure effective components, thereby causing high cost of the desulfurization and denitration agent. How to use industrial waste to produce desulfurization and denitrification agents has become a hot research topic.
电石渣是电石与水反应生成乙炔气体的过程中产生的工业废弃物。电石渣的主要成分是Ca(OH) 2，同时还含有多种杂质，例如硫化物、氰化物，铁镁铝钙的氧化物等。电石渣中的Ca(OH) 2溶出速率大于CaCO 3，因而其可以用于烟气脱硫。例如，CN101642674B公开了一种电石渣预处理的湿法烟气脱硫工艺，以电石渣浆液作为脱硫剂对烟气进行湿法脱硫处理，在电石渣浆液中加入催化剂，并鼓入空气进行氧化反应，氧化反应后的电石渣浆液再作为脱硫剂进行烟气湿法脱 硫处理。CN101816891A公开了一种电石渣预处理的臭氧法湿法烟气脱硫工艺，以电石渣作为脱硫剂对烟气进行湿法脱硫，在电石渣化渣过程中通入臭氧和氧气的混合气，进行氧化反应，氧化后的电石渣浆液作为脱硫剂进行烟气脱硫。 Carbide slag is industrial waste generated in the process of reacting calcium carbide with water to form acetylene gas. The main component of the calcium carbide slag is Ca(OH) 2 , and also contains various impurities such as sulfides, cyanides, oxides of iron magnesium aluminum, and the like. The Ca(OH) 2 dissolution rate in the carbide slag is greater than CaCO 3 , so it can be used for flue gas desulfurization. For example, CN101642674B discloses a wet flue gas desulfurization process for calcium carbide slag pretreatment, which uses a calcium carbide slag slurry as a desulfurizing agent to carry out a wet desulfurization treatment on a flue gas, a catalyst is added to the calcium carbide slag slurry, and air is blasted for oxidation reaction. The calcium carbide slurry after the oxidation reaction is further used as a desulfurizing agent for the flue gas wet desulfurization treatment. CN101816891A discloses an ozone method wet flue gas desulfurization process for pretreatment of calcium carbide slag, wherein the calcium slag is used as a desulfurizing agent to perform wet desulfurization of the flue gas, and in the process of calcium carbide slag slag, a mixture of ozone and oxygen is introduced. The oxidation reaction, the oxidized calcium carbide slurry is used as a desulfurizing agent for flue gas desulfurization.
一方面，上述工艺均将电石渣单独的脱硫剂使用，并没有考虑将其作为脱硝剂使用。同时，上述工艺均为湿法脱硫工艺，容易产生大量工业废液。另一方面，从电石渣脱硫脱硝的有效成分含量为25～30wt％，如果采用单一的电石渣进行脱硫脱硝，在满足较高脱硫脱硝效率的前提下，单位脱除量需要大量的电石渣，从而导致设备庞大和操作费用高昂。On the one hand, the above processes all use the calcium carbide slag alone as a desulfurizing agent, and do not consider it as a denitration agent. At the same time, the above processes are all wet desulfurization processes, and it is easy to produce a large amount of industrial waste liquid. On the other hand, the effective component content of desulfurization and denitrification from calcium carbide slag is 25-30% by weight. If a single calcium carbide slag is used for desulfurization and denitration, a large amount of calcium carbide slag is required for the unit removal amount under the premise of satisfying the high desulfurization and denitration efficiency. This results in a large equipment and high operating costs.
因此，目前仍然需要开发基于电石渣的烟气处理剂，其可以同时将烟气中的SO 2和NO X脱除。此外，仍然需要一种脱硫脱硝剂，在满足较高的脱硫脱硝效率的前提下，单位脱除量需要的电石渣用量显著降低。 Thus, there is still a need to develop flue gas treating agent based carbide slag, which may be the flue gas while the removal of SO 2 and NO X. In addition, there is still a need for a desulfurization and denitration agent. Under the premise of satisfying the high desulfurization and denitration efficiency, the amount of calcium carbide slag required for unit removal is significantly reduced.
发明内容Summary of the invention
本发明的一个目的在于提供一种烟气脱硫脱硝剂，其可以同时将烟气中的SO 2和NO X脱除。根据本发明进一步的目的，在满足较高的脱硫脱硝效率的前提下，单位脱除量需要的电石渣用量显著降低。 An object of the present invention is to provide a flue gas desulfurization and denitration agent, which may be the flue gas while the removal of SO 2 and NO X. According to a further object of the present invention, the amount of calcium carbide slag required for unit removal is significantly reduced on the premise of satisfying higher desulfurization and denitration efficiency.
本发明的另一个目的在于提供一种烟气脱硫脱硝剂的制备方法，其制备工艺简单。Another object of the present invention is to provide a method for preparing a flue gas desulfurization and denitration agent, which is simple in preparation process.
本发明的再一个目的在于提供一种烟气脱硫脱硝剂的应用，其可以有效脱除烟气中的SO 2和NO X，并且可以降低单位脱除量下的电石渣用量。 A further object of the present invention is to provide a flue gas desulfurization applications denitration agent which can effectively remove flue gas SO 2 and NO X, and may reduce the amount of carbide slag removal unit amount.
本发明提供一种烟气脱硫脱硝剂，其包括如下组分：The invention provides a flue gas desulfurization denitration agent, which comprises the following components:
电石渣    70～93重量份，Carbide slag 70-93 parts by weight,
氧化镁    5～25重量份，和Magnesium oxide 5 to 25 parts by weight, and
催化剂    1～5重量份；1 to 5 parts by weight of the catalyst;
其中，所述的催化剂选自TiO 2、Al(OH) 3、V 2O 5、WO 3、K 2O、双核酞菁钴铁(II)或CaSiO 3中的一种或多种； Wherein the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 , WO 3 , K 2 O, dinuclear cobalt phthalocyanine iron (II) or CaSiO 3 ;
其中，所述的烟气脱硫脱硝剂不含有氧化钙。Wherein, the flue gas desulfurization denitration agent does not contain calcium oxide.
根据本发明的烟气脱硫脱硝剂，优选地，其包括如下组分：The flue gas desulfurization denitration agent according to the present invention preferably comprises the following components:
电石渣    80～92重量份，Calcium carbide slag 80-92 parts by weight,
氧化镁    5～15重量份，和Magnesium oxide 5 to 15 parts by weight, and
催化剂    2～3重量份。The catalyst is 2 to 3 parts by weight.
根据本发明的烟气脱硫脱硝剂，优选地，所述的催化剂选自TiO 2、Al(OH) 3、V 2O 5中的一种或多种。 According to the flue gas desulfurization denitration agent of the present invention, preferably, the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 .
根据本发明的烟气脱硫脱硝剂，优选地，所述的电石渣为干法乙炔工艺产生的电石渣产物经研磨后得到的粒度小于200目的成品；所述的氧化镁为粒度小于100目的粉体，其活性氧化镁含量大于70wt％。According to the flue gas desulfurization denitration agent of the present invention, preferably, the calcium carbide slag is a finished product having a particle size of less than 200 mesh obtained by grinding a calcium carbide slag product produced by a dry acetylene process; and the magnesium oxide is a powder having a particle size of less than 100 mesh. The body has an active magnesium oxide content of more than 70% by weight.
根据本发明的烟气脱硫脱硝剂，优选地，所述氧化镁中的活性氧化镁含量为80wt％～85wt％。According to the flue gas desulfurization denitration agent of the present invention, preferably, the active magnesium oxide content in the magnesium oxide is from 80% by weight to 85% by weight.
根据本发明的烟气脱硫脱硝剂，优选地，所述烟气脱硫脱硝剂由以下组分组成：According to the flue gas desulfurization denitration agent of the present invention, preferably, the flue gas desulfurization denitration agent is composed of the following components:
(1)92重量份电石渣，5重量份氧化镁和3重量份二氧化钛；或者(1) 92 parts by weight of carbide slag, 5 parts by weight of magnesium oxide and 3 parts by weight of titanium dioxide;
(2)87.6重量份电石渣，10重量份氧化镁和2.4重量份氢氧化铝；或者(2) 87.6 parts by weight of calcium carbide slag, 10 parts by weight of magnesium oxide and 2.4 parts by weight of aluminum hydroxide;
(3)83重量份电石渣，15重量份氧化镁和2重量份五氧化二钒。(3) 83 parts by weight of calcium carbide slag, 15 parts by weight of magnesium oxide and 2 parts by weight of vanadium pentoxide.
根据本发明的烟气脱硫脱硝剂，优选地，所述的烟气脱硫脱硝剂为干粉状。According to the flue gas desulfurization denitration agent of the present invention, preferably, the flue gas desulfurization denitration agent is in the form of a dry powder.
本发明还提供上述烟气脱硫脱硝剂的制备方法，包括将电石渣、 氧化镁和催化剂混合的步骤。The invention also provides a preparation method of the above flue gas desulfurization denitration agent, comprising the steps of mixing calcium carbide slag, magnesium oxide and a catalyst.
本发明也提供上述烟气脱硫脱硝剂的应用，其用于干法烟气脱硫脱硝。The invention also provides the use of the above flue gas desulfurization denitration agent for dry flue gas desulfurization and denitrification.
根据本发明的应用，优选地，所述干法烟气脱硫脱硝在包括烟气进口和烟气出口的烟气脱硫脱硝设备中进行，烟气进口的烟气流量为1000000～1250000m 3/h、温度为110～130℃、二氧化硫浓度为350mg/m 3以上、且氮氧化物浓度为350mg/m 3以上；烟气出口的烟气流量为800000～900000m 3/h、温度为50～70℃、二氧化硫浓度为35mg/m 3以下、且氮氧化物浓度为70mg/m 3以下。 According to the application of the present invention, preferably, the dry flue gas desulfurization and denitration is carried out in a flue gas desulfurization and denitration device including a flue gas inlet and a flue gas outlet, and the flue gas flow rate of the flue gas inlet is 1000000 to 12.5 million m 3 /h, The temperature is 110-130 ° C, the sulfur dioxide concentration is 350 mg/m 3 or more, and the nitrogen oxide concentration is 350 mg/m 3 or more; the flue gas flow rate of the flue gas outlet is 800,000 to 900,000 m 3 /h, and the temperature is 50 to 70 ° C, The sulfur dioxide concentration is 35 mg/m 3 or less, and the nitrogen oxide concentration is 70 mg/m 3 or less.
与现有技术相比，本发明实现了电石渣的二次利用，达到了以废治废的目的。本发明的脱硫脱硝剂可以同时将烟气中的SO 2和NO X脱除。根据本发明优选的技术方案，在满足较高脱硫脱硝效率的前提下，单位脱除量需要的电石渣用量显著降低。此外，脱硫脱硝剂成本低廉、配制方法简单。 Compared with the prior art, the invention realizes the secondary utilization of calcium carbide slag, and achieves the purpose of treating waste by waste. Desulfurization agent of the present invention can simultaneously denitration of flue gas SO 2 and NO X removal. According to the preferred technical solution of the present invention, the amount of calcium carbide slag required for the unit removal amount is remarkably reduced on the premise of satisfying the high desulfurization and denitration efficiency. In addition, the desulfurization and denitration agent is low in cost and simple in preparation method.
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.
<烟气脱硫脱硝剂及其制备方法><Fume gas desulfurization denitration agent and preparation method thereof>
本发明的烟气脱硫脱硝剂为一种烟气处理剂，兼具脱硫和脱硝功能。本发明的烟气脱硫脱硝剂以电石渣为主料，氧化镁为辅料，并添加合适的催化剂。这样可以使得电石渣的功能得以充分发挥，兼具脱硫和脱硝功能，并且可以降低单位脱除量下的电石渣用量。本发明的烟气脱硫脱硝剂不含有氧化钙。所谓单位脱除量下的电石渣用量表示脱除相同量的烟气所需要的电石渣的重量。本发明发现，氧化钙并不 能显著降低单位脱除量下的电石渣用量。The flue gas desulfurization denitration agent of the invention is a flue gas treatment agent, and has the functions of desulfurization and denitration. The flue gas desulfurization and denitration agent of the invention mainly comprises calcium carbide slag, magnesium oxide as an auxiliary material, and a suitable catalyst is added. This can make the function of the calcium carbide slag fully exerted, has both desulfurization and denitration functions, and can reduce the amount of calcium carbide slag under the unit removal amount. The flue gas desulfurization denitration agent of the present invention does not contain calcium oxide. The amount of calcium carbide slag used in the unit removal amount represents the weight of the carbide slag required to remove the same amount of flue gas. The present inventors have found that calcium oxide does not significantly reduce the amount of calcium carbide slag per unit removal.
本发明的烟气脱硫脱硝剂包括如下组分：电石渣、氧化镁和催化剂。电石渣的用量为70～93重量份，优选为80～92重量份，更优选为83～86重量份。氧化镁的用量为5～25重量份，优选为5～15重量份，更优选为10～15重量份。催化剂的用量为1～5重量份，优选为2～3重量份，更优选为2～2.5重量份。将上述组分的用量控制在上述范围，可以改善在相同用量的烟气脱硫脱硝剂下的脱硫效果和脱硝效果。The flue gas desulfurization denitration agent of the present invention comprises the following components: calcium carbide slag, magnesium oxide and a catalyst. The calcium carbide slag is used in an amount of 70 to 93 parts by weight, preferably 80 to 92 parts by weight, more preferably 83 to 86 parts by weight. The magnesium oxide is used in an amount of 5 to 25 parts by weight, preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight. The catalyst is used in an amount of 1 to 5 parts by weight, preferably 2 to 3 parts by weight, more preferably 2 to 2.5 parts by weight. By controlling the amount of the above components in the above range, the desulfurization effect and the denitration effect under the same amount of flue gas desulfurization and denitration agent can be improved.
在本发明中，电石渣为工业废物，从而实现了以废治废的目的。本发明的电石渣优选为干法乙炔工艺产生的电石渣产物经研磨后得到的粒度小于200目的成品。电石渣的粒度可以小于200目，优选小于300目，更优选小于350目。采用上述电石渣，有利于改善脱硫脱硝效果。In the present invention, the carbide slag is industrial waste, thereby achieving the purpose of waste disposal. The calcium carbide slag of the present invention is preferably a finished product having a particle size of less than 200 mesh obtained by grinding the calcium carbide slag product produced by the dry acetylene process. The carbide slag may have a particle size of less than 200 mesh, preferably less than 300 mesh, more preferably less than 350 mesh. The use of the above calcium carbide slag is beneficial to improve the desulfurization and denitration effect.
在本发明中，氧化镁可以为粒度小于100目的粉体，优选小于200目的粉体。本发明的氧化镁中，活性氧化镁含量可以大于70wt％，优选为70wt％～85wt％，更优选为80wt％～85wt％。采用上述氧化镁，有利于改善脱硫脱硝效果。In the present invention, the magnesium oxide may be a powder having a particle size of less than 100 mesh, preferably a powder having a particle size of less than 200 mesh. In the magnesium oxide of the present invention, the active magnesium oxide content may be more than 70% by weight, preferably 70% by weight to 85% by weight, more preferably 80% by weight to 85% by weight. The use of the above magnesium oxide is beneficial to improve the desulfurization and denitration effect.
在本发明中，催化剂可以选自TiO 2、Al(OH) 3、V 2O 5、WO 3、K 2O、双核酞菁钴铁(II)或CaSiO 3中的一种或多种。优选地，所述的催化剂选自TiO 2、Al(OH) 3、V 2O 5中的一种或多种。更优选地，所述的催化剂为TiO 2、Al(OH) 3或V 2O 5。根据本发明的一个实施方式，所述的催化剂为Al(OH) 3或V 2O 5。V 2O 5是最优选的。 In the present invention, the catalyst may be selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 , WO 3 , K 2 O, dinuclear cobalt phthalocyanine iron (II) or CaSiO 3 . Preferably, the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 . More preferably, the catalyst is TiO 2 , Al(OH) 3 or V 2 O 5 . According to an embodiment of the invention, the catalyst is Al(OH) 3 or V 2 O 5 . V 2 O 5 is most preferred.
根据本发明的一个具体实施方式，所述烟气脱硫脱硝剂由以下组分组成：92重量份电石渣，5重量份氧化镁和3重量份二氧化钛。根据本发明的另一个具体实施方式，所述烟气脱硫脱硝剂由以下组分组成87.6重量份电石渣，10重量份氧化镁和2.4重量份氢氧化铝。根据 本发明的再一个具体实施方式，所述烟气脱硫脱硝剂由以下组分组成：83重量份电石渣，15重量份氧化镁和2重量份五氧化二钒。本发明发现，上述组分和用量的所述烟气脱硫脱硝剂可以更好地改善脱硫脱硝效果，并且降低单位脱除量下的电石渣用量。According to a specific embodiment of the present invention, the flue gas desulfurization denitration agent is composed of 92 parts by weight of calcium carbide slag, 5 parts by weight of magnesium oxide and 3 parts by weight of titanium dioxide. According to another embodiment of the present invention, the flue gas desulfurization denitration agent comprises 87.6 parts by weight of calcium carbide slag, 10 parts by weight of magnesium oxide and 2.4 parts by weight of aluminum hydroxide. According to still another embodiment of the present invention, the flue gas desulfurization denitration agent is composed of 83 parts by weight of calcium carbide slag, 15 parts by weight of magnesium oxide, and 2 parts by weight of vanadium pentoxide. The present invention has found that the above-mentioned components and amounts of the flue gas desulfurization denitration agent can better improve the desulfurization and denitration effect, and reduce the amount of calcium carbide slag per unit removal amount.
在本发明中，所述的烟气脱硫脱硝剂可以为干粉状。这样可以直接将烟气脱硫脱硝剂与烟气混合，进而对烟气进行SO 2和NO X的脱除。例如，将脱硫脱硝剂干粉与预除尘后的烟气在烟气管道充分混合，然后进入吸收塔进行脱硫脱硝处理，脱硫脱硝后的烟气由烟囱排出。 In the present invention, the flue gas desulfurization denitration agent may be in the form of a dry powder. This direct flue gas desulfurization and denitrification agent mixed with the flue gas, flue gas and further to removal of SO 2 and NO X. For example, the dry powder of the desulfurization and denitrification agent and the pre-dusting flue gas are thoroughly mixed in the flue gas pipeline, and then enter the absorption tower for desulfurization and denitration treatment, and the flue gas after desulfurization and denitration is discharged by the chimney.
本发明的烟气脱硫脱硝剂可以采用常规的方法制备。例如将电石渣、氧化镁和催化剂混合均匀得到产品。此外，本发明的制备方法还包括电石渣的处理步骤：将电石渣产物经过烘干、破碎和筛分步骤获得粒度小于200目的电石渣。The flue gas desulfurization denitration agent of the present invention can be produced by a conventional method. For example, calcium carbide slag, magnesium oxide and a catalyst are uniformly mixed to obtain a product. In addition, the preparation method of the present invention further comprises the step of treating the calcium carbide slag: the calcium carbide slag product is subjected to a drying, crushing and sieving step to obtain a carbide slag having a particle size of less than 200 mesh.
<烟气脱硫脱硝剂的应用><Application of flue gas desulfurization and denitration agent>
本发明的烟气脱硫脱硝剂用于干法烟气脱硫脱硝。根据本发明的一个实施方式，将脱硫脱硝剂干粉与预除尘后的烟气在烟气管道充分混合，然后进入吸收塔进行脱硫脱硝处理，脱硫脱硝后的烟气由烟囱排出。本发明的干法烟气脱硫脱硝在包括烟气进口和烟气出口的烟气脱硫脱硝设备中进行。烟气进口的烟气流量为1000000～1250000m 3/h、温度为110～130℃、二氧化硫浓度为350mg/m 3以上、且氮氧化物浓度为350mg/m 3以上。优选地，烟气进口的烟气流量为1050000～1100000m 3/h、温度为120～130℃、二氧化硫浓度为500mg/m 3以上、且氮氧化物浓度为400mg/m 3以上。烟气出口的烟气流量为800000～900000m 3/h、温度为50～70℃、二氧化硫浓度为35mg/m 3以下、且氮氧化物浓度为70mg/m 3以下。优选地，烟气出口的烟气流量为850000～900000m 3/h、温度为55～65℃、二氧化硫浓度 为28mg/m 3以下、且氮氧化物浓度为65mg/m 3以下。这样，更有利于降低单位脱除量下的电石渣用量。 The flue gas desulfurization denitration agent of the invention is used for dry flue gas desulfurization and denitrification. According to an embodiment of the present invention, the dry powder of the desulfurization and denitrification agent and the pre-dusting flue gas are thoroughly mixed in the flue gas pipeline, and then enter the absorption tower for desulfurization and denitration treatment, and the flue gas after the desulfurization and denitration is discharged by the chimney. The dry flue gas desulfurization and denitration of the present invention is carried out in a flue gas desulfurization and denitration apparatus including a flue gas inlet and a flue gas outlet. The flue gas inlet has a flue gas flow rate of 1,000,000 to 12.5 million m 3 /h, a temperature of 110 to 130 ° C, a sulfur dioxide concentration of 350 mg/m 3 or more, and a nitrogen oxide concentration of 350 mg/m 3 or more. Preferably, the flue gas inlet has a flue gas flow rate of 150,000 to 110,000 m 3 /h, a temperature of 120 to 130 ° C, a sulfur dioxide concentration of 500 mg/m 3 or more, and a nitrogen oxide concentration of 400 mg/m 3 or more. The flue gas flow rate of the flue gas outlet is 800,000 to 900,000 m 3 /h, the temperature is 50 to 70 ° C, the sulfur dioxide concentration is 35 mg/m 3 or less, and the nitrogen oxide concentration is 70 mg/m 3 or less. Preferably, the flue gas outlet has a flue gas flow rate of 850,000 to 900,000 m 3 /h, a temperature of 55 to 65 ° C, a sulfur dioxide concentration of 28 mg/m 3 or less, and a nitrogen oxide concentration of 65 mg/m 3 or less. In this way, it is more advantageous to reduce the amount of calcium carbide slag under the unit removal amount.
以下实施例和对比例中的“份”表示重量份，除非特别声明。The "parts" in the following examples and comparative examples represent parts by weight unless otherwise stated.
以下实施例和对比例的烟气进口的参数如下表所示。The parameters of the flue gas inlets of the following examples and comparative examples are shown in the following table.
Figure PCTCN2018103040-appb-000001
Figure PCTCN2018103040-appb-000001
对比例1Comparative example 1
本对比例的脱硫剂由100重量份电石渣组成。采用该脱硫剂脱硫脱硝后，检测出口处的烟气数据，如下表所示。The desulfurizing agent of this comparative example consisted of 100 parts by weight of carbide slag. After desulfurization and denitrification using the desulfurizer, the flue gas data at the outlet is detected as shown in the following table.
Figure PCTCN2018103040-appb-000002
Figure PCTCN2018103040-appb-000002
由表可知，该脱硫剂的脱硫效率可达95wt％，脱硝效率仅为65wt％。It can be seen from the table that the desulfurization agent has a desulfurization efficiency of 95% by weight and a denitration efficiency of only 65 wt%.
对比例2Comparative example 2
本对比例的脱硫剂由5重量份氧化钙、3重量份催化剂和92重量份电石渣组成。催化剂为TiO 2，电石渣为干法乙炔工艺产生的电石渣产物经研磨后得到的粒度小于200目的成品。 The desulfurizing agent of the present comparative composition was composed of 5 parts by weight of calcium oxide, 3 parts by weight of a catalyst, and 92 parts by weight of calcium carbide slag. The catalyst is TiO 2 , and the calcium carbide slag is a finished product having a particle size of less than 200 mesh obtained by grinding the calcium carbide slag product produced by the dry acetylene process.
采用该脱硫剂脱硝后，检测出口处的烟气数据，如下表所示。After denitration with the desulfurizing agent, the flue gas data at the outlet is detected as shown in the following table.
Figure PCTCN2018103040-appb-000003
Figure PCTCN2018103040-appb-000003
由表可知，该脱硫剂的脱硫效率可达95wt％，脱硝效率仅为70wt％。对比例1和2中，单位脱除量的电石渣用量相当。It can be seen from the table that the desulfurization agent has a desulfurization efficiency of 95% by weight and a denitration efficiency of only 70% by weight. In Comparative Examples 1 and 2, the amount of calcium carbide slag per unit removal amount was equivalent.
实施例1Example 1
本实施例的脱硫脱硝剂由5重量份氧化镁、3重量份催化剂和92重量份电石渣组成。氧化镁的活性氧化镁大于70wt％、粒度小于100目的粉体，催化剂为TiO 2，电石渣为干法乙炔工艺产生的电石渣产物 经研磨后得到的粒度小于200目的成品。电石渣、氧化镁和催化剂混合均匀后得到脱硫脱硝剂A1。 The desulfurization denitration agent of this example consisted of 5 parts by weight of magnesium oxide, 3 parts by weight of a catalyst, and 92 parts by weight of calcium carbide slag. Magnesium oxide has an active magnesium oxide of more than 70% by weight and a particle size of less than 100 mesh. The catalyst is TiO 2 , and the calcium carbide slag is a finished product of a calcium carbide slag product produced by a dry acetylene process having a particle size of less than 200 mesh. The calcium carbide slag, the magnesium oxide and the catalyst are uniformly mixed to obtain a desulfurization and denitration agent A1.
采用脱硫脱硝剂A1脱硫脱硝后，检测出口处的烟气数据，如下表所示。After desulfurization and denitrification by desulfurization and denitrification agent A1, the flue gas data at the outlet is detected as shown in the following table.
Figure PCTCN2018103040-appb-000004
Figure PCTCN2018103040-appb-000004
由表可知，该脱硫脱硝剂的脱硫效率可达95wt％，脱硝效率可达85wt％。与对比例1、2相比，单位脱除量的电石渣用量减少了30％。It can be seen from the table that the desulfurization denitration agent has a desulfurization efficiency of 95 wt% and a denitration efficiency of 85 wt%. Compared with Comparative Examples 1, 2, the amount of calcium carbide slag removed per unit was reduced by 30%.
实施例2Example 2
本实施例的脱硫脱硝剂由10重量份氧化镁、2.4重量份催化剂和87.6重量份电石渣组成。氧化镁的活性氧化镁大于75wt％、粒度小于100目的粉体，催化剂为Al(OH) 3，电石渣为干法乙炔工艺产生的电石渣产物经研磨后得到的粒度小于200目的成品。电石渣、氧化镁和催化剂混合均匀后得到脱硫脱硝剂A2。 The desulfurization denitration agent of this example consisted of 10 parts by weight of magnesium oxide, 2.4 parts by weight of a catalyst, and 87.6 parts by weight of calcium carbide slag. Magnesium oxide has an active magnesium oxide of more than 75 wt% and a particle size of less than 100 mesh. The catalyst is Al(OH) 3 , and the calcium carbide slag is a finished product of a calcium carbide slag product produced by a dry acetylene process having a particle size of less than 200 mesh. The calcium carbide slag, the magnesium oxide and the catalyst are uniformly mixed to obtain a desulfurization and denitration agent A2.
采用脱硫脱硝剂A2脱硫脱硝后，检测出口处的烟气数据，如下表所示。After desulfurization and denitrification using desulfurization and denitrification agent A2, the flue gas data at the outlet is detected as shown in the following table.
Figure PCTCN2018103040-appb-000005
Figure PCTCN2018103040-appb-000005
由表可知，该脱硫脱硝剂的脱硫效率可达96wt％，脱硝效率可达86wt％。与对比例1、2相比，单位脱除量的电石渣用量减少了35％。It can be seen from the table that the desulfurization denitration agent has a desulfurization efficiency of 96 wt% and a denitration efficiency of 86 wt%. Compared with Comparative Examples 1, 2, the amount of calcium carbide slag removed per unit was reduced by 35%.
实施例3Example 3
本实施例的脱硫脱硝剂由15重量份氧化镁、2重量份催化剂和83重量份电石渣组成。氧化镁的活性氧化镁大于80wt％、粒度小于100目的粉体，催化剂为V 2O 5，电石渣为干法乙炔工艺产生的电石渣产物经研磨后得到的粒度小于200目的成品。电石渣、氧化镁和催化剂混合均匀后得到脱硫脱硝剂A3。 The desulfurization denitration agent of this example consisted of 15 parts by weight of magnesium oxide, 2 parts by weight of a catalyst, and 83 parts by weight of calcium carbide slag. Magnesium oxide has an active magnesium oxide of more than 80% by weight and a particle size of less than 100 mesh. The catalyst is V 2 O 5 , and the calcium carbide slag is a finished product of a calcium carbide slag product produced by a dry acetylene process having a particle size of less than 200 mesh. The calcium carbide slag, the magnesium oxide and the catalyst are uniformly mixed to obtain a desulfurization and denitration agent A3.
采用脱硫脱硝剂A3脱硫脱硝后，检测出口处的烟气数据，如下表所示。After desulfurization and denitrification with desulfurization and denitrification agent A3, the flue gas data at the outlet is detected as shown in the following table.
Figure PCTCN2018103040-appb-000006
Figure PCTCN2018103040-appb-000006
由表可知，脱硫脱硝剂A3的脱硫效率可达98wt％，脱硝效率可达90wt％。与对比例1、2相比，单位脱除量的电石渣用量减少了37％。It can be seen from the table that the desulfurization denitration agent A3 has a desulfurization efficiency of 98 wt% and a denitration efficiency of 90 wt%. Compared with Comparative Examples 1, 2, the amount of calcium carbide slag removed per unit was reduced by 37%.
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. 一种烟气脱硫脱硝剂，其特征在于，其包括如下组分：A flue gas desulfurization denitration agent characterized by comprising the following components:
    电石渣   70～93重量份，Carbide slag 70-93 parts by weight,
    氧化镁   5～25重量份，和Magnesium oxide 5 to 25 parts by weight, and
    催化剂   1～5重量份；1 to 5 parts by weight of the catalyst;
    其中，所述的催化剂选自TiO 2、Al(OH) 3、V 2O 5、WO 3、K 2O、双核酞菁钴铁(II)或CaSiO 3中的一种或多种； Wherein the catalyst is selected from one or more of TiO 2 , Al(OH) 3 , V 2 O 5 , WO 3 , K 2 O, dinuclear cobalt phthalocyanine iron (II) or CaSiO 3 ;
    其中，所述的烟气脱硫脱硝剂不含有氧化钙。Wherein, the flue gas desulfurization denitration agent does not contain calcium oxide.
  2. 根据权利要求1所述的烟气脱硫脱硝剂，其特征在于，其包括如下组分：The flue gas desulfurization denitration agent according to claim 1, which comprises the following components:
    电石渣   80～92重量份，Calcium carbide slag 80-92 parts by weight,
    氧化镁   5～15重量份，和Magnesium oxide 5 to 15 parts by weight, and
    催化剂   2～3重量份。The catalyst is 2 to 3 parts by weight.
  3. 根据权利要求1所述的烟气脱硫脱硝剂，其特征在于，所述的催化剂选自TiO 2、Al(OH) 3、V 2O 5中的一种或多种。 The flue gas desulfurization denitration agent according to claim 1, wherein the catalyst is one or more selected from the group consisting of TiO 2 , Al(OH) 3 , and V 2 O 5 .
  4. 根据权利要求1所述的烟气脱硫脱硝剂，其特征在于，所述的电石渣为干法乙炔工艺产生的电石渣产物经研磨后得到的粒度小于200目的成品；所述的氧化镁为粒度小于100目的粉体，其活性氧化镁含量大于70wt％。The flue gas desulfurization denitration agent according to claim 1, wherein the calcium carbide slag is a finished product having a particle size of less than 200 mesh obtained by grinding a calcium carbide slag product produced by a dry acetylene process; and the magnesium oxide is a particle size. The powder of less than 100 mesh has an active magnesium oxide content of more than 70% by weight.
  5. 根据权利要求1所述的烟气脱硫脱硝剂，其特征在于，所述氧化镁中的活性氧化镁含量为80wt％～85wt％。The flue gas desulfurization denitration agent according to claim 1, wherein the magnesium oxide has an active magnesium oxide content of 80% by weight to 85% by weight.
  6. 根据权利要求1所述的烟气脱硫脱硝剂，其特征在于，所述烟气脱硫脱硝剂由以下组分组成：The flue gas desulfurization denitration agent according to claim 1, wherein the flue gas desulfurization denitration agent is composed of the following components:
    (1)92重量份电石渣，5重量份氧化镁和3重量份二氧化钛；或者(1) 92 parts by weight of carbide slag, 5 parts by weight of magnesium oxide and 3 parts by weight of titanium dioxide;
    (2)87.6重量份电石渣，10重量份氧化镁和2.4重量份氢氧化 铝；或者(2) 87.6 parts by weight of calcium carbide slag, 10 parts by weight of magnesium oxide and 2.4 parts by weight of aluminum hydroxide;
    (3)83重量份电石渣，15重量份氧化镁和2重量份五氧化二钒。(3) 83 parts by weight of calcium carbide slag, 15 parts by weight of magnesium oxide and 2 parts by weight of vanadium pentoxide.
  7. 根据权利要求1～6任一项所述的烟气脱硫脱硝剂，其特征在于，所述的烟气脱硫脱硝剂为干粉状。The flue gas desulfurization denitration agent according to any one of claims 1 to 6, wherein the flue gas desulfurization denitration agent is in the form of a dry powder.
  8. 根据权利要求1～7任一项所述的烟气脱硫脱硝剂的制备方法，其特征在于，包括将电石渣、氧化镁和催化剂混合的步骤。The method for producing a flue gas desulfurization and denitration agent according to any one of claims 1 to 7, which comprises the step of mixing calcium carbide slag, magnesium oxide and a catalyst.
  9. 根据权利要求1～7任一项所述的烟气脱硫脱硝剂的应用，其特征在于，其用于干法烟气脱硫脱硝。Use of the flue gas desulfurization and denitration agent according to any one of claims 1 to 7, which is characterized in that it is used for dry flue gas desulfurization and denitration.
  10. 根据权利要求9所述的应用，其特征在于，所述干法烟气脱硫脱硝在包括烟气进口和烟气出口的烟气脱硫脱硝设备中进行，烟气进口的烟气流量为1000000～1250000m 3/h、温度为110～130℃、二氧化硫浓度为350mg/m 3以上、且氮氧化物浓度为350mg/m 3以上；烟气出口的烟气流量为800000～900000m 3/h、温度为50～70℃、二氧化硫浓度为35mg/m 3以下、且氮氧化物浓度为70mg/m 3以下。 The application according to claim 9, wherein the dry flue gas desulfurization and denitration is carried out in a flue gas desulfurization and denitration device including a flue gas inlet and a flue gas outlet, and the flue gas flow rate of the flue gas inlet is 1000000 to 12.5 million m. 3 / h, the temperature is 110 ~ 130 ° C, the sulfur dioxide concentration is 350mg / m 3 or more, and the nitrogen oxide concentration is 350mg / m 3 or more; the flue gas flow rate of the flue gas outlet is 800000 ~ 90000m 3 / h, the temperature is 50 ～70° C., the sulfur dioxide concentration is 35 mg/m 3 or less, and the nitrogen oxide concentration is 70 mg/m 3 or less.
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CN111359653A (en) * 2020-04-07 2020-07-03 中海油天津化工研究设计院有限公司 Catalyst for improving desulfurization performance of calcium oxide
CN113499724A (en) * 2021-07-12 2021-10-15 翱华工程技术股份有限公司 Carbide slag slurry manufacturing equipment, carbide slag slurry manufacturing method and carbide slag slurry
CN116272334A (en) * 2022-12-26 2023-06-23 杭州尚善若水环保科技有限公司 Coupling desulfurization and denitrification medicament, preparation method and use method thereof
CN116272334B (en) * 2022-12-26 2023-08-15 杭州尚善若水环保科技有限公司 Coupling desulfurization and denitrification medicament, preparation method and use method thereof

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