JPH0230739B2 - DATSURYUZAINOSEIZOHOHO - Google Patents
DATSURYUZAINOSEIZOHOHOInfo
- Publication number
- JPH0230739B2 JPH0230739B2 JP57073377A JP7337782A JPH0230739B2 JP H0230739 B2 JPH0230739 B2 JP H0230739B2 JP 57073377 A JP57073377 A JP 57073377A JP 7337782 A JP7337782 A JP 7337782A JP H0230739 B2 JPH0230739 B2 JP H0230739B2
- Authority
- JP
- Japan
- Prior art keywords
- desulfurization
- agent
- present
- alumina cement
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003795 chemical substances by application Substances 0.000 claims description 55
- 239000002245 particle Substances 0.000 claims description 34
- 230000003009 desulfurizing effect Effects 0.000 claims description 30
- 239000004568 cement Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 description 56
- 230000023556 desulfurization Effects 0.000 description 56
- 230000008929 regeneration Effects 0.000 description 15
- 238000011069 regeneration method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 238000006703 hydration reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000036571 hydration Effects 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 2CaO・Al 2 O 3・8H 2 O Chemical class 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Fluidized-Bed Combustion And Resonant Combustion (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】
本発明は脱硫剤の製造方法に関し、特に流動床
燃焼装置の炉内脱流に好適な脱硫剤の製造方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a desulfurizing agent, and more particularly to a method for producing a desulfurizing agent suitable for deflowing in a furnace of a fluidized bed combustion apparatus.
流動層ボイラ等の流動床燃焼装置は、従来のよ
うに燃焼装置外に排ガス脱硫装置を別置すること
なく、燃焼炉の流動床に脱硫剤を存在させ、炉内
脱硫を行なうことができるという利点がある。 Fluidized bed combustion equipment such as fluidized bed boilers can perform in-furnace desulfurization by having a desulfurizing agent present in the fluidized bed of the combustion furnace, without having to separately install an exhaust gas desulfurization device outside the combustion equipment as in conventional methods. There are advantages.
一般に、流動床ボイラにおける脱硫剤は、流動
床温度域（700〜1000℃）で、石炭の燃焼に伴つ
て生成する亜硫酸ガス（SO2）と反応する、流動
媒体を兼ねた固体粒子である。しかし、一般に高
温における固体粒子とSO2との反応性は高くない
ので、脱硫剤は過剰に添加する必要がある。添加
脱硫剤の過剰率は、脱硫レベルによつて決められ
るが、高い脱硫率を達成しようとするほど多くな
り、このような場合、使用済脱硫剤を廃棄するこ
とは、廃棄物量が多くなり、その処理が問題とな
ることから、これを再成し循環使用することが望
まれる。 Generally, the desulfurization agent in a fluidized bed boiler is a solid particle that also serves as a fluidizing medium and reacts with sulfur dioxide gas (SO 2 ) generated as coal is burned in the fluidized bed temperature range (700 to 1000° C.). However, since the reactivity between solid particles and SO 2 is generally not high at high temperatures, it is necessary to add an excess of the desulfurization agent. The excess rate of added desulfurization agent is determined by the desulfurization level, but the higher the desulfurization rate is achieved, the higher the excess rate. Since its treatment poses a problem, it is desirable to regenerate and recycle it.
従来、脱硫剤としては主に、石灰石、ドロマイ
ト等の安価な天然の含カルシウム鉱物が使用され
ているがSO2との反応性（脱硫性）が充分高くな
いため、過剰に添加しなければならず、さらに流
動床内での摩耗強度が高くないために粉化飛散に
よる損失が多く、脱硫・再成を繰り返し使用する
には問題がある。このため、一方では、繰返し使
用できる人工の合成脱硫剤の研究も進められ、こ
れまでにチタン酸バリウム、酸化カルシウムをア
ルミナに担持したもの、アルミナセメント等が提
案されている。これらのうち、アルミナセメント
は工業的に大量に生産され、他の合成脱硫剤より
安価で入手しやすく、有望なものと考えられる。
しかし、アルミナセメントそのものは、溶融状の
ものを冷却固化したものであり、強度的には優れ
ているが、内部細孔がほとんどないため、被脱硫
ガスとの反応では粒子表面しか利用されないこと
になり、数百μｍ〜数mmの数径でアルミナセメン
トをそのまま脱硫剤として用いることには無理が
ある。そこでアルミナセメントを流動床ボイラの
脱硫剤として用いるには、通常、市販の数＋μｍ
以下の微粉末を水と混練して水和硬化させ、流動
床ボイラに適した粒径にペレツト化する方法がと
られている。しかし、この方法においては造粒工
程が必要であり、さらに造粒の際に均一に水和固
化するには理論水和量以上の水分添加が必要で、
このことは一般に脱硫剤の強度を低下させること
になり、繰返し使用する脱硫剤にとつては好まし
いことではない。 Conventionally, inexpensive natural calcium-containing minerals such as limestone and dolomite have been mainly used as desulfurizing agents, but their reactivity with SO 2 (desulfurizing properties) is not high enough, so they must be added in excess. Furthermore, since the abrasion strength in the fluidized bed is not high, there is a lot of loss due to powdering and scattering, and there is a problem in repeatedly using desulfurization and regeneration. For this reason, on the other hand, research into artificial synthetic desulfurization agents that can be used repeatedly is progressing, and so far barium titanate, calcium oxide supported on alumina, alumina cement, etc. have been proposed. Among these, alumina cement is industrially produced in large quantities, is cheaper and easier to obtain than other synthetic desulfurization agents, and is considered to be promising.
However, alumina cement itself is made by cooling and solidifying a molten substance, and although it has excellent strength, it has almost no internal pores, so only the particle surface is used in the reaction with the desulfurized gas. Therefore, it is impossible to use alumina cement as it is as a desulfurization agent with a diameter of several hundred μm to several mm. Therefore, in order to use alumina cement as a desulfurization agent in a fluidized bed boiler, it is usually necessary to
A method is used in which the following fine powders are kneaded with water, hydrated and hardened, and pelletized to a particle size suitable for a fluidized bed boiler. However, this method requires a granulation step, and in order to achieve uniform hydration and solidification during granulation, it is necessary to add water in excess of the theoretical hydration amount.
This generally reduces the strength of the desulfurizing agent, which is not desirable for desulfurizing agents that are used repeatedly.
本発明の目的は、上記従来の脱硫剤の有する欠
点を除き、脱硫性能が良好で、しかも再成繰返し
使用可能で損耗の少ない脱硫剤の製造方法を提供
することにある。 An object of the present invention is to provide a method for producing a desulfurizing agent that eliminates the drawbacks of the conventional desulfurizing agents, has good desulfurizing performance, can be repeatedly reused, and has little wear and tear.
本発明者は、流動床ボイラ等の脱硫において、
再生可能で、しかも耐久性が良好な脱硫剤を種々
追求し、アルミナセメントクリンカーを原料する
本発明の脱硫剤の製造方法に到達したものであ
る。 The present inventor has discovered that in desulfurization of fluidized bed boilers, etc.
We have searched for various desulfurizing agents that are recyclable and have good durability, and have finally arrived at the method for producing a desulfurizing agent of the present invention using alumina cement clinker as a raw material.
本発明の脱硫剤の製造方法は、通常市販されて
いる微粉末アルミナセメントの前工程で製造され
る塊状のアルミナセメントクリンカーを流動床ボ
イラの流動媒体に適するように破枠して粒径調整
を行つた後、水に浸潰して粒子内部にまで水和さ
せ、その後加熱脱水することを特徴とする。 The method for producing the desulfurization agent of the present invention involves breaking the bulk alumina cement clinker, which is usually produced in the pre-process of commercially available fine powder alumina cement, into a frame to make it suitable for the fluid medium of a fluidized bed boiler, and adjusting the particle size. After this, the particles are soaked in water to hydrate the inside of the particles, and then heated and dehydrated.
本発明に用いるアルミナセメントクリンカー
は、よく知られているように、その化学成分とし
てCaO35〜44％、Al2O335〜45％、Fe2O34〜20
％、SiO23〜11％を含み、水と速やかに結合し
て、2CaO・Al2O3・8H2O、Al2O3・3H2Oなど水
和化合物を生成する。 As is well known, the alumina cement clinker used in the present invention has chemical components of CaO 35-44%, Al 2 O 3 35-45%, Fe 2 O 3 4-20
%, SiO 2 3-11%, and quickly combines with water to form hydrated compounds such as 2CaO・Al 2 O 3・8H 2 O, Al 2 O 3・3H 2 O, etc.
本発明においては、予めセメントクリンカー粒
子を破砕し、流動床ボイラ内の流動条件に適する
ような粒径、一般には0.5〜３mmの範囲になるよ
うに粒径が調整される。しかる後、水を加え、粒
子内部まで水和反応せしめる。アルミナセメント
クリンカーは元来、半溶融状態から冷却固化させ
たものであるから、半ガラス状で気孔性に乏しい
ので、本発明の如く比較的粗大なクリンカー粒子
では、粒子表面から徐々にしか水和反応は進行せ
ず、内部まで水和反応を進行させるのに長時間を
要する。しかしながら、このようにして得られた
水和物は、後述の実施例で具体的に示すように、
通常のアルミナセメント微粉末を水と混練して水
和硬化させたものより強度的には一段と優れたも
のが得られ、しかも製造法も簡単である。 In the present invention, cement clinker particles are crushed in advance and the particle size is adjusted to a particle size suitable for the fluidization conditions in a fluidized bed boiler, generally in the range of 0.5 to 3 mm. After that, water is added to cause a hydration reaction to occur inside the particles. Since alumina cement clinker is originally cooled and solidified from a semi-molten state, it is semi-vitreous and has poor porosity. Therefore, with relatively coarse clinker particles as in the present invention, hydration occurs only gradually from the particle surface. The reaction does not proceed, and it takes a long time for the hydration reaction to proceed to the inside. However, the hydrate obtained in this way, as specifically shown in the examples below,
The strength is much superior to that obtained by kneading ordinary fine alumina cement powder with water and hydration-hardening it, and the manufacturing method is also simple.
本発明において、アルミナセメントクリンカー
破砕粒子の水浸時間は、脱硫性能に大きく影響
し、長時間ほど好ましい。粒径が小さいほど短時
間でよいが、0.5mm以上の粒径では少なくとも100
時間以上、好ましくは300時間以上で工程の許す
限り長時間の方がよい。また、水和の際、粒子同
志の接着は水和後、改めて粒度調整を行う必要が
あるので好ましくない。その防止策としては、水
への浸潰の初期において撹拌すればよい。粒子の
表面の水和が完了すれば、粒子同志が固着するこ
とはなく、初期の30〜50時間の撹拌で十分であ
る。上記のように水和した粒子は、加熱により水
を放出し、僅かの収縮を伴うが、水を放出したあ
との細孔が形成され多孔体となるので、脱硫性能
を有するに到る。 In the present invention, the water immersion time of the crushed alumina cement clinker particles greatly affects the desulfurization performance, and a longer time is preferable. The smaller the particle size, the shorter the time, but if the particle size is 0.5 mm or more,
It is better to carry out the treatment for as long as the process allows, preferably for at least 300 hours. Further, adhesion of particles to each other during hydration is not preferable since it is necessary to adjust the particle size again after hydration. To prevent this, stirring may be performed at the initial stage of immersion in water. Once the hydration of the surface of the particles is completed, the particles will not stick together, and stirring for an initial period of 30 to 50 hours is sufficient. The hydrated particles as described above release water when heated and undergo slight shrinkage, but after water is released, pores are formed and the particles become porous, so they have desulfurization performance.
以上のようにして得られた脱硫剤は700〜1000
℃の温度域で、酸素存在下で亜硫酸ガス（SO2）
と容易に反応するが、この反応温度領域は、通常
の流動床ボイラの層温度が約700〜1000℃程度で
あることから、実用に適したものである。 The desulfurization agent obtained in the above manner has a concentration of 700 to 1000
Sulfur dioxide gas (SO 2 ) in the presence of oxygen at a temperature range of ℃
However, this reaction temperature range is suitable for practical use since the bed temperature of a normal fluidized bed boiler is about 700 to 1000°C.
SO2と反応した後の上記脱硫剤は、一酸化炭素
（CO）、水素（H2）、メタン（CH4）等の炭化水
素などの環元性ガスにより850℃〜1100℃好まし
くは950℃〜1100℃において、SO2を放出して再
成される。この場合、還元ガスの種類による影響
は、CO、H2、CH4のいずれかを使用してもほと
んど差はなかつた。したがつて、実際には流動床
ボイラで使用する石炭を不完全燃焼させて発生す
るガス（CO、H2を含む）などを用いた方が好適
である。 After reacting with SO 2 , the desulfurization agent is heated to 850°C to 1100°C, preferably 950°C, by a cyclic gas such as carbon monoxide (CO), hydrogen ( H2 ), and hydrocarbons such as methane ( CH4 ). At ~1100°C, it is regenerated with the release of SO2 . In this case, there was almost no difference in the effect of the type of reducing gas, whether CO, H 2 or CH 4 was used. Therefore, it is actually more suitable to use gas (including CO and H 2 ) generated by incomplete combustion of coal used in a fluidized bed boiler.
本発明によつて製造した脱硫剤は、流動床ボイ
ラの温度領域で脱硫性能を有し、また再生も850
℃以上で可能であり、且つ強度的に優れているこ
とから、脱硫・再生サイクルで問題となる脱硫剤
損耗が少いという効果がある。さらに、本発明の
脱硫剤は、前述のようにアルミナセメントクリン
カーを粗砕したものを用いるが、これは現在アル
ミナセメントの製造工程における微粉砕される前
のクリンカーを抜き出して粗砕し、適当な粒径の
ものを取り出して脱硫剤原料とすればよく、ここ
で生じた微細粒子は一般のアルミナセメント製造
の微粉砕工程に回せばよいので、脱硫剤の粒径調
整における損失は全くなく、また、セメントをさ
らにペレツト化する必要がないので製造工程が著
しく簡単であり、コスト面でも非常に有利であ
る。 The desulfurization agent produced according to the present invention has desulfurization performance in the temperature range of a fluidized bed boiler, and can be regenerated at 850 °C.
℃ or higher and has excellent strength, it has the effect of reducing desulfurization agent loss, which is a problem in the desulfurization/regeneration cycle. Furthermore, the desulfurization agent of the present invention uses coarsely crushed alumina cement clinker as described above, but this is done by extracting the clinker that has not been pulverized in the current alumina cement manufacturing process and coarsely crushing it. The particle size can be taken out and used as a desulfurizing agent raw material, and the fine particles generated here can be sent to the pulverization process for general alumina cement production, so there is no loss in adjusting the particle size of the desulfurizing agent. Since there is no need to further pelletize the cement, the manufacturing process is extremely simple, and it is also very advantageous in terms of cost.
以下、本発明を実施例により具体的に説明す
る。 Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例 １
化学成分として、CaO37％、Al2O340％、
Fe2O316％（いずれも重量％）を有する塊状のア
ルミナセメントクリンカーをスクリーンミルで破
砕した後、粒径が0.5〜1.0mmの範囲のものを用
い、これを過剰の水中に投入し、撹拌しながら水
和させ、所定時間毎に取り出し、電気炉中で500
℃で１時間加熱脱水して、本発明の脱硫剤を製造
した。Example 1 Chemical components: CaO 37%, Al 2 O 3 40%,
After crushing alumina cement clinker in the form of a block containing 16% Fe 2 O 3 (both weight %) with a screen mill, using particles with a particle size in the range of 0.5 to 1.0 mm, this was poured into excess water, Hydrate with stirring, take out at predetermined intervals, and heat in an electric furnace for 500 min.
The desulfurization agent of the present invention was produced by heating and dehydrating at ℃ for 1 hour.
また、上記アルミナセメントを200メツシユ
（74μｍ）以下に微粉砕し、この微粉末に対し、
各々46及び65重量％の水を加えて混練し、３日間
放置して水和硬化させた後、スクリーンミルで破
砕し、0.5〜１mmの粒径範囲のものを上記同様熱
処理して、本発明の比較例である他の脱硫剤を製
造した。 In addition, the above alumina cement is finely ground to 200 mesh (74 μm) or less, and to this fine powder,
After adding 46 and 65% by weight of water and kneading them, leaving them to stand for 3 days to cure by hydration, they were crushed with a screen mill, and the particles in the particle size range of 0.5 to 1 mm were heat-treated in the same manner as described above. Another desulfurizing agent was manufactured as a comparative example.
以上のようにして得た脱硫剤を用い、流動床脱
硫模擬試験を行つた。試験は、内径40mmの目皿付
の反応管に静止層高100mmの脱硫剤を充填し、電
気炉で850℃に温度保持しながら、0.3％SO2、３
％O2、10％H2O、残部N2の模擬ガスを管内流速
１ｍ／ｓで流入させ脱硫剤を流動化させて出口
SO2濃度をモニターし、脱硫率の経時変化を追跡
した。 A fluidized bed desulfurization simulation test was conducted using the desulfurization agent obtained as described above. The test was carried out by filling a reaction tube with a perforated plate with an inner diameter of 40 mm with a desulfurizing agent with a static bed height of 100 mm, and heating it with 0.3% SO 2 , 3% while maintaining the temperature at 850°C in an electric furnace.
%O 2 , 10% H 2 O, and the balance N 2 are introduced into the pipe at a flow rate of 1 m/s to fluidize the desulfurization agent and exit the pipe.
The SO 2 concentration was monitored and the desulfurization rate was followed over time.
上記本発明により製造した脱硫剤と、上記水と
混練して水和硬化させて得た比較例の脱硫剤を対
比した測定結果を第１図に示す。図中１は水と全
く接触させないセメントクリンカー粒子である
が、脱硫性能はほとんど示さない。図中２、３、
４は、図中１の粒子を本発明に係る水との浸漬を
100、200300時間行つて得た脱硫剤で、浸漬時間
が長くなるほど脱硫性能は向上することがわか
る。図中点線５、６は微細アルミナセメント粒子
を水和硬化させて得た前記比較例の脱硫剤であ
り、点線５の脱硫剤は混水量46％、点線６のもの
は混水量65％で得たものであるが、混水量が多い
方が脱硫性能に優れていることが分る。 FIG. 1 shows the measurement results comparing the desulfurizing agent produced according to the present invention with the desulfurizing agent of a comparative example obtained by kneading with the water and hydrating and curing the desulfurizing agent. In the figure, 1 is a cement clinker particle that is not brought into contact with water at all, but shows almost no desulfurization performance. 2, 3, in the figure
4 shows the particles of 1 in the figure immersed in water according to the present invention.
It can be seen that the desulfurization performance of the desulfurization agents obtained after 100, 200, and 300 hours of immersion improves as the immersion time increases. In the figure, dotted lines 5 and 6 indicate the desulfurization agent of the comparative example obtained by hydration hardening of fine alumina cement particles. However, it can be seen that the desulfurization performance is better when the amount of mixed water is larger.
第１図の結果から、本発明に係る脱硫剤２，
３，４はアルミナセメント微粉末を水和硬化させ
て得た脱硫剤に近い性能を示すことが分る。 From the results shown in FIG. 1, desulfurization agent 2 according to the present invention,
It can be seen that samples 3 and 4 exhibit performance similar to that of a desulfurizing agent obtained by hydration-hardening of fine alumina cement powder.
再生型脱硫剤で、脱硫再生を繰返し使用される
ため、上記脱硫性能の他に再生性能、さらに耐摩
耗性に優れたものでなければならない。これら脱
硫再生繰返しでの摩耗粉化については、後述の実
施例で具体的に説明するが、摩耗粉化程度の目安
となる脱硫剤強度（耐圧強度）は、粒径によつて
も異なるが、本発明に係る２，３，４は大体５〜
10Kg、比較例の５は２〜４Kg、６は１〜３Kgで本
発明に係るものが強度的に優れていることが分つ
た。以上のように本発明方法により製造した脱硫
剤は、強度的に強く且つ、充分な脱硫性能を示
す。 Since it is a regenerated desulfurization agent and is used repeatedly for desulfurization and regeneration, it must have excellent regeneration performance and wear resistance in addition to the desulfurization performance described above. The abrasion powdering caused by repeated desulfurization regeneration will be specifically explained in the Examples below, but the desulfurizing agent strength (pressure strength), which is a guideline for the degree of abrasion powderization, varies depending on the particle size, but 2, 3, and 4 according to the present invention are approximately 5 to 5
It was found that the strength of Comparative Example 5 was 10 kg, Comparative Example 5 was 2 to 4 kg, and Comparative Example 6 was 1 to 3 kg. As described above, the desulfurization agent produced by the method of the present invention has strong strength and exhibits sufficient desulfurization performance.
実施例 ２
実施例１の第１図中４に示した本発明方法によ
り製造した脱硫剤において、脱硫温度の適用性を
見るため、熱天秤により所定温度でSO2の吸収特
性を調べた。Example 2 In order to examine the applicability of the desulfurization temperature in the desulfurization agent produced by the method of the present invention shown in 4 in FIG .
脱硫剤約２ｇを内径100mmの反応管に吊された
石英バスケツトに入れて所定温度に保ち、これに
SO20.3％、O24％、水分８％、残部N2の模擬ガス
を１／mmの流速で流通させ、脱硫剤のSO2との
反応に伴う重量変化を熱天秤により検出した。 Approximately 2 g of desulfurization agent is placed in a quartz basket suspended in a reaction tube with an inner diameter of 100 mm, maintained at a specified temperature, and then
A simulated gas containing 0.3% SO 2 , 4% O 2 , 8% moisture, and the balance N 2 was passed through at a flow rate of 1/mm, and the weight change due to the reaction of the desulfurizing agent with SO 2 was detected using a thermobalance.
各温度において、100分後のSO2吸収量を測定
した結果を第２図に示す。本発明に係る脱硫剤は
700〜1000℃好ましくは800〜1000℃において脱硫
性能を有することが分る。 Figure 2 shows the results of measuring the amount of SO 2 absorbed after 100 minutes at each temperature. The desulfurizing agent according to the present invention is
It can be seen that it has desulfurization performance at 700 to 1000°C, preferably 800 to 1000°C.
実施例 ３
本発明方法により製造した脱硫の再生性能をみ
るために、実施例１の脱硫後の脱硫剤４を用い、
実施例２と同じ装置で所定温度に保ち、CO3％、
残部N2のガスを１／mmの速度で流通させ、還
元に伴なう重量変化を経時的に測定し、重量減少
が認められなくなつた後、空気を流入させて冷却
後、試料を取出し、脱硫剤中の硫黄分を固体中硫
黄分析計を用いて測定して、還元前の硫黄分に対
する減少率から再生率を求めた。各温度における
再生率を第３図に示す。750℃以上で再生反応が
行なわれ、温度が高いほど反応率が高く、特に
850℃〜1100℃で良好に再生されることが分る。Example 3 In order to examine the regeneration performance of desulfurization produced by the method of the present invention, desulfurization agent 4 after desulfurization of Example 1 was used,
Maintained at a specified temperature using the same equipment as in Example 2, CO3%,
Gas with the remainder N 2 flowing through it at a rate of 1/mm, measuring the weight change over time due to reduction, and after no weight loss is observed, air is introduced to cool it down, and then the sample is taken out. The sulfur content in the desulfurization agent was measured using a solid sulfur analyzer, and the regeneration rate was determined from the reduction rate relative to the sulfur content before reduction. Figure 3 shows the regeneration rate at each temperature. The regeneration reaction takes place above 750℃, and the higher the temperature, the higher the reaction rate, especially
It can be seen that good regeneration is achieved between 850°C and 1100°C.
尚、本実験においては、還元ガスとして、CO
の他にH2、CH3を用いたが、結果は第３図とほ
ぼ同じであり、COの他にこれら環元ガスも用い
られることがわかつた。 In addition, in this experiment, CO was used as the reducing gas.
In addition, H 2 and CH 3 were used, but the results were almost the same as in Figure 3, indicating that these ring gases can also be used in addition to CO.
実施例 ４
実施例１において、850℃で脱硫後、炉内温度
を950℃にしてCO3％、N2残部のガスを管内流速
１ｍ／ｓで流入させて流動化させ、出口ガスを
SO2分析計で監視し、SO2発生が認められなくな
るまで還元再生し、さらに実施例１に従つて脱硫
し、また再生を繰返した。脱硫・再生を１サイク
ルしこれを20回繰返した後、抜き出して脱硫剤の
重量を測定し、もとの脱硫剤の重量との減少量か
ら１サイクル当りの摩耗粉化率を求めた。その結
果、本発明に係る第１図中２および４の脱硫剤で
は0.02％であつたが、比較例の５および６の脱硫
剤ではそれぞれ0.05％および0.08％であり、本発
明方法により製造した脱硫剤は摩耗が少ないこと
が分つた。Example 4 In Example 1, after desulfurization at 850°C, the temperature inside the furnace was raised to 950°C, and gases containing CO3% and the remainder N2 were flowed at a flow rate of 1 m/s into the pipe to fluidize, and the outlet gas was
Monitoring was performed using an SO 2 analyzer, and reductive regeneration was performed until no SO 2 generation was observed, followed by desulfurization and regeneration in accordance with Example 1. After one cycle of desulfurization and regeneration was repeated 20 times, the weight of the desulfurizing agent was measured, and the abrasion powdering rate per cycle was determined from the amount of decrease from the weight of the original desulfurizing agent. As a result, it was 0.02% for the desulfurizing agents 2 and 4 in FIG. It was found that the desulfurization agent caused less wear.
以上の実施例は、本発明方法により製造した脱
硫剤を、流動床ボイラのような流動床燃焼装置に
用いる場合について述べたものであるが、本発明
方法により製造した脱硫剤は、流動床燃焼装置の
みならず、移動床反応装置など、脱硫剤の耐摩耗
性、耐久性が要求される反応装置にも適用するこ
とができる。 The above examples describe the case where the desulfurizing agent produced by the method of the present invention is used in a fluidized bed combustion device such as a fluidized bed boiler. It can be applied not only to apparatuses but also to reaction apparatuses such as moving bed reactors that require wear resistance and durability of the desulfurizing agent.
以上、本発明によれば、良好な脱硫および再生
性能を有する上、従来のアルミナセメントを水と
混和してペレツト化したものより、粉化損失が少
なく、繰返し再生循環可能な脱硫剤を比較的簡単
に、かつ安価に製造することができる。 As described above, according to the present invention, a desulfurizing agent that has good desulfurization and regeneration performance, has less powder loss than conventional alumina cement mixed with water and made into pellets, and can be recycled and recycled repeatedly. It can be manufactured easily and at low cost.
第１図は、本発明の実施例および比較例の脱硫
剤の脱硫性能を比較する図、第２図は、本発明の
実施例における好適脱硫温度を示す図、第３図
は、本発明の実施例における好適還元再生温度を
示す図である。
２，３，４……本発明の場合、１，５，６……
比較例の場合。
FIG. 1 is a diagram comparing the desulfurization performance of the desulfurization agents of Examples and Comparative Examples of the present invention, FIG. 2 is a diagram showing the preferred desulfurization temperature in the Examples of the present invention, and FIG. FIG. 3 is a diagram showing suitable reduction and regeneration temperatures in Examples. 2, 3, 4... In the case of the present invention, 1, 5, 6...
For comparative example.
Claims (1)
と接触させて水和した後、加熱脱水することを特
徴とする脱硫剤の製造方法。 ２ 特許請求の範囲第１項において、前記アルミ
ナセメントクリンカーの破砕粒子径は0.5〜３mm
で、かつその水への接触時間は100時間以上であ
ることを特徴とする脱硫剤の製造方法。[Scope of Claims] 1. A method for producing a desulfurizing agent, which comprises bringing crushed particles of alumina cement clinker into contact with water to hydrate them, and then heating and dehydrating them. 2 In claim 1, the crushed particle diameter of the alumina cement clinker is 0.5 to 3 mm.
and the contact time with water is 100 hours or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57073377A JPH0230739B2 (en) | 1982-05-04 | 1982-05-04 | DATSURYUZAINOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57073377A JPH0230739B2 (en) | 1982-05-04 | 1982-05-04 | DATSURYUZAINOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58193727A JPS58193727A (en) | 1983-11-11 |
| JPH0230739B2 true JPH0230739B2 (en) | 1990-07-09 |
Family
ID=13516427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57073377A Expired - Lifetime JPH0230739B2 (en) | 1982-05-04 | 1982-05-04 | DATSURYUZAINOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0230739B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732482A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(北京) | One kind targeting anchoring agent and its preparation method and application |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100101A (en) * | 1985-04-01 | 1986-08-20 | 清华大学 | Granular desulfuration agent |
| JP5383960B2 (en) * | 2001-03-01 | 2014-01-08 | 荏原環境プラント株式会社 | Desulfurization method and apparatus |
| JP5719658B2 (en) * | 2010-03-31 | 2015-05-20 | 住友大阪セメント株式会社 | Method for producing desulfurizing agent |
| FR3021046B1 (en) * | 2014-05-16 | 2016-06-10 | Kerneos | ULTRA-RAPID CEMENT WITH AMORPHOUS CALCIUM ALUMINATE COMPRISING SURFACE TREATMENT |
| FR3021047B1 (en) * | 2014-05-16 | 2017-11-10 | Kerneos | ULTRA-RAPID CEMENT WITH AMORPHOUS CALCIUM ALUMINATE |
-
1982
- 1982-05-04 JP JP57073377A patent/JPH0230739B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732482A (en) * | 2017-02-23 | 2017-05-31 | 中国石油大学(北京) | One kind targeting anchoring agent and its preparation method and application |
| CN106732482B (en) * | 2017-02-23 | 2019-08-06 | 中国石油大学(北京) | A kind of targeting anchoring agent and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58193727A (en) | 1983-11-11 |
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