WO2004020077A1 - METHOD AND APPARATUS FOR DESULFURIZATION COMPRISING INCORPORATING NO AND/OR NO2 IN GAS TO BE TREATED, TO RECOVER SO2 AS CaSO4 - Google Patents

Abstract

A method for desulfurization, characterized in that it comprises incorporating 10 to 5000 ppm of NO and/or NO2 in a SO2-containing gas to be treated, contacting a SO2 desulfurizing agent comprising carrier particles having a large particle diameter and, coated thereon, finely particulate Ca(OH)2 with the resulting gas to be treated in the state of a fluidized layer in a reaction tower, elevating them while reacting, allowing them to flow to a first gas-solid separator via the top of the reaction tower, precipitating and separating said carrier particles from a gas containing CaSO4 having been formed by the reaction of Ca(OH)2 on the surface of the above carrier particles with SO2 and been exfoliated, while allowing said gas containing CaSO4 to flow to a second gas-solid separator from the top of the above first gas-solid separator, and separating and recovering the above CaSO4 from the gas to be treated in the second gas-solid separator.

Description

Treated NO in the gas and / / or N 0 ₂ to coexist S 0 ₂ to C a S 0 ₄ and to desulfurization process for recovering and desulfurization apparatus Ming

Technical field

The present invention, the gas to be treated, for example the gas to be treated which has improved recovery of C a S 0 ₄ to SO ₂ in the field if the exhaust gas in the C a SO ₄ and to separate and recover the desulfurization method Contact Yopi desulfurization apparatus the desulfurization process and the desulfurization apparatus, 1 0 ppm to as least to be treated in the gas, especially, preferred properly is to be treated in the gas, characterized that you coexist 1 0 0 ppm NO and Z or N 0 ₂ 3 0 ₂ . a S 0 ₄ and then on the desulfurization process you and desulfurization apparatus for separating recovered.

Background art

So ₂ is a substance that has a significant impact on the environment and human health, and SO ₂ generated from the coal burning process is a major social problem. Therefore, systems that absorb and remove so ₂ have been studied. One of them is an absorption removal method using C a O. The C a O absorption removal of SO ₂ with is performed through the diffusion of so _2, the process of formation of _{C a SO 4 / C a S} 0 3 by solid reaction. Therefore, the characteristics of the C a O particles, that is, the surface area, pore size, pore volume, etc., have a great influence on the adsorption reaction. Commercially available Ca _II does not have a good calcium utilization in terms of SO ₂ absorption and removal properties.

Sanders et al. (Sanders et al.) Used fly ash and Reported that absorption removal characteristics of the mixed slurries the use if so ₂ of ash is improved Rereru (Sanders et al. Ind. Eng . Chem. Res. 1995, 34 (4), 302-307) . In that report, the improvement in the absorption and removal characteristics of SO ₂ was attributed to the presence of calcium silicate hydrate generated by the hydration reaction between calcium and alumina silicate. It explains that it is in the structure of the object. In addition, slurry from γ-alumina-CaO adsorbent (Svoboda et al.), CaO, calcium sulfate, and fly ash were aged at about 100 ° C and dried. Adsorbent (Hiroaki et al.) (It is thought that ettringite is formed. A similar technique is disclosed in Japanese Patent Publication No. 3-59737). However, the methods of preparing these adsorbents use relatively large amounts of water, have poor availability in areas with poor water use, and require long and / or many times to remove water. energy one is required this and, and S 0 ₂ forming composition to improve the adsorption characteristics at the time of preparation of the adsorbent since the management of the process is difficult, the desulfurization device manufacturing apparatus S o ₂ adsorbent However, there was an inconvenience that it was difficult to design a desulfurization unit that would be directly connected to the plant.

On the other hand, the present inventors have found that the mechanism of the hydration process in the process of mixing CaO and fly ash in water to prepare an adsorbent makes it possible to reduce the amount of the raw material. We have been keenly researching the production of desulfurizing agents that exhibit active SO ₂ adsorption properties that can be used in practical processes (Energy & Fuels, Vol. 13, No. 5, 1015-1020, 1999. Reference A). However, here, the amount of water used to prepare the desulfurizing agent is such that the weight ratio of H ₂ O / (carrier particles + C a (OH) ₂ ) is relatively large at 1.5. However, under such water use conditions, water resources are low. In areas where it does not exist, improvement is still needed to use it as a desulfurization method. Furthermore, at that time, it was important to improve the utilization of by-products and the efficiency of the use of the added desulfurizing agent in order to minimize waste. Accordingly, the present inventors have a dry desulfurization process further advance the technology to study the desulfurizing agent can be designed in almost practical level, relatively the absorption desulfurization component of SO ₂ has a large particle size C a ( OH) Ri by the the use of the wire carrier re yer _{particles 2} can be coated on the surface, to improve the C a (OH) utilization ₂ C a is absorption desulfurization components so _2, and efficiently, usability A desulfurization method and a desulfurization device invention capable of separating and recovering CaSO ₄ as a by-product with high purity have been completed and announced (Japanese Patent Application Laid-Open No. 2002-113326). Further, the present inventors [Fuel, 78/9, 1089 - in 1095 (1999)], but has published the effect of chain reaction of the NO _x present in the gas in the desulfurization process, a large particle size Canon Lyer with SO ₂ desulfurizing agent coated with C a (OH) ₂ fine particles on the particle surface, in the desulfurization method of separating and recovering as a 3 0 ₂ 〇 a S 0 ₄ of the treated gas, C a S 0 _The effect of _{4 on} the recovery rate has not been studied at all.

It is an object of the present invention to provide a desulfurization method capable of recovering a useful by-product Caso ₄ at a higher rate by using a SO ₂ desulfurizing agent in which large-sized carrier particles are coated with fine particles of Ca (OH) ₂ . The method is to provide a desulfurization device. In the desulfurization method and desulfurization apparatus using the desulfurizing agent,

C a (OH) C a S 0 4 which reacts with S 0 ₂ in the treatment month ₂ Kiyariya particle surface with a large particle size coated with it, to be peeled off efficiently from the wire carrier rear surface C is important for high rate recovered Ri by a a S 0 _4. What factors are involved in the improvement of the peeling efficiency is unknown.However, in order to improve the desulfurization method using the desulfurizing agent, NO _x in the desulfurization treatment disclosed by the present inventors has been described. (X is 1 or more and 2 or less.) focusing on coexistence effect, was allowed to coexist NO and // or N 0 _2, found that recovery properties of C a S 0 ₄ is improved, the I was able to solve the problem. Disclosure of the invention

The first of the present invention, the 3_Rei ₂ of the process gas by the NO Oyopi or N 0 ₂ to 1 0~ 5 0 0 0 ppm coexisting in the exhaust gas. a desulfurization process of separating and recovering as a a S 0 _4. Preferably, the NO and Z or N 0 ₂ to be processed gas containing a so ₂ is 1 0~ 5 0 0 0 ppm coexist, the wire carrier rear particle surface of large diameter C a (OH) ₂ fine particles coated the S o ₂ desulfurizing agent are contacted in a reaction column at a state of forming a fluidized bed and treated gas containing the so _2, wherein the reaction column together with the pre-Symbol subject gas while reacting the desulfurizing agent and SO ₂ medium was elevated to said C a SO ₄ that I Ri formed in the reaction with the C a (OH) ₂ fine particles from the upper portion of the reactor the S◦ ₂ and Canon rear surface of the particles Canon Li Ya particles Contact Yo Pi to flow to the first gas primary solids separator together with the process gas, the reaction with the C a (OH) ₂ and S 0 ₂ of the Kiyariya particle surface in the first gas one solid body separator in Ri precipitated the wire carrier Li Ya particles from a gas containing C a S 0 ₄ which are formed, detached and separated, the C a S 0 ₄ wherein the gas containing a first gas one From the body separator top to flow into the second gas primary solids separator, the gas to be treated and separating. Recovering said C a 3 0 ₄ from the processing gas in the second gas primary solids separator So ₂ inside C a S 0 ₄ and to desulfurization process of separating and recovering, yo Ri preferably, be treated NO and / or N 0 ₂ 1 0-5 0 0 0 to ppm co exist in the treated gas in the gas of S 0 ₂ to C a S 0 ₄ and desulfurized method for separating recovered does not include nO and / or nO ₂ in the exhaust gas forces, included nO external case insufficient though and Z or N 0 is ₂ the features and this supplying S 0 ₂ of each of the treated gas at C a S_〇 ₄ and to desulfurization process of separating and recovering, more preferably, N in the gas to be treated 0 ₂ not included, both N 0 ₂ coexist with ≤ of the treated gas 0 ₂ 〇 a S 0 ₄ and desulfurized method for separating recovered less, NO is present in the gas to be treated in this case, by way of the processing means for converting a portion also less of nO to be treated in the gas to nO _2, also in the case where nO and N 0 ₂ does not exist less of nO Fine rather the even part power supplying NO before processing means for converting the N 0 _2, after supplying N 0 ₂ in the treated gas from the outside, the treated gas to the carrier particle surfaces of the large particle size the S_〇 ₂ of each of the treated gas is to separate and recover the C a S_〇 _4, characterized in that the feed to the reactor to SO ₂ desulfurizing agent coated with C a (OH) ₂ of the child is present a desulfurization process, more preferably Ri yo, methanol have your least for the even part of NO N 0 ₂ processing means for converting within 3 0 0 ° C~ 4 0 0 ° C, t one Petit helper O wherein the features and this de a is for oxidizing Ri by that atomized press-fitted least a part of NO in the gas to be treated was via the processing means for converting the N 0 ₂ to be processed gas the 3_Rei ₂ is a 〇 a 3 0 ₄ and to desulfurization process for separating and recovering.

A second aspect of the present invention is a reaction tower 1 in which a SO ₂ desulfurizing agent having large-sized carrier particles coated with fine particles of Ca (OH) ₂ forms a fluidized bed by supplying a gas to be treated, In the reaction tower, the surface of large carrier particles C a (OH) ₂ is desulfurizing agent supply device for supplying the SO ₂ desulfurizing agent coated particulate, device coexist NO Oyopi or N 0 ₂ to be treated in a gas containing S 0 _2, NO and _ or N 0 ₂ to S 0 ₂ coexisted the blowing including treated gas to be treated gas blowing device, the contact in a reaction column with the desulfurizing agent in a state of forming a fluidized bed and treated gas containing S o ₂ Then, the desulfurizing agent and so ₂ are allowed to react with each other and rise in the reaction tower together with the gas to be treated, and from the upper part of the reaction tower, the so ₂ and C a (OH) ₂ of the fine particles on the surface of the carrier particles are raised. treated containing C a S 0 ₄ of the C a S 0 ₄ where Ri formed by the reaction the Kiyariya blown with particles and the gas to be treated was the wire carrier rear particles the Kiyariya formed by the surface-desorbed with A first gas-solid separator for sedimenting and separating the carrier particles from the gas; Preliminary the first gas - the gas to be treated from the solid separator containing the C a S 0 ₄ is blown, the from the process gas blown C a S 0 ₄ second gas primary solids separator for separating it is S 0 ₂ to C a S 0 ₄ and to separation recovery for desulfurization of the treated gas, characterized in that with. Preferably, the apparatus coexist NO and / or N 0 ₂ to be treated in a gas containing so _2, to form a fluidized bed gas to be treated to separate and recover in the S 0 ₂ and C a S o ₄ reaction is arranged before the test sheet to the tower, the NO and / or N 0 ₂ to 1 0 to 50 0 NO and externally to ppm Z or N 0 ₂ supplies device and / or NO in the gas to be treated NO wherein characterized in that it is intended to include co Nbata be converted to ₂ so ₂ of the treated gas is desulfurizer of separating and recovering as a C a 30 _4, yo Ri preferably, the reaction tower to form a fluidized bed in a 1 and a S 0 ₄ first gas primary solids separator for separating precipitated the wire carrier rear particles from a gas to be treated containing The S_〇 ₂ of the each of the treated gas, characterized in that you are forming a circulating fluidized bed is a C a S 0 ₄ and to desulfurization apparatus for separating and recovering. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a conceptual diagram of the desulfurization device of the present invention. The apparatus includes: 1 a fluidized bed forming reaction tower 1, a first gas-solid separator 2, a second gas-solid separator 3, a gas injection section 4, a reflux line 5 for separation carrier particles, a S 0 ₄ transfer pipe 6 of a gas containing the treated gas to be treated 7, recovered C a S 0 ₄ solid reaction Monotori out pipe 8 including, SO ₂ desulfurizing agent supplying section (SO ₂ desulfurizing agent manufacturing. supply device) 9, N 0 ₂ co Nbata CV, acid agent supplying means OD, the boiler (treated gas generating source) B main constituent.

Figure 2 is a 3 0 ₂ when allowed to coexist NO and N 0 ₂ to S 0 ₂ containing treated gas. showing a correlation time course of a S 0 ₄ the characteristic of separating and recovering by the quantity of particles splash. BEST MODE FOR CARRYING OUT THE INVENTION

 The present invention will be described in more detail.

A. The first figure was NO and / or the treated gas containing SO ₂ in the present invention is N 0 ₂ was 1 0 to 5 0 0 ppm coexist, the wire carrier re catcher grain terminal surface of the large particle size A SO ₂ desulfurizing agent coated with fine particles of C a (OH) ₂ is brought into contact with the gas to be treated containing SO ₂ in a reaction tower in a state of forming a fluidized bed, and 30 ₂ in the gas to be treated is converted to a 30 ₄ FIG. 1 is a conceptual diagram of a desulfurization apparatus for separating and recovering as follows. 1 is a fluidized bed formation reactor equipped with a perforated plate (PP). Below the perforated plate PP of the reaction tower 1, for example, a boiler Apparatus for supplying a gas to be treated (the gas to be treated) in 1 0~ 5 0 0 ppm of NO contact and / or N 0 gas to be treated was ₂ coexist from B, blower pump is connected, for example. In order to make NO and / or NO ₂ coexist in the gas to be treated, a device for supplying NO and Z or NO ₂ before the device for supplying the gas to be treated, and NO that coexists in the gas to be treated or the least even that have ◦ D is provided to blow the oxidizing agent that promotes the N 0 ₂ converts the device CV and the conversion part.

Above the perforated plate PP, a SO ₂ desulfurizing agent supply device 9, in this case, a desulfurizing agent production device is directly connected to the reaction tower 1. The desulfurizing agent and the equipment after the reaction tower are described in detail in the above-mentioned Japanese Patent Application Laid-Open No. 2002-113336, which has already been proposed by the present inventors. State technical description according to the publication, in which the so ₂ desulfurizing agent in wire carrier re yer particle surface of the large particle size coated with C a (OH) ₂ fine particles to form a fluidized bed and treated gas containing so ₂ 3 0 ₂ in the treated gas is contacted in a reaction column. Except for the technical features of the present invention referred to as "the treated gas NO and / or N 0 ₂ coexist" in the desulfurizing method and desulfurizing apparatus to separate and recover as a a S 0 ₄ is closely related to the present invention Therefore, they should be understood as forming part of the technical description of the present invention. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

 Example 1

As the gas to be treated, S 0 ₂ content of 1 5 0 0 ppm, the C 0 ₂ content 1 _2%, O 2 content was what 8% with the sample. As the desulfurizing agent, fly ash having the chemical composition shown in Table 1 below and having an average particle diameter of 13 μm and a surface area of 126 m ² / g was used as the carrier particles. a, was used as the weight ratio of the C a (OH) ₂ and (Kiyariya particles + C a (OH) ₂₎ is 1. 5 and made by Uni coating. This was supplied so that the Ca 3 ratio became 1.7, the gas superficial velocity was 0.75 m / s, the reactor (circulating fluidized bed formation reactor) temperature was 350 ° C, and the gas phase was The residence time was 1.5 seconds (s) and the pressure loss was 1 kPa (corresponding to the desulfurizing agent particle filling rate).

表 2に記載の N Oまたは N 0₂を共存 （ p p m) させて脱硫した 時と、 これら N O _xが共存しなかった時の脱硫特性 （％ ) を表 2に 示す。 NOまたは N 0₂の共存効果を比較する と、 同じ共存量にお いて、 N 0₂の共存効果の方が大きいことが表 2から理解される。 このことから、 N Oを N 0₂に変換するコンバーター C Vを設ける ことが、 30₂を。 a S 0₄と して分離回収する脱硫法において顕著 な改善をもたらすことは明らかである。 また N Oおよび Zまたは N 〇 ₂の共存量が 5 0 p p m〜 3 0 0 p p m以上ではこれらの共存効 果はほぼ飽和しており、 被処理ガス中に共存すべき最低濃度は 1 0 p m mであるが上限はない。 表 2

And when desulfurization of NO or N 0 ₂ coexist (ppm) shown in Table 2, the desulfurization characteristics when these NO _x does not coexist (%) shown in Table 2. Comparing the coexistence effect of NO or N 0 _2, and have contact to the same coexistence amount, it is understood from Table 2 towards the coexistence effect of N 0 ₂ is large. Therefore, it is provided with a converter CV for converting NO to N 0 _2, 30 _2. It is clear that results in a significant improvement in a S 0 ₄ and by desulfurization of separating and recovering it. Also these coexistence effect in coexistence of NO and Z or N 〇 ₂ 5 0 ppm~ 3 0 0 ppm or more is nearly saturated, the lowest concentration should coexist in the gas to be treated is 1 0 PMM Has no upper limit. Table 2

実施例 2

Example 2

NO, the result of coexistence of N 0 ₂ were experiments the effect of desulfurization rate at 4 8 0 ppm respectively (C a / S) shown in Table 3.

The experiments, as the gas to be treated, S 0 ₂ content of 1 5 0 0 ppm, CO ₂ content of 1 2% O ₂ content of the sample from 8% as a desulfurizing agent, Fly ash having the same chemical composition, average particle size and surface area as those used in Example 1 was used, and the weight of Ca (OH) ₂ was compared with (Carrying particles + Ca (OH) ₂ ). The test was carried out using a material coated so that the ratio became 1.5. The results in Table 3, a clear effect of the coexistence of NO and N 0 ₂ with respect to the desulfurization rate, the effect of the upward direction of the desulfurization rate of coexisting N 0 _2, the effect of the improvement of the desulfurization rate of coexisting NO It was also found to be more stable than. This coexistence of N 0 ₂ It is understood that the effect on the stable reaction of desulfurization. Table 3

実施例 3

Example 3

Here, in the case of using the SO ₂ desulfurizing agent coated with C a (OH) ₂ fine particles to the wire carrier rear particle surface of large diameter, wire carrier rear and C a (OH) ₂ fine particles of particle Table surfaces 30 ₂ coexistence effect of NO (4 8 0 ppm) and _{N 0 2 (4 8 O ppm} ) for desorption characteristics of the C a S 0 ₄ where Ri formed by the reaction from the wire carrier rear particle surface and the amount of particles splash Table 4 and Fig. 2 show the change with time in the test.

Table 4

粒子飛沫量 = (飛沫した粒子の う ちの C a の量 g /分） ÷ (供給 した脱硫剤の C a量 g Z分） である。 N O (□ ) および N 0₂ (▲) の添加によ り 、 飛沫粒子が増えている 〔N O も N 0₂も共存しな い場合は （♦) で示した。〕。 このこ とは N Oも N 0₂の共存によ り脱硫剤が有効にはたらき、 効率よ く石膏が得られているこ とを 意味する。 N Oの場合は、 経時と飛沫量の関係を示す上記結果を 見る と、 変動が大き く 、 飛沫量が安定していない、 換言すれば安 定な反応が進行していなく 、 制御性あま り 良く ない。 これに対し て、 N 0₂の共存の場合には飛沫量が非常に安定している。 この こ とから、 N 0₂の共存下で S 0₂含有被処理ガス中の S 0₂を C a S 0₄と して分離回収する脱硫法がよ り効果的であるこ とが理 解される。 産業上の利用可能性

Particle droplet amount = (Ca amount of droplets g / min) ÷ (Ca amount of supplied desulfurizing agent g Z minutes). NO (□) and N 0 ₂ (▲) Added by the of Ri, the case [NO which has increased splash particles N 0 ₂ yet such coexist indicated by (♦). ]. NO also N 0 by the _second coexisting Ri desulfurizing agent effectively works and Conoco, which means that the O efficiency rather gypsum is obtained. In the case of NO, the above results showing the relationship between aging and the amount of droplets show that the fluctuation is large and the amount of droplets is not stable, in other words, a stable reaction has not progressed, and the controllability is better. Absent. And the other hand, in the case of coexistence of N 0 ₂ is the amount of splash is very stable. From this this is this TogaMakoto solution of S 0 ₂ of the S 0 ₂ containing treated gas is C a S 0 ₄ and then desulfurization is good Ri effectively be separated and recovered by in the presence of N 0 ₂ You. Industrial applicability

The present invention relates to SO in which NO and / or NO ₂ is present in the gas to be treated containing SO ₂ in an amount of 10 to 500 ppm, and the surface of large-size carrier particles is coated with fine particles of Ca (OH) _{2. 2} Establish a desulfurization method to separate and recover SO ₂ as Ca ₄ by contacting with a desulfurizing agent, and make it possible to recover so ₂ as Ca SO ₄ , a highly efficient and useful by-product. It provides the above-mentioned highly available environmental improvement technology, which greatly contributes to society.

Claims

1. NO and / or N 0 ₂ to coexist 1 0 ~ 5 0 0 ppm to the 3 0 ₂ of the treated gas to be treated in the gas. a S 0 ₄ and to desulfurization process to yield separate times. 2. 10 to 500 ppm of NO and / or N 0 ₂ coexist in the gas to be treated including S 0 ₂ , and 4 C a (OH) contacting the S 0 ₂ desulfurizing agent coated with ₂ in a reaction column at a state of forming a fluidized bed and treated gas containing the S 0 _2, wherein the desulfurizing agent circumference And the so ₂ are reacted with each other to rise in the reaction tower together with the gas to be treated. From the upper part of the reaction tower, the reaction between the so ₂ and the fine particles C a (OH) ₂ on the surface of the carrier particles. the C a S 0 ₄ formed Ri good to flow to the first gas primary solids separator together with the wire carrier Li Ya particles Contact Yopi treated gas, the wire carrier Li Ya in the first gas primary solids separator in formed Ri by the reaction of the C a (OH) ₂ and S 〇 ₂ of particle surface - separated by settling the wire carrier Li Ya particles from exfoliated C a S 〇 ₄ gas containing, the C a S 0 ₄ is flowed from the upper part of the first gas-solid separator to the second gas-solid separator, and the CaSO ₄ is separated from the gas to be treated in the second gas-solid separator. desulfurization process for separating and recovering by the so ₂ of the treated gas according the C a S 0 ₄ to claim 1, wherein, wherein the recovery to Turkey. 3. NO and / or N 0 ₂ 1 0 ~ 5 0 0 ppm coexisted allowed by 3 0 ₂ 〇 a S 0 ₄ and to desulfurization process to yield separate times of the treated gas to be treated in the gas, If NO and / or NO ₂ is not contained in the exhaust gas, or if it is insufficient, NO and / or NO / Or N 0 ₂ S 0 ₂ The C a S 0 ₄ and to desulfurization how to separate and recover the treated gas to in 1 or 2 claims wherein the this supplies. 4. NO Oyopi or N 0 ₂ to 1 0 ~ 5 0 0 ppm coexisted allowed to S 0 ₂ to C a S 0 ₄ and to desulfurization process to yield separate times of the treated gas in the gas to be treated is , and this is supplied either nO and drink other to be treated in the gas does not contain N 0 _2, nO and / or nO ₂ from insufficient when external be included containing the S 0 ₂ Ri by the, C a of fine particles in the NO and Z or N 0 ₂ 1 0 after pretreatment ~ 5 0 0 ppm treated gas coexist, a large particle size Canon Li yer particle surface during the gas to be treated (OH) ₂ and S 0 ₂ desulfurizing agent coated is contacted in a reaction column at a state of forming a fluidized bed and treated gas containing the S 0 _2, said while reacting the de agent and SO ₂ The reaction together with the gas to be treated. The reaction gas is raised in the column, and C a S formed from the reaction of the so ₂ with the fine particles C a (OH) ₂ on the surface of the carrier particles from the top of the reaction column. 0 ₄ the Canon With yer particles and the treated gas to flow to the first gas primary solids separator, said first gas - in the solid separator in the key catcher Li Ya particle surfaces C a (OH) ₂ and the S 0 ₂ from a gas containing C a S 0 ₄ formed Ri by the reaction and stripping was allowed to settle and the wire carrier Li Ja particles were separated, the C a S 0 ₄ the first gas primary solids separator gas containing to flow from the upper to the second gas primary solids separator, the gas to be treated according to the range section 1 according to yield separated. times the C a S 0 ₄ from the processing gas in the second gas primary solids separator desulfurization process for separating and recovering the S 0 ₂ in as a C a SO _4. 5. At least no NO ₂ is contained in the gas to be treated N 0 ₂ coexist with S 0 ₂ to C a S 0 ₄ and then desulfurization process for separating and recovering it to be treated in the gas, if the NO is present in the gas to be treated, NO of the treated gas least a part of the by way of the processing means to convert the N 0 _2, also in the case where nO and N 0 ₂ is not present in the processing means for converting the least a part of nO to N 0 ₂ of is being supplied or the NO before, after supplying NO ₂ in the treated gas from the outside, S 0 coated with C a (OH) ₂ fine particles to the wire carrier re yer particle surfaces of large particle size to be processed gas the placing serial to claim 1, wherein supplying the reaction _{column 2} desulfurizing agent is present the S 0 ₂ of the treated gas. desulfurization process for separating and recovering as a a S 0 _4. 6. not include a NO ₂ in the gas to be treated, less the desulfurization process for separating and recovering the S 〇 _second treated gas as a C a S 0 ₄ also coexist NO ₂ is to be processed when the nO is present in the gas, if by way of the processing means for converting a portion also less of nO in the processing gas to N 0 _2, also there is no nO and N 0 ₂ is either by supplying NO before the processing means for converting NO in the least also partially N 0 _2, after supplying NO ₂ in the treated gas from the outside, the large particle size of the treated gas wire carrier Lyer particles the S 〇 ₂ C a S to be processed in the gas according to claim 4, wherein the so ₂ desulfurizing agent coated with C a (OH) ₂ fine particles on the surface is characterized the this supplied to the reaction column that exists 0 ₄ and to desulfurization process for separating and recovering. . 7 processing means for converting NO in the least also partially N 0 ₂ is 3 0 0 ° C~ 4 0 0 ° methanol in C, t - petit helper O wherein de in the child atomization pressed the S 0 ₂ of the treated gas of the mounting serial in a range 5 claims is intended to oxidize to separate and recover as a C a S 0 ₄ Ri Desulfurization method. 8. NO of least be partially N 0 ₂ processing means for converting the 3 0 0 ° C~ 4 0 0 ° methanol in C, and t one-butylperoxy O wherein de in the child atomization pressed Ri mounting serial ranges 6 claims is intended to oxidize 3 0 ₂ of the treated gas. desulfurization process for separating and recovering as a a S 0 _4. 9. Anti応塔1 S 0 ₂ desulfurizing agent coated with C a (OH) ₂ fine particles to the wire carrier re yer particle surface with a large particle size to form a fluidized bed Ri by the supply of the gas to be treated, said reactor desulfurizing agent supply device for supplying the SO ₂ desulfurizing agent C a (OH) ₂ fine particles to the wire carrier re yer particle surface with a large particle size is coated, NO in the treated gas containing S 0 ₂ and / or N 0 ₂ device coexist, NO and / or N 0 treated gas blowing device for blowing a gas to be treated containing ₂ S 0 ₂ which are allowed to coexist, the desulfurizing agent and gas to be treated containing SO ₂ in a fluidized bed in formation states are contacted in a reaction column, wherein while reacting the desulfurizing agent and so ₂ raises the reaction tower to the gas to be treated and co, and from said upper 3 0 ₂ of the reaction tower key C a (OH) ₂ to C a S 0 ₄ where I Ri formed in the reaction with the Canon Li Ya particles Contact Yopi gas to be treated of the fine particles of the catcher Li yer particle surface Is incorporated can blow with, separating the key Ya Li Ya particles precipitated the wire carrier Li Ya particle child from a gas to be treated containing the key Ya C a S 0 ₄ formed-desorbed by Li yer surface wherein the first gas primary solids separator and the first gas primary solids separator C a S 0 ₄ is incorporated blows a gas to be treated containing, said from the processing gas blown C a S 0 ₄ separation second gas primary solids separator SO ₂ in the treated gas, wherein the child with C a S 0 ₄ and to desulfurization apparatus for separating and recovering the. 1 0. S 0 ₂ device to coexist NO and / or N 0 ₂ to be treated gas containing is treated gas be separated and recovered by the S_〇 ₂ and C a S 0 ₄ is a fluidized bed It disposed before being fed to the reactor to form the external from the device for supplying NO and / or N 0 ₂ to NO and / or N 0 ₂ in the processing gas to 1 0~ 5 0 0 O ppm the S 0 ₂ to to separate and recover the C a S 〇 ₄ of the treated gas description and / or the NO in the range 9 claims, characterized in it to contain compounding Isseki one to convert into N 0 ₂ Desulfurization equipment. Forming a circulating fluidized bed with solid separator - 1 1 • first gas to separate the serial calibration Rya one grain from the process gas containing the reaction column 1 and C a S 0 ₄ to form a fluidized bed allowed to settle to have claimed S 0 ₂ a 〇 a S 0 ₄ and to desulfurization apparatus for separating and recovering the treated gas in the aspect of the ninth. . 1 2 • first gas to separate the刖記calibration rear particles from the process gas containing a reaction column 1 and C a S 0 ₄ to form a fluidized bed allowed to settle - to form a circulating fluidized bed in the solids separation and it is S 0 ₂ to C a S 0 ₄ and to desulfurization apparatus for separating and recovering of the processing gas according to the range 1 0 claims.