JP2000061253A - Dry type exhaust gas treatment and treating device - Google Patents
Dry type exhaust gas treatment and treating deviceInfo
- Publication number
- JP2000061253A JP2000061253A JP10237245A JP23724598A JP2000061253A JP 2000061253 A JP2000061253 A JP 2000061253A JP 10237245 A JP10237245 A JP 10237245A JP 23724598 A JP23724598 A JP 23724598A JP 2000061253 A JP2000061253 A JP 2000061253A
- Authority
- JP
- Japan
- Prior art keywords
- carbonaceous material
- exhaust gas
- gas
- tower
- regeneration
- 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.)
- Granted
Links
- 239000007789 gas Substances 0.000 claims abstract description 119
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 81
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000000694 effects Effects 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 230000008929 regeneration Effects 0.000 claims description 43
- 238000011069 regeneration method Methods 0.000 claims description 43
- 238000001179 sorption measurement Methods 0.000 claims description 24
- 238000003795 desorption Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 64
- 229910021529 ammonia Inorganic materials 0.000 abstract description 32
- 239000000428 dust Substances 0.000 abstract description 8
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 18
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 9
- 229910052815 sulfur oxide Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000009615 deamination Effects 0.000 description 2
- 238000006481 deamination reaction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- 102100033040 Carbonic anhydrase 12 Human genes 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 101150042515 DA26 gene Proteins 0.000 description 1
- 101000867855 Homo sapiens Carbonic anhydrase 12 Proteins 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000607626 Homo sapiens Ubiquilin-1 Proteins 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102100039934 Ubiquilin-1 Human genes 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は乾式排ガス処理方
法及び処理装置に関し、特に、炭素質材を使用して排ガ
ス中の窒素酸化物及びその他の有害物質を除去する乾式
排ガス処理方法及び処理装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry exhaust gas treatment method and treatment apparatus, and more particularly to a dry exhaust gas treatment method and treatment apparatus for removing nitrogen oxides and other harmful substances in exhaust gas by using a carbonaceous material. It is a thing.
【０００２】[0002]
【従来技術およびその問題点】炭素質材を使用する乾式
排ガス処理装置は、比較的低温で排ガスを処理すること
ができるとともに、硫黄酸化物、窒素酸化物、ダスト等
の有害物質を同時に除去することができることから、ボ
イラ排ガス等の処理に多く使用されている。また、最近
では、焼却炉排ガス等に含まれるダイオキシンを除去す
ることもできることから、その利用分野が拡大してい
る。2. Description of the Related Art A dry type exhaust gas treatment apparatus using a carbonaceous material is capable of treating exhaust gas at a relatively low temperature and simultaneously removes harmful substances such as sulfur oxides, nitrogen oxides and dust. Therefore, it is often used for treating boiler exhaust gas. Further, recently, since it is also possible to remove dioxin contained in incinerator exhaust gas and the like, the field of use thereof is expanding.
【０００３】このような乾式排ガス処理装置は、充填し
た炭素質材と排ガスとを固気接触させることにより、排
ガス中に含まれる窒素酸化物及びその他の有害物質を除
去する移動層式吸着塔と、有害物質により活性の低下し
た炭素質材を加熱再生する再生塔とを同一の場所に設置
して使用することが多い。Such a dry type exhaust gas treatment apparatus is a moving bed type adsorption tower for removing nitrogen oxides and other harmful substances contained in the exhaust gas by bringing the filled carbonaceous material into solid gas contact with the exhaust gas. In many cases, a regeneration tower that heats and regenerates a carbonaceous material whose activity has decreased due to harmful substances is installed in the same place and used.
【０００４】粒状の炭素質材を充填した吸着塔に排ガス
を供給すると、炭素質材は次のように作用して有害物質
を除去することができる。When the exhaust gas is supplied to the adsorption tower filled with the granular carbonaceous material, the carbonaceous material acts as follows to remove harmful substances.
【０００５】すなわち、排ガス中のダストは、炭素質材
の表面に付着するので、このろ過作用によって除去する
ことができる。That is, since the dust in the exhaust gas adheres to the surface of the carbonaceous material, it can be removed by this filtering action.
【０００６】排ガス中の硫黄酸化物、塩化水素及びダイ
オキシン等は炭素質材に吸着されるので除去することが
できる。このとき、二酸化硫黄は、排ガス中の酸素及び
水と反応して硫酸の状態で吸着される。
２ＳＯ2 ＋Ｏ2 →２ＳＯ3 （１）
ＳＯ3 ＋Ｈ2 Ｏ→Ｈ2 ＳＯ4 （２）Sulfur oxides, hydrogen chloride, dioxins, etc. in the exhaust gas can be removed because they are adsorbed on the carbonaceous material. At this time, sulfur dioxide reacts with oxygen and water in the exhaust gas and is adsorbed in the state of sulfuric acid. 2SO 2 + O 2 → 2SO 3 (1) SO 3 + H 2 O → H 2 SO 4 (2)
【０００７】また、排ガス中にアンモニアを注入する
と、炭素質材の触媒作用により、排ガス中の窒素酸化物
は、アンモニアと反応して窒素と水とに分解するので、
除去することができる。
４ＮＯ＋４ＮＨ3 ＋Ｏ2 →４Ｎ2 ＋６Ｈ2 Ｏ （３）When ammonia is injected into the exhaust gas, the nitrogen oxides in the exhaust gas react with ammonia and decompose into nitrogen and water due to the catalytic action of the carbonaceous material.
Can be removed. 4NO + 4NH 3 + O 2 → 4N 2 + 6H 2 O (3)
【０００８】排ガスに注入されたアンモニアは、（３）
式の反応に使用されるだけでなく、その一部が硫黄酸化
物の吸着によって生成した硫酸とも反応する。
ＮＨ3 ＋Ｈ2 ＳＯ4 →ＮＨ4 ＨＳＯ4 （４）
ＮＨ3 ＋ＮＨ4 ＨＳＯ4 →（ＮＨ4 ）2 ＳＯ4 （５）Ammonia injected into the exhaust gas is (3)
Not only is it used in the reaction of the equation, but part of it also reacts with sulfuric acid produced by the adsorption of sulfur oxides. NH 3 + H 2 SO 4 → NH 4 HSO 4 (4) NH 3 + NH 4 HSO 4 → (NH 4 ) 2 SO 4 (5)
【０００９】吸着塔内の炭素質材は、ダストの付着によ
り吸着性能が低下するとともに、吸着した硫酸によって
窒素酸化物を分解する触媒性能が低下するので、再生す
る必要がある。炭素質材の再生は、通常次のようにして
行われる。The carbonaceous material in the adsorption tower needs to be regenerated because the adsorption performance is deteriorated by the adhesion of dust and the catalytic performance for decomposing nitrogen oxides by the adsorbed sulfuric acid is deteriorated. Regeneration of the carbonaceous material is usually performed as follows.
【００１０】先ず、活性の低下した炭素質材を再生塔に
供給し、４００℃程度の高温に加熱することにより、吸
着した有害物質を脱着する。ダイオキシン類は完全に分
解される。このとき、硫酸は後述の反応式により二酸化
硫黄として放出される。First, a carbonaceous material with reduced activity is supplied to a regeneration tower and heated to a high temperature of about 400 ° C. to desorb the adsorbed harmful substances. Dioxins are completely decomposed. At this time, sulfuric acid is released as sulfur dioxide by the reaction formula described later.
【００１１】次に、大気中で発火しない温度まで冷却し
た後、再生塔から排出する。そして、分級機によって付
着したダスト及び粉化した炭素質材が除去された後、再
び、吸着塔に供給される。Next, after cooling to a temperature at which ignition does not occur in the atmosphere, it is discharged from the regeneration tower. Then, after the attached dust and the pulverized carbonaceous material are removed by the classifier, the dust is supplied again to the adsorption tower.
【００１２】再生塔に供給された炭素質材には、（１）
及び（２）式の反応で生成した硫酸と、（４）及び
（５）式によって生成したＮＨ4 ＨＳＯ4 及び（Ｎ
Ｈ4 ）2 ＳＯ4 が吸着されており、これらは次の反応に
よって脱着される。
Ｈ2 ＳＯ4 →ＳＯ3 ＋Ｈ2 Ｏ （６）
２ＳＯ3 ＋Ｃ→２ＳＯ2 ＋ＣＯ2 （７）
（ＮＨ4 ）2 ＳＯ4 →ＮＨ3 ＋ＮＨ4 ＨＳＯ4 （８）
ＮＨ4 ＨＳＯ4 →ＮＨ3 ＋Ｈ2 ＳＯ4 （９）
２ＮＨ3 ＋３ＳＯ3 →Ｎ2 ＋３Ｈ2 Ｏ＋３ＳＯ2 （１０）The carbonaceous material supplied to the regeneration tower includes (1)
And sulfuric acid generated by the reaction of the formula (2), and NH 4 HSO 4 and (N generated by the formulas (4) and (5).
H 4 ) 2 SO 4 is adsorbed and these are desorbed by the following reaction. H 2 SO 4 → SO 3 + H 2 O (6) 2SO 3 + C → 2SO 2 + CO 2 (7) (NH 4 ) 2 SO 4 → NH 3 + NH 4 HSO 4 (8) NH 4 HSO 4 → NH 3 + H 2 SO 4 (9) 2NH 3 + 3SO 3 → N 2 + 3H 2 O + 3SO 2 (10)
【００１３】上記の反応により発生するガスは、窒素等
の不活性ガスをキャリアガスとして再生塔から排出され
る。通常、この脱離ガスは、高濃度の二酸化硫黄を含む
ので、硫酸や硫黄等を製造して副産物として回収するこ
とができる。The gas generated by the above reaction is discharged from the regeneration tower using an inert gas such as nitrogen as a carrier gas. Usually, this desorbed gas contains a high concentration of sulfur dioxide, so that sulfuric acid, sulfur and the like can be produced and recovered as a by-product.
【００１４】しかし、上記の各反応は、全て完全に行わ
れるものではなく、脱離ガス中には、少量の三酸化硫黄
及びアンモニアが混入することになる。脱離ガス中のア
ンモニアは、再びＮＨ4 ＨＳＯ4 又は（ＮＨ4 ）2 ＳＯ
4 を生成し、温度の低下に伴って装置内で固体として析
出することになるので、配管の閉塞等のトラブルを起こ
す原因となる。However, all of the above reactions are not completely carried out, and a small amount of sulfur trioxide and ammonia are mixed in the desorbed gas. Ammonia in the desorbed gas is converted to NH 4 HSO 4 or (NH 4 ) 2 SO again.
Since 4 is generated and precipitates as a solid in the apparatus as the temperature decreases, it causes troubles such as blockage of piping.
【００１５】このようなトラブルを防ぐ方法として、脱
離ガスを水洗することにより、アンモニアを除去する方
法が考えられる。しかし、脱離ガス中のアンモニアを完
全に除去することは難しく、また、除去したアンモニア
を処理するための装置も必要となる。As a method of preventing such troubles, a method of removing ammonia by washing the desorbed gas with water can be considered. However, it is difficult to completely remove the ammonia in the desorbed gas, and an apparatus for treating the removed ammonia is required.
【００１６】また、このようなトラブルを防ぐ他の方法
が、特公昭６０−３４４１３号公報に記載されている。
この方法は、再生塔の上部に上段の移動床を設け、この
移動床において、疲弊吸着剤と脱離ガスとを接触させて
（２）、（４）及び（５）式の反応を行わせることによ
り、脱離ガス中の三酸化硫黄及びアンモニアを吸着剤で
捕捉するようにしたものである。そして、この後、吸着
剤は再生塔に送られて前述の反応によって再生されるも
のである。Another method for preventing such trouble is described in Japanese Patent Publication No. 60-34413.
In this method, an upper moving bed is provided in the upper part of the regeneration tower, and the exhausted adsorbent and the desorbed gas are brought into contact with each other in the moving bed to carry out the reactions of the expressions (2), (4) and (5). As a result, the sulfur trioxide and the ammonia in the desorbed gas are captured by the adsorbent. Then, after this, the adsorbent is sent to the regeneration tower and regenerated by the above-mentioned reaction.
【００１７】しかし、このような方法にあっても、本発
明者らが確認テストを行った結果、必ずしも常に良好な
結果が得られるとは限らず、多くの場合アンモニアの除
去が不充分となることが分かった。However, even with such a method, as a result of the confirmation test conducted by the present inventors, a good result is not always obtained, and in many cases, removal of ammonia is insufficient. I found out.
【００１８】この発明は前記のような従来のもののもつ
問題点を解決したものであって、活性の低下した炭素質
材を再生塔において加熱再生する際に発生する脱離ガス
中に含まれるアンモニアを完全に除去することができる
乾式排ガス処理方法及び処理装置を提供することを目的
とするものである。The present invention solves the problems of the above-mentioned conventional ones, in which ammonia contained in the desorbed gas generated when the carbonaceous material with reduced activity is heated and regenerated in the regeneration tower. It is an object of the present invention to provide a dry exhaust gas treatment method and a treatment apparatus capable of completely removing the gas.
【００１９】[0019]
【問題点を解決するための手段】上記の問題点を解決す
るためにこの発明は、内部に粒子状の炭素質材を充填し
て移動層を形成するとともに、該移動層に排ガスを流通
させて炭素質材と排ガスとの固気接触を行うことによ
り、排ガス中に含まれる窒素酸化物及びその他の有害物
質を除去する移動層式吸着塔と、有害物質により活性の
低下した炭素質材を加熱再生させる再生塔とを備えた乾
式排ガス処理装置において、吸着塔から抜き出した活性
の低下した炭素質材を再生塔に供給する前に一時保留す
る脱安塔を設け、該脱安塔に再生塔で発生する脱離ガス
及び酸素含有ガスを供給して炭素質材との固気接触を行
うように構成した手段を採用したものである。また、内
部に粒子状の炭素質材を充填して移動層を形成した移動
層式吸着塔に排ガスを流通させて、炭素質材と排ガスと
の固気接触を行うことにより、排ガス中に含まれる窒素
酸化物及びその他の有害物質を除去し、この後、有害物
質により活性の低下した炭素質材を吸着塔から抜き出し
て脱安塔に一時保留するとともに、再生塔で発生する脱
離ガス及び酸素含有ガスを脱安塔に供給して炭素質材と
の固気接触を行い、この後、炭素質材を脱安塔から抜き
出して再生塔に供給して加熱再生を行うように構成した
手段を採用したものである。さらに、前記脱安塔内の炭
素質材に、実質上飽和量の硫酸を担持させるように構成
した手段を採用したものである。そして、前記脱安塔内
に実質上飽和量の硫酸を担持させた炭素質材を充填し、
この後運転を開始するように構成した手段を採用したも
のである。In order to solve the above problems, the present invention is to fill a particulate carbonaceous material inside to form a moving bed and to allow exhaust gas to flow through the moving bed. By moving the carbonaceous material and the exhaust gas into solid gas, a moving bed adsorption tower that removes nitrogen oxides and other harmful substances contained in the exhaust gas, and a carbonaceous material whose activity has decreased due to the harmful substances In a dry exhaust gas treatment apparatus equipped with a regeneration tower for heating and regeneration, a deaeration tower for temporarily holding the carbonaceous material with reduced activity extracted from the adsorption tower before supplying it to the regeneration tower is provided, and the deaeration tower is regenerated. A means configured to supply a desorbed gas generated in the tower and an oxygen-containing gas to perform solid-gas contact with the carbonaceous material is adopted. Further, the exhaust gas is circulated through a moving bed type adsorption tower in which a particulate carbonaceous material is filled inside to form a moving bed, and solid gas contact between the carbonaceous material and the exhaust gas is carried out to thereby be included in the exhaust gas. Nitrogen oxides and other harmful substances are removed.After that, the carbonaceous material whose activity has been reduced by the harmful substances is withdrawn from the adsorption tower and is temporarily retained in the desorption column, and the desorbed gas generated in the regeneration tower and A means configured to supply an oxygen-containing gas to the deaeration tower for solid-gas contact with the carbonaceous material, and then to withdraw the carbonaceous material from the deaeration tower and supply it to a regeneration tower for heating regeneration. Is adopted. Further, means for supporting a substantially saturated amount of sulfuric acid on the carbonaceous material in the deaeration tower is adopted. Then, a carbonaceous material supporting a substantially saturated amount of sulfuric acid is filled in the deaeration tower,
After that, the means configured to start the operation is adopted.
【００２０】[0020]
【作用】この発明は前記のような手段を採用したことに
より、吸着塔に排ガスを流通させて、炭素質材と排ガス
との固気接触を行うことにより、排ガス中に含まれる窒
素酸化物及びその他の有害物質が除去される。そして、
有害物質によって活性の低下した炭素質材を吸着塔から
抜出して脱安塔に一時保留するとともに、再生塔で発生
した離脱ガス及び酸素含有ガスを脱安塔に供給し、炭素
質材との固気接触を行うことにより、離脱ガス中に含ま
れるアンモニアが除去されることになる。そして、この
後、炭素質材を脱安塔から抜き出して再生塔に供給し、
加熱再生を行うことにより、炭素質材に吸着した有害物
質を脱着することができることになる。According to the present invention, by adopting the above-mentioned means, the exhaust gas is circulated in the adsorption tower, and the carbonaceous material and the exhaust gas are brought into solid-gas contact with each other. Other harmful substances are removed. And
The carbonaceous material whose activity has decreased due to harmful substances is withdrawn from the adsorption tower and is temporarily held in the deaeration tower, and the desorbed gas and oxygen-containing gas generated in the regeneration tower are supplied to the deaeration tower to solidify with the carbonaceous material. By carrying out the gas contact, the ammonia contained in the released gas is removed. Then, after this, the carbonaceous material is extracted from the deaeration tower and supplied to the regeneration tower,
By carrying out the heating regeneration, the harmful substances adsorbed on the carbonaceous material can be desorbed.
【００２１】[0021]
【発明の実施の形態】前述したように、特公昭６０−３
４４１３号公報に記載されている方法は、必ずしも常に
良好な結果が得られるとは限らず、多くの場合アンモニ
アの除去が不充分となる。そこで、本願発明者らはその
原因の究明を行った。その結果、次のことが明らかとな
った。BEST MODE FOR CARRYING OUT THE INVENTION As described above, Japanese Patent Publication No. 60-3.
The method described in Japanese Patent No. 4413 does not always give good results, and in many cases, the removal of ammonia is insufficient. Therefore, the inventors of the present application investigated the cause. As a result, the following things became clear.
【００２２】前述の公報には、脱離ガス中のアンモニア
と脱離ガス中の三酸化硫黄によって（２）、（４）及び
（５）式の反応が行われることが記載されている。しか
し、確認テストの結果ではアンモニアの除去が不充分で
あり、これは脱離ガス中のアンモニアの量に対して、脱
離ガス中の三酸化硫黄の量が不足するためと考えられ、
アンモニアの除去を完全に行うためには、脱離ガス中の
三酸化硫黄の量を増加する必要がある。The above-mentioned publication describes that the reactions of the formulas (2), (4) and (5) are carried out by ammonia in the desorbed gas and sulfur trioxide in the desorbed gas. However, the result of the confirmation test showed that the removal of ammonia was insufficient, which is considered to be due to the insufficient amount of sulfur trioxide in the desorbed gas with respect to the amount of ammonia in the desorbed gas.
In order to completely remove ammonia, it is necessary to increase the amount of sulfur trioxide in the desorbed gas.
【００２３】再生塔内は不活性ガス雰囲気であり、しか
も高温の炭素質材が存在するので、極めて強い還元雰囲
気となっている。即ち、三酸化硫黄が還元されて二酸化
硫黄になり易い雰囲気である。従って、吸着した有害物
質の脱着を完全に行おうとすればする程、（７）式の反
応が完全に進行して、脱離ガス中に含まれる三酸化硫黄
の量は少なくなり、アンモニアとの反応に必要な量が不
足することが確認された。The inside of the regeneration tower is in an inert gas atmosphere, and since a high-temperature carbonaceous material is present, it has an extremely strong reducing atmosphere. That is, it is an atmosphere in which sulfur trioxide is easily reduced to sulfur dioxide. Therefore, the more complete the desorption of the adsorbed harmful substances, the more the reaction of the formula (7) proceeds, and the amount of sulfur trioxide contained in the desorbed gas decreases, so It was confirmed that the amount required for the reaction was insufficient.
【００２４】また、再生塔の本来の目的である有害物質
の脱着と、上記反応に必要な三酸化硫黄を脱離ガス中に
確保することを同時に満足する、再生塔の運転条件を求
めることを試みたが、困難であることが確認された。Further, it is necessary to determine the operating conditions of the regeneration tower, which simultaneously satisfy the desorption of harmful substances, which is the original purpose of the regeneration tower, and the securing of sulfur trioxide necessary for the above reaction in the desorbed gas. I tried, but it was confirmed to be difficult.
【００２５】そして、本願発明者らは、このような場合
にアンモニアの除去率を向上させる手段を模索した。そ
の結果、上記の脱離ガス中に酸素を添加して疲弊吸着剤
と接触させることにより、脱離ガス中の二酸化硫黄を硫
酸として吸着剤に担持させることが可能であること、吸
着剤の硫酸担持量を実質的に飽和量とすることが可能で
あること、これによって、脱離ガスに含まれるアンモニ
アを完全に除去することができることを発見し、本発明
を完成するに至った。Then, the present inventors sought a means for improving the removal rate of ammonia in such a case. As a result, it is possible to support sulfur dioxide in the desorbed gas as sulfuric acid on the adsorbent by adding oxygen to the desorbed gas and bringing it into contact with the exhausted adsorbent. The present invention has been completed by discovering that the supported amount can be substantially saturated and that the ammonia contained in the desorbed gas can be completely removed.
【００２６】本発明は、吸着塔から抜き出された炭素質
材を、再生塔に供給する前に一時保留する脱安塔を設
け、この脱安塔に再生塔で発生する脱離ガスを供給する
と同時に、酸素含有ガスを導入して炭素質材と固気接触
を行うものである。そして、前記脱安塔内の炭素質材
が、実質上飽和量の硫酸を担持した状態で運転すること
により、脱離ガスに含まれるアンモニアを完全に除去す
ることができるものである。The present invention is provided with a desorption column for temporarily holding the carbonaceous material withdrawn from the adsorption column before feeding it to the regeneration column, and supplies desorption gas generated in the regeneration column to this desorption column. At the same time, an oxygen-containing gas is introduced to make solid-gas contact with the carbonaceous material. Then, the carbonaceous material in the desorption column is operated in a state where a substantially saturated amount of sulfuric acid is carried, whereby ammonia contained in the desorbed gas can be completely removed.
【００２７】以下、本発明の原理について、図１を参照
しつつ説明する。図１は、本発明をＲＤＦ（廃棄物燃
料）の燃焼排ガスに適用した例であって、内部に粒状の
炭素質材を充填して移動層を形成した移動層式吸着塔１
と、吸着塔１から抜き出した活性の低下した炭素質材を
加熱再生する再生塔３と、活性の低下した炭素質材を再
生塔３に供給する前に一時保留する脱安塔２と、再生塔
３で加熱再生した炭素質材に付着しているダスト及び粉
化した炭素質材を除去する分級機４と、吸着塔１から炭
素質材を抜き出して脱安塔２に供給するロックホッパ５
と、脱安塔２から炭素質材を抜き出して再生塔３に供給
するロックホッパ６と、再生塔３から炭素質材を抜き出
して分級機４に供給するロックホッパ７とを備えてい
る。The principle of the present invention will be described below with reference to FIG. FIG. 1 is an example in which the present invention is applied to combustion exhaust gas of RDF (waste fuel), and a moving bed type adsorption tower 1 in which a granular carbonaceous material is filled inside to form a moving bed
A regeneration tower 3 for heating and regenerating the carbonaceous material with reduced activity extracted from the adsorption tower 1, a deaeration tower 2 for temporarily holding the carbonaceous material with reduced activity before supplying it to the regeneration tower 3, and regeneration A classifier 4 that removes dust and powdered carbonaceous material adhering to the carbonaceous material heated and regenerated in the tower 3, and a lock hopper 5 that extracts the carbonaceous material from the adsorption tower 1 and supplies it to the deaeration tower 2.
And a lock hopper 7 for extracting the carbonaceous material from the desorption tower 2 and supplying it to the regeneration tower 3, and a lock hopper 7 for extracting the carbonaceous material from the regeneration tower 3 and supplying it to the classifier 4.
【００２８】再生塔３は、炭素質材を高温に加熱するた
めに不活性雰囲気で運転する必要があり、一般に、脱離
ガスは窒素等の不活性ガスをキャリアガスとして、高濃
度の二酸化硫黄と少量の三酸化硫黄及びアンモニア等を
含むものである。The regeneration tower 3 needs to be operated in an inert atmosphere in order to heat the carbonaceous material to a high temperature. In general, the desorbed gas is a highly concentrated sulfur dioxide using an inert gas such as nitrogen as a carrier gas. And a small amount of sulfur trioxide and ammonia.
【００２９】不活性雰囲気では（１）式の反応が起こら
ないので、二酸化硫黄を硫酸として炭素質材に担持する
ことができない。Since the reaction of the formula (1) does not occur in an inert atmosphere, sulfur dioxide cannot be supported on the carbonaceous material as sulfuric acid.
【００３０】しかし、脱安塔２に脱離ガスと共に酸素含
有ガスを供給すると、（１）及び（２）式の反応が起こ
り、脱安塔２内の炭素質材に硫酸が担持されることにな
る。酸素含有ガスとしては、大気、又は排ガスの一部を
利用することができる。なお、この反応は発熱反応であ
るために、脱安塔内に冷却手段を設けている。However, when the oxygen-containing gas is supplied to the desorption column 2 together with the desorbed gas, the reactions of the formulas (1) and (2) occur, and the carbonaceous material in the desorption column 2 is loaded with sulfuric acid. become. As the oxygen-containing gas, the atmosphere or part of the exhaust gas can be used. Since this reaction is an exothermic reaction, a cooling means is provided in the deaeration tower.
【００３１】硫酸を担持した炭素質材は再生塔３に送ら
れて、（６）及び（７）式により二酸化硫黄を放出し、
脱離ガスとして脱安塔２に送られる。The carbonaceous material supporting sulfuric acid is sent to the regeneration tower 3 to release sulfur dioxide by the formulas (6) and (7),
It is sent to the desorption column 2 as desorption gas.
【００３２】つまり、硫黄酸化物は、硫酸又は二酸化硫
黄の形で脱安塔２と再生塔３との間を循環することにな
るので、脱安塔２内の炭素質材には次第に硫酸が蓄積す
る。That is, since the sulfur oxides circulate between the deamination tower 2 and the regeneration tower 3 in the form of sulfuric acid or sulfur dioxide, the carbonaceous material in the deaeration tower 2 is gradually depleted of sulfuric acid. accumulate.
【００３３】したがって、吸着塔１から再生塔３に送ら
れる炭素質材に少量の硫酸しか吸着されていない場合で
あっても、脱安塔２内の炭素質材には硫酸が蓄積するこ
とになり、最終的に脱安塔２内の炭素質材は、実質的に
飽和量の硫酸が担持されることになる。Therefore, even if a small amount of sulfuric acid is adsorbed on the carbonaceous material sent from the adsorption tower 1 to the regeneration tower 3, sulfuric acid accumulates on the carbonaceous material in the deaeration tower 2. Eventually, the carbonaceous material in the deaeration tower 2 will carry a substantially saturated amount of sulfuric acid.
【００３４】この結果、再生塔３からの脱離ガス中に含
まれるアンモニアは、多量の硫酸を担持した炭素質材と
接触することになり、アンモニアは完全に除去されるこ
とになる。As a result, the ammonia contained in the desorbed gas from the regeneration tower 3 comes into contact with the carbonaceous material supporting a large amount of sulfuric acid, and the ammonia is completely removed.
【００３５】脱離ガス中の硫黄酸化物は、脱安塔２内の
炭素質材が飽和量の硫酸を担持するまで吸着されるの
で、この間、脱安塔２から排出されるガスには、硫黄酸
化物が殆ど含まれない。The sulfur oxides in the desorbed gas are adsorbed until the carbonaceous material in the desorption column 2 carries a saturated amount of sulfuric acid. It contains almost no sulfur oxides.
【００３６】脱安塔２内の炭素質材が飽和量の硫酸を担
持した後は、脱安塔２から排出されるガスに吸着塔１で
吸着した硫黄酸化物の量に等しい量の硫黄酸化物が含ま
れることになる。この定常状態は、従来の方法における
場合と全く同様である。After the carbonaceous material in the deamination tower 2 carries a saturated amount of sulfuric acid, the amount of sulfur oxide equal to the amount of sulfur oxide adsorbed in the adsorption tower 1 in the gas discharged from the deaeration tower 2. Things will be included. This steady state is exactly the same as in the conventional method.
【００３７】運転開始後、短時間でこの定常状態を達成
するために、予め脱安塔２内に飽和量の硫酸を担持した
炭素質材を充填しておくことが好ましい。In order to achieve this steady state in a short time after the start of operation, it is preferable to fill the deaeration tower 2 with a carbonaceous material carrying a saturated amount of sulfuric acid in advance.
【００３８】以上の通り、本発明は、脱離ガス中のアン
モニアを除去するために有効であるが、更に、炭素質材
の性能を向上する賦活効果を伴うものである。As described above, the present invention is effective for removing ammonia in the desorbed gas, but is accompanied by an activating effect for improving the performance of the carbonaceous material.
【００３９】すなわち、一般に炭素質材は、前記の
（７）式の反応を行うことにより、比表面積が増大する
と共に活性化され、その触媒性能を向上することができ
る。本発明は、脱安塔２で飽和量の硫酸を担持した後、
再生塔３で（７）式の反応を積極的に受けるので、大き
な賦活効果を得ることができる。That is, generally, the carbonaceous material is activated by increasing the specific surface area by carrying out the reaction of the above-mentioned formula (7), and the catalytic performance thereof can be improved. According to the present invention, after supporting a saturated amount of sulfuric acid in the desorption column 2,
Since the regeneration tower 3 positively receives the reaction of the formula (7), a large activation effect can be obtained.
【００４０】吸着塔１に供給される排ガスの成分は、概
ね次の通りである。
ダスト ： ２０ｍｇ／Ｎｍ3 ＤＢ
ＳＯｘ ： 〜５０ｐｐｍＤＢ
ＮＯｘ ： ５０〜１５０ｐｐｍＤＢ
ＨＣｌ ： ５０〜２００ｐｐｍＤＢ
ＤＸＮ ： ５〜３０ｎｇ−ＴＥＱ／Ｎｍ3 ＤＢ
脱安塔２には再生塔３からの脱離ガスと排ガスの一部を
供給している。また、脱安塔２から排出されるガスは焼
却炉８に供給し、焼却炉８の炉内又はバグフィルタ９の
上流に供給される消石灰によって硫黄酸化物及び塩化水
素等が除去される。なお、１０は脱塩装置、１１は重金
属除去装置である。The components of the exhaust gas supplied to the adsorption tower 1 are as follows. Dust: 20 mg / Nm 3 DB SOx: -50 ppmDB NOx: 50-150 ppmDB HCl: 50-200 ppmDB DXN: 5-30 ng-TEQ / Nm 3 DB In the desorption tower 2, one of the desorbed gas from the regeneration tower 3 and the exhaust gas. Supply department. Further, the gas discharged from the desorption tower 2 is supplied to the incinerator 8, and sulfur oxide, hydrogen chloride, etc. are removed by slaked lime supplied in the furnace of the incinerator 8 or upstream of the bag filter 9. In addition, 10 is a desalination apparatus and 11 is a heavy metal removal apparatus.
【００４１】[0041]
【発明の効果】この発明は前記のように構成して、吸着
塔から抜き出した炭素質材を再生塔に供給する前に一時
保留する脱安塔を設け、この脱安塔に再生塔で発生する
脱離ガスを供給すると同時に、酸素含有ガスを導入して
炭素質材との固気接触を行うようにしたことにより、脱
離ガスに含まれるアンモニアを完全に除去することがで
きることになる。したがって、脱離ガス中にアンモニア
が残っていることにより、ＮＨ4 ＨＳＯ4 又は（Ｎ
Ｈ4 ）2 ＳＯ4 が生成され、それらが温度の低下に伴っ
て固体として析出して配管の閉塞等のトラブルを起こす
ようなことがなくなり、効率的に排ガスの処理を行うこ
とができることになる等の優れた効果を奏するものであ
る。The present invention is constructed as described above, and is provided with a desorption column for temporarily holding the carbonaceous material withdrawn from the adsorption column before supplying it to the regeneration column. By supplying the desorbed gas, the oxygen-containing gas is introduced and the solid-gas contact with the carbonaceous material is performed, whereby ammonia contained in the desorbed gas can be completely removed. Therefore, due to the ammonia remaining in the desorbed gas, NH 4 HSO 4 or (N
H 4 ) 2 SO 4 is not generated, and the precipitation of H 4 ) 2 SO 4 as a solid with a decrease in temperature does not cause troubles such as clogging of pipes, and exhaust gas can be efficiently treated. It has excellent effects such as.
【図１】この発明による乾式排ガス処理装置の一実施の
形態を示した概略説明図である。FIG. 1 is a schematic explanatory view showing an embodiment of a dry exhaust gas treatment apparatus according to the present invention.
１……吸着塔 ２……脱安塔 ３……再生塔 ４……分級機 ５、６、７……ロックホッパ ８……焼却炉 ９……バグフィルタ １０……脱塩装置 １１……重金属除去装置 1 ... Adsorption tower 2 ... The relief tower 3 ... Regeneration tower 4 ... Classifier 5, 6, 7 ... Rock hopper 8 …… Incinerator 9: Bug filter 10 ... Desalination device 11 ... Heavy metal removal device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 20/34 Ｆターム(参考） 4D002 AA02 AA12 AA21 AC04 BA03 BA04 BA12 BA13 BA14 CA08 CA13 DA05 DA12 DA26 DA41 EA02 EA08 EA12 GA02 GB02 GB03 4D012 CA12 CA15 CA16 CC07 CD03 CE02 CF04 CF05 CG01 CG03 CH01 CJ10 CK06 4G066 AA05B AA12B AA17B AA47B BA09 CA23 CA28 CA33 DA02 FA01 GA01 GA06 GA23 GA32 GA39 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 20/34 F term (reference) 4D002 AA02 AA12 AA21 AC04 BA03 BA04 BA12 BA13 BA14 CA08 CA13 DA05 DA12 DA26 DA41 EA02 EA08 EA12 GA02 GB02 GB03 4D012 CA12 CA15 CA16 CC07 CD03 CE02 CF04 CF05 CG01 CG03 CH01 CJ10 CK06 4G066 AA05B AA12B AA17B AA47B BA09 CA23 CA28 CA33 DA02 FA01 GA01 GA06 GA23 GA32 GA39
Claims (4)
層を形成するとともに、該移動層に排ガスを流通させて
炭素質材と排ガスとの固気接触を行うことにより、排ガ
ス中に含まれる窒素酸化物及びその他の有害物質を除去
する移動層式吸着塔と、有害物質により活性の低下した
炭素質材を加熱再生させる再生塔とを備えた乾式排ガス
処理装置において、 吸着塔から抜き出した活性の低下した炭素質材を再生塔
に供給する前に一時保留する脱安塔を設け、該脱安塔に
再生塔で発生する脱離ガス及び酸素含有ガスを供給して
炭素質材との固気接触を行うように構成したことを特徴
とする乾式排ガス処理装置。1. In the exhaust gas, the inside of the exhaust gas is filled with a particulate carbonaceous material to form a moving bed, and the exhaust gas is passed through the moving bed to make solid-gas contact between the carbonaceous material and the exhaust gas. In a dry exhaust gas treatment device equipped with a moving bed type adsorption tower that removes nitrogen oxides and other harmful substances contained in, and a regeneration tower that heats and regenerates the carbonaceous material whose activity has decreased due to harmful substances, A desorption column for temporarily holding the extracted carbonaceous material with reduced activity before it is supplied to the regeneration column is provided, and the desorption gas and the oxygen-containing gas generated in the regeneration column are supplied to the desorption column to supply the carbonaceous material. A dry type exhaust gas treatment device, which is configured to make solid-gas contact with the exhaust gas treatment device.
層を形成した移動層式吸着塔に排ガスを流通させて、炭
素質材と排ガスとの固気接触を行うことにより、排ガス
中に含まれる窒素酸化物及びその他の有害物質を除去
し、この後、有害物質により活性の低下した炭素質材を
吸着塔から抜き出して脱安塔に一時保留するとともに、
再生塔で発生する脱離ガス及び酸素含有ガスを脱安塔に
供給して炭素質材との固気接触を行い、この後、炭素質
材を脱安塔から抜き出して再生塔に供給して加熱再生を
行うように構成したことを特徴とする乾式排ガス処理方
法。2. Exhaust gas is produced by flowing exhaust gas through a moving bed type adsorption tower in which a particulate carbonaceous material is filled inside to form a moving bed to make solid-gas contact between the carbonaceous material and the exhaust gas. Nitrogen oxides and other harmful substances contained in it are removed, and thereafter, the carbonaceous material whose activity has been reduced by the harmful substances is extracted from the adsorption tower and temporarily retained in the deaeration tower,
The desorbed gas and oxygen-containing gas generated in the regeneration tower are supplied to the desorption column to make solid-gas contact with the carbonaceous material, and then the carbonaceous material is extracted from the desorption column and supplied to the regeneration tower. A dry exhaust gas treatment method characterized in that it is configured to perform heating regeneration.
量の硫酸を担持させるように構成した請求項１記載の乾
式排ガス処理装置又は請求項２記載の乾式排ガス処理方
法。3. The dry exhaust gas treatment apparatus according to claim 1, or the dry exhaust gas treatment method according to claim 2, wherein the carbonaceous material in the deaeration tower is configured to support a substantially saturated amount of sulfuric acid.
持させた炭素質材を充填し、この後運転を開始するよう
に構成した請求項１記載の乾式排ガス処理装置又は請求
項２記載の乾式排ガス処理方法。4. The dry exhaust gas treatment apparatus according to claim 1, wherein the deaeration tower is filled with a carbonaceous material supporting a substantially saturated amount of sulfuric acid, and then the operation is started. 2. The dry exhaust gas treatment method according to 2.
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|---|---|---|---|
| JP23724598A JP4429404B2 (en) | 1998-08-24 | 1998-08-24 | Dry exhaust gas treatment method and treatment apparatus |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23724598A JP4429404B2 (en) | 1998-08-24 | 1998-08-24 | Dry exhaust gas treatment method and treatment apparatus |
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| Publication Number | Publication Date |
|---|---|
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| Country | Link |
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| JP (1) | JP4429404B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002282646A (en) * | 2001-03-28 | 2002-10-02 | Sumitomo Heavy Ind Ltd | Desulfurization equipment |
| JP2003053135A (en) * | 2001-08-21 | 2003-02-25 | Mitsui Mining Co Ltd | Apparatus for treating exhaust gas |
| WO2010071018A1 (en) * | 2008-12-16 | 2010-06-24 | 株式会社クレハエンジニアリング | Activated carbon regenerative furnace, and gas purification method and apparatus using same |
| WO2010106625A1 (en) * | 2009-03-16 | 2010-09-23 | ジェイパワー・エンテック株式会社 | Dry exhaust-gas treating apparatus |
-
1998
- 1998-08-24 JP JP23724598A patent/JP4429404B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002282646A (en) * | 2001-03-28 | 2002-10-02 | Sumitomo Heavy Ind Ltd | Desulfurization equipment |
| JP2003053135A (en) * | 2001-08-21 | 2003-02-25 | Mitsui Mining Co Ltd | Apparatus for treating exhaust gas |
| WO2010071018A1 (en) * | 2008-12-16 | 2010-06-24 | 株式会社クレハエンジニアリング | Activated carbon regenerative furnace, and gas purification method and apparatus using same |
| WO2010106625A1 (en) * | 2009-03-16 | 2010-09-23 | ジェイパワー・エンテック株式会社 | Dry exhaust-gas treating apparatus |
| US8518165B2 (en) | 2009-03-16 | 2013-08-27 | J—Power Entech, Inc. | Dry exhaust-gas treating apparatus |
| JP5396464B2 (en) * | 2009-03-16 | 2014-01-22 | ジェイパワー・エンテック株式会社 | Dry exhaust gas treatment equipment |
| CN102348490B (en) * | 2009-03-16 | 2014-01-22 | 电源开发工程技术株式会社 | Dry exhaust-gas treating apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4429404B2 (en) | 2010-03-10 |
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