JPH06179882A - Method and apparatus for eliminating carbon - Google Patents
Method and apparatus for eliminating carbonInfo
- Publication number
- JPH06179882A JPH06179882A JP33469192A JP33469192A JPH06179882A JP H06179882 A JPH06179882 A JP H06179882A JP 33469192 A JP33469192 A JP 33469192A JP 33469192 A JP33469192 A JP 33469192A JP H06179882 A JPH06179882 A JP H06179882A
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- JP
- Japan
- Prior art keywords
- oxygen
- thermal decomposition
- carbon
- gas
- coal
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、石炭の効率的な利用を
目的とする石炭急速熱分解プロセスにおいて、析出した
炭素分を除去する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing precipitated carbon in a rapid coal pyrolysis process for the efficient use of coal.
【０００２】[0002]
【従来の技術】石炭急速熱分解は１９７０年代に始まっ
た技術であり、比較的歴史が浅い。石炭の利用技術には
燃焼以外にガス化、液化等があるが、ガス化は１５００
℃以上の高温が、液化は２００ａｔｍ程度の高圧が必要
であり装置への負荷が大きいために、設備投資、安定操
業の点で実用化へのハードルが高い。急速熱分解技術の
メリットは、１０００℃以下の熱分解反応温度と常圧付
近の反応圧力でマイルドな反応を行うため通常の炉材を
応用でき、低コストで負担の少ない装置構成を可能にす
る点にあり、特願平４−１２２８９７号に炭素質を酸素
でガス化した高温ガスによって熱分解することを特徴と
する石炭急速熱分解装置が示されている。2. Description of the Related Art Rapid coal pyrolysis is a technology that started in the 1970s and has a relatively short history. Coal utilization technologies include gasification and liquefaction in addition to combustion, but gasification is 1500
A high temperature of ℃ or more requires a high pressure of about 200 atm for liquefaction and a heavy load on the equipment, so there are high hurdles to commercialization in terms of capital investment and stable operation. The advantage of the rapid pyrolysis technology is that it can be applied to ordinary furnace materials because it carries out a mild reaction at a pyrolysis reaction temperature of 1000 ° C or less and a reaction pressure near atmospheric pressure, enabling a low-cost, low-burden equipment configuration. In this regard, Japanese Patent Application No. 4-122897 discloses a coal rapid thermal decomposition apparatus characterized by thermally decomposing carbonaceous matter with a high temperature gas obtained by gasifying with oxygen.
【０００３】酸素透過膜を利用する技術は成膜技術や固
定担体開発により開花した。その目的とするところは、
一つは化学反応の制御、特に反応系に酸素のフリーラジ
カルが存在することを嫌う系における酸化反応を制御す
ることであり、一つは燃料電池に使われる固体電解質の
使用である。本発明における酸素透過膜は前者の技術に
入るが、炭素分除去方法として使用された例は本例が始
めてである。The technology utilizing the oxygen permeable membrane has flourished by the film forming technology and the development of a fixed carrier. The purpose is to
One is to control the chemical reaction, especially to control the oxidation reaction in a system that dislikes the presence of free radicals of oxygen in the reaction system, and the other is to use a solid electrolyte used in a fuel cell. The oxygen permeable membrane in the present invention falls into the former technique, but this example is the first to be used as a carbon removal method.
【０００４】[0004]
【発明が解決しようとする課題】石炭の急速熱分解を行
なうと、気体、液体（タール、水）、固体（チャー）の
混合物が熱分解部で発生する。プロセスでは固体、液体
の順に分離し各々を生成物として使用するが、熱分解反
応部では、気−液−固混合状態において、タールや気相
中炭化水素が熱分解反応部壁と接触して化学反応を起こ
し析出したり、チャー、未反応石炭がタールをバインダ
ーとして付着したりする場合がある。本発明では、析出
炭素および、チャーまたは石炭のタールをバインダーと
した付着物を一括して、炭素分と表現する。一旦析出し
た炭素は安定であり、酸素等の強い酸化剤が存在しなけ
れば除去されることはない。またチャーや石炭が付着し
た場合、徐々にコークス化し、強度を持つことになる。
系内には炭化水素が存在するため、爆発限界以上の濃度
での酸素は許容できず、酸素による直接的な除去は考え
にくい。析出量は短時間であれば問題ないが、長持間や
連続操業を考える場合、装置内容積の変化による反応系
の変化、熱移動の障害、さらには最悪の場合閉塞まで考
えられることになる。これはプロセスとして考えたとき
致命傷になりかねない。この急速熱分解においての炭素
分析出、付着への対策は成長途上の技術であるため存在
しておらず。前記特願平４−１２２８９７号の装置でも
扱われていない。付着物への対策としては、急速熱分解
技術ではないが、特開平１−２７６５６号の高温排ガス
除塵用サイクロンに示された衝撃粒子によるダスト除去
法などに物理的手法が示されているが、除去対象の性質
が異なることや、化学的に生成した析出炭素は剥離しに
くい等の点で応用が難しい。When rapid thermal decomposition of coal is performed, a mixture of gas, liquid (tar, water) and solid (char) is generated in the thermal decomposition section. In the process, solids and liquids are separated in order and used as products.In the thermal decomposition reaction part, tar and hydrocarbons in the gas phase contact the walls of the thermal decomposition reaction part in a gas-liquid-solid mixed state. There is a case where a chemical reaction occurs and deposits, or char and unreacted coal adhere as tar as a binder. In the present invention, the deposited carbon and the deposit using char or coal tar as a binder are collectively expressed as carbon content. The carbon once deposited is stable and will not be removed unless a strong oxidizing agent such as oxygen is present. When char or coal adheres, it gradually becomes coke and has strength.
Since hydrocarbons are present in the system, oxygen at concentrations above the explosion limit cannot be tolerated, and direct removal by oxygen is unlikely. The amount of precipitation does not pose a problem for a short period of time, but when considering long-term operation or continuous operation, changes in the reaction system due to changes in the internal volume of the apparatus, heat transfer obstacles, and in the worst case even blockage can be considered. This can be fatal when considered as a process. There is no measure for carbon analysis and adhesion in this rapid pyrolysis because it is a growing technology. It is not handled by the device of Japanese Patent Application No. 4-122897. As a measure against the adhered matter, although it is not a rapid thermal decomposition technique, a physical method is shown in the dust removal method using impact particles shown in the cyclone for high temperature exhaust gas dust removal in JP-A-1-27656, It is difficult to apply because it has different properties to be removed, and chemically deposited carbon is difficult to peel off.
【０００５】[0005]
【課題を解決しようとするための手段】本発明は、以上
の課題を解決するための酸素透過膜を利用した炭素分除
去方法および熱分解部内層に酸素透過膜を有する石炭急
速熱分解装置である。熱分解部内層と外層の間に導入さ
れた含酸素ガスが、酸素透過膜を介し、熱分解反応が行
なわれている熱分解部内層の内側に酸素イオンの形で移
動し、酸化剤供給ガスと熱分解反応気流が直接接触する
こと無く酸素と炭素分が反応できる。酸素透過膜材料と
しては、酸化物と金属の変移が容易であり、膜内で酸素
濃度勾配により酸素イオンの形で移動が可能である材料
が望まれる。推奨する金属はＰｂ、Ｓｎであるが、複数
のイオン価を持ち、酸素と化合する材料であれば特に制
限はない。DISCLOSURE OF THE INVENTION The present invention provides a method for removing carbon content using an oxygen permeable membrane and a rapid coal pyrolysis apparatus having an oxygen permeable membrane in the inner layer of the thermal decomposition section for solving the above problems. is there. The oxygen-containing gas introduced between the inner layer and the outer layer of the thermal decomposition part moves in the form of oxygen ions to the inside of the inner layer of the thermal decomposition part where the thermal decomposition reaction takes place through the oxygen permeable membrane, and the oxidant supply gas Oxygen and carbon can react without direct contact with the pyrolysis reaction gas stream. As the oxygen permeable membrane material, a material that is easily displaced between an oxide and a metal and is capable of moving in the form of oxygen ions due to an oxygen concentration gradient in the membrane is desired. The recommended metals are Pb and Sn, but there is no particular limitation as long as they are materials that have a plurality of ionic valences and can combine with oxygen.
【０００６】即ち、本発明の要旨とするところは、
（１）石炭を高温ガス気流中に吹き込み急速に熱分解さ
せる石炭急速熱分解装置において、析出または付着した
炭素分を、６００℃から１０００℃の温度範囲で、酸素
透過膜を介して含酸素ガスから供給した酸素で酸化する
ことを特徴とする炭素分除去方法、（２）前記石炭急速
熱分解装置において、熱分解部が酸素透過膜よりなる内
層部と、熱分解部外壁である外層部からなる二層構造で
あることを特徴とする炭素分除去装置、（３）酸素透過
膜が複数のイオン価を持つ金属の酸化物であることを特
徴とする前記（１）または前記（２）に記載の炭素分除
去方法または装置、（４）酸素透過膜がＰｂまたはＳｎ
の酸化物であることを特徴とする前記（１）または前記
（２）記載の炭素分除去方法または装置、（５）含酸素
ガスとして、Ｏ2 、空気、ＣＯ、ＣＯ2 、ＮＯ、Ｎ
Ｏ2 、Ｎ2 Ｏ、ＳＯ2 、ＳＯ3 、ＣＨ3 ＯＨ、Ｃ2 Ｈ5
ＯＨのいずれか１種類のガスまたは２種類以上の組み合
せで混合した含酸素ガスを使用し、含酸素ガス中の酸素
原子数が、前記熱分解部へ供給する石炭中の炭素原子数
の５％以上の速度で供給されることを特徴とする前記
（１）乃至前記（４）記載の炭素分除去方法または装置
である。That is, the gist of the present invention is that
(1) In a coal rapid thermal decomposition apparatus that blows coal into a high-temperature gas stream for rapid thermal decomposition, the precipitated or attached carbon content is oxygen-containing gas through an oxygen permeable membrane in a temperature range of 600 ° C to 1000 ° C. (2) In the coal rapid thermal decomposition apparatus, the thermal decomposition section comprises an inner layer section composed of an oxygen permeable membrane and an outer layer section which is an outer wall of the thermal decomposition section. A carbon content removing device having a two-layer structure, and (3) the above (1) or (2), wherein the oxygen-permeable film is an oxide of a metal having a plurality of ionic valencies. The method or apparatus for removing carbon content according to (4), wherein the oxygen permeable membrane is Pb or Sn.
The carbon content removing method or apparatus according to (1) or (2) above, wherein (5) the oxygen-containing gas is O 2 , air, CO, CO 2 , NO, N.
O 2 , N 2 O, SO 2 , SO 3 , CH 3 OH, C 2 H 5
Using any one kind of OH gas or an oxygen containing gas mixed in a combination of two or more kinds, the number of oxygen atoms in the oxygen containing gas is 5% of the number of carbon atoms in the coal supplied to the thermal decomposition part. The carbon content removing method or apparatus according to (1) to (4) above, wherein the carbon content is supplied at the above rate.
【０００７】ここで、石炭急速熱分解装置とは、図４に
工程の概要図を示すように、６００〜１０００℃、１〜
５０ａｔｍで急速熱分解を行なう熱分解部７、高温ガス
を供給する高温ガス供給装置８、石炭を供給する石炭供
給装置９、チャーを分離する固体分離装置１０、タール
を分離する気液分離装置１１からなる装置である。Here, the coal rapid pyrolysis apparatus is, as shown in the schematic view of the process in FIG.
Pyrolysis part 7 for rapid pyrolysis at 50 atm, high temperature gas supply device 8 for supplying high temperature gas, coal supply device 9 for supplying coal, solid separation device 10 for separating char, gas-liquid separation device 11 for separating tar It is a device consisting of.
【０００８】[0008]
【作用】以下、本発明について詳細に説明する。The present invention will be described in detail below.
【０００９】本発明の酸素透過概念を酸素透過膜断面図
として図１に示す。ここで、Ａは熱分解反応部、Ｂは酸
化剤供給部、Ｃは酸素透過膜である。炭素分１は、析出
炭素と、チャー及び石炭に分かれるが、析出炭素は芳香
族や脂肪族の炭化水素を生成源とし、壁面に吸着するこ
とで電子の授受を容易にして炭素の重合体として酸素透
過膜Ｃの熱分解反応部Ａ側に化学的に析出する。チャー
及び石炭は、タールをバインダーとして物理的に熱分解
反応部Ａ側に付着する。通常は析出炭素を足掛かりとし
て、炭素分全体で層厚を増しながら成長する。本発明の
場合、酸素透過膜が組成として酸素を含み、さらに酸素
数の変化しやすい金属を使用するため、電荷が変化しや
すく（鉛を使用すると、金属鉛（０）−酸化鉛（＋２）
−二酸化鉛（＋４）、スズを使用すると、金属スズ
（０）−一酸化スズ（＋２）−二酸化スズ（＋４））、
酸化物内酸素はエネルギー的に不安定で反応しやすい。
従って炭素分との化学反応が起こり、一酸化炭素２とな
って熱分解反応部Ａに拡散する。反応で酸素が使われる
ため、熱分解反応部Ａ側酸素濃度と酸化剤供給部Ｂ側酸
素濃度に勾配ができる。酸素透過膜Ｃ自体は連続した分
子であるため、濃度の高い酸化剤供給部Ｂ側から、濃度
の低い熱分解反応部Ａ側への酸素イオンの移動５がおこ
る。このとき酸素透過膜Ｃ内の酸素量が減少するため全
体の電荷バランスが崩れ（被還元状態）、酸化剤供給部
Ｂ側表面が酸素を受け入れやすい状態になる。酸化剤４
は酸素透過膜Ｃの酸化剤供給部Ｂ側に吸着し、金属酸化
物の酸素として吸収され、電気的にバランスがとれる。
供給される酸化剤４は反応性の面からすれば酸素がよい
が、酸素原子を含む分子であれば特に限定されない。炭
素分の反応速度は、酸素供給速度即ち酸素透過膜Ｃ内で
の酸素移動速度が全体の速度を律速するため材質に大き
く依存する。なかでもＰｂやＳｎの酸化物は結合安定性
が高い状態を複数持ち（０価、２価、４価）、しかも安
定状態間の相変移エネルギーが小さいことで酸素イオン
が容易に移動する特徴を持つことから、酸化物内の酸素
移動の点で有利である。The concept of oxygen permeation according to the present invention is shown in FIG. 1 as a sectional view of an oxygen permeable membrane. Here, A is a thermal decomposition reaction part, B is an oxidizing agent supply part, and C is an oxygen permeable film. Carbon 1 is divided into precipitated carbon and char and coal. Precipitated carbon uses aromatic or aliphatic hydrocarbons as a generation source, and by adsorbing on the wall surface, it facilitates the transfer of electrons and becomes a polymer of carbon. It is chemically deposited on the side of the thermal decomposition reaction part A of the oxygen permeable film C. Char and coal physically adhere to the pyrolysis reaction section A side using tar as a binder. Usually, the deposited carbon is used as a stepping stone to grow while increasing the layer thickness of the entire carbon content. In the case of the present invention, since the oxygen permeable film contains oxygen as a composition and a metal whose oxygen number is easily changed is used, the charge is easily changed (when lead is used, metallic lead (0) -lead oxide (+2) is used).
-Lead dioxide (+4), when tin is used, metal tin (0) -tin monoxide (+2) -tin dioxide (+4)),
Oxygen in the oxide is energetically unstable and easily reacts.
Therefore, a chemical reaction with the carbon content occurs, and carbon monoxide 2 is diffused into the thermal decomposition reaction part A. Since oxygen is used in the reaction, the oxygen concentration in the thermal decomposition reaction section A side and the oxygen concentration in the oxidant supply section B side have a gradient. Since the oxygen permeable film C itself is a continuous molecule, movement 5 of oxygen ions occurs from the high-concentration oxidant supply section B side to the low-concentration thermal decomposition reaction section A side. At this time, since the amount of oxygen in the oxygen permeable film C decreases, the overall charge balance is disrupted (reduced state), and the surface on the oxidant supply unit B side easily receives oxygen. Oxidizer 4
Is adsorbed on the oxidant supply part B side of the oxygen permeable film C, is absorbed as oxygen of the metal oxide, and is electrically balanced.
The supplied oxidant 4 is preferably oxygen from the viewpoint of reactivity, but is not particularly limited as long as it is a molecule containing an oxygen atom. The reaction rate of carbon content largely depends on the material because the oxygen supply rate, that is, the oxygen transfer rate in the oxygen permeable film C, determines the overall rate. Among them, oxides of Pb and Sn have a plurality of states with high bond stability (0 valence, 2 valences, 4 valences), and because the phase transition energy between the stable states is small, oxygen ions easily move. Since it has, it is advantageous in terms of oxygen transfer in the oxide.
【００１０】酸素透過膜Ｃから供給される酸素量は基本
的には析出、付着炭素を酸化してガス化する最小限、即
ち一酸化炭素生成に必要な酸素：炭素＝１：１モル比で
良い。不必要に多く酸素が存在すると、気相中の含水素
基や含炭素基と反応してしまうし、不足すると析出、付
着炭素が成長してしまう。従来の石炭急速熱分解では、
石炭種にも大きく影響されるが、平均して投入石炭の３
〜４ｗｔ％程度を最大とした付着が観察されており、原
子数換算では４〜５％にもなる。酸素供給は酸化物中の
酸素移動速度と酸化物膜厚でほぼ決るが、この温度領域
では比較的速く、ＰｂやＳｎでは含酸素ガス供給量で決
まると考えて良い。即ち、供給石炭中の炭素原子数の５
％以上の酸素原子供給速度が適切である。The amount of oxygen supplied from the oxygen permeable film C is basically the minimum amount for precipitation and oxidation of adhered carbon to gasify, that is, at the oxygen: carbon = 1: 1 molar ratio necessary for carbon monoxide production. good. If there is an unnecessarily large amount of oxygen, it reacts with the hydrogen-containing groups and carbon-containing groups in the gas phase, and if insufficient, precipitation and adhered carbon will grow. In conventional coal rapid pyrolysis,
Depending on the type of coal, it is 3
Adhesion with a maximum of about 4 wt% is observed, which is 4 to 5% in terms of the number of atoms. The oxygen supply is almost determined by the oxygen transfer rate in the oxide and the oxide film thickness, but it is relatively fast in this temperature range, and it can be considered that it is determined by the oxygen-containing gas supply amount for Pb and Sn. That is, the number of carbon atoms in the supplied coal is 5
An oxygen atom supply rate of not less than% is suitable.
【００１１】従来の急速熱分解装置の熱分解部では、付
着や析出トラブル、炉内耐火物強度の低下を防ぐため内
壁はなめらかで突起や複雑な形状は好まれなかった。本
発明の利点の一つとして、酸素透過膜を使用する事で形
状にこだわらなくても良くなったことが挙げられる。即
ち、図２に示した円筒状のもの、図３に示した複雑な絞
りの入ったものなどが該当する。図２では、二重円筒の
外筒部６と内筒部を兼ねた酸素透過膜Ｃの間が酸化剤供
給部Ｂとなり酸化ガスが流通し、内筒部内が熱分解反応
部Ａとなって熱分解反応が起こる。図３は図２と基本的
ガス流れは同じだが、形状が複雑になっており、断面積
を絞ることによって流速を増してタール凝縮を防止でき
る効果が期待されるにもかかわらず、炭素分析出・付着
の弊害により使用されなかったタイプである。In the thermal decomposition section of the conventional rapid thermal decomposition apparatus, in order to prevent adhesion and precipitation troubles and decrease in the strength of the refractory in the furnace, the inner wall is smooth, and projections and complicated shapes are not preferred. One of the advantages of the present invention is that the use of the oxygen permeable membrane eliminates the need for sticking to the shape. That is, the cylindrical shape shown in FIG. 2 and the complicated diaphragm shown in FIG. 3 are applicable. In FIG. 2, the oxidant supply section B serves as the oxidant supply section B between the double cylinder outer cylinder section 6 and the oxygen permeable membrane C also serving as the inner cylinder section, and the inside of the inner cylinder section serves as the thermal decomposition reaction section A. A thermal decomposition reaction occurs. Although FIG. 3 has the same basic gas flow as FIG. 2, it has a complicated shape, and although it is expected that the flow velocity can be increased and the tar condensation can be prevented by narrowing the cross-sectional area, carbon analysis can be performed. -It is a type that was not used due to the adverse effect of adhesion.
【００１２】[0012]
【実施例】表１で、図２に示した円筒状の熱分解反応部
を使用した本発明による石炭急速熱分解装置での析出・
付着物データと、図４で示した構成の、従来の石炭急速
熱分解装置での析出・付着物データを、反応温度７００
℃、反応時間４時間、太平洋炭という条件で比較した。
数値は、挿入石炭に対する析出・付着物の重量％、熱分
解部酸素ガス体積濃度である。本発明例１は、酸化剤ガ
スに空気を使用した結果である。本発明例２は、酸化剤
ガスとして１００％酸素を使用した結果である。酸素透
過膜には、ポーラスなアルミナ円筒管に硝酸鉛を塗布
し、窒素焼成して酸化鉛にしたものを使用した。アルミ
ナ円筒管の肉厚は約１ｍｍである。アルミナ細孔中に酸
化鉛が存在するため正確な膜厚が測定できないが、この
肉厚の分は連続するため、１ｍｍを近似膜厚と考える。
本発明例１、２とも、従来と比較して析出炭素分が少な
く、特に本発明例２は劇的に炭素分除去効果があった。
また本発明例１、２とも内筒への酸素流出はみられず、
酸素ガスの直接的な通過は見られなかった。[Examples] In Table 1, deposition / deposition in a coal rapid pyrolysis apparatus according to the present invention using the cylindrical pyrolysis reaction section shown in FIG.
The deposit data and the deposit / attachment data in the conventional coal rapid thermal decomposition apparatus having the configuration shown in FIG.
The comparison was made under the conditions of ℃, reaction time of 4 hours, and Pacific charcoal.
The numerical values are the weight% of the deposit / adhered matter with respect to the inserted coal and the oxygen gas volume concentration of the thermal decomposition part. Inventive Example 1 is the result of using air as the oxidant gas. Inventive Example 2 is the result of using 100% oxygen as the oxidant gas. As the oxygen permeable film, a porous alumina cylindrical tube coated with lead nitrate and baked in nitrogen to obtain lead oxide was used. The wall thickness of the alumina cylindrical tube is about 1 mm. An accurate film thickness cannot be measured because lead oxide exists in the alumina pores, but since this thickness is continuous, 1 mm is considered as an approximate film thickness.
In both Inventive Examples 1 and 2, the precipitated carbon content was smaller than that in the prior art, and in particular, Inventive Example 2 had a dramatic carbon content removing effect.
In addition, in each of Invention Examples 1 and 2, no oxygen outflow to the inner cylinder was observed,
No direct passage of oxygen gas was observed.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表２に、鉛、スズの酸化物と亜鉛、鉄、ア
ンチモンの酸化物を取り上げ、表１と同様の条件で比較
を行なった。ポーラスアルミナ円筒管を担体として硝酸
塩塗布、焼成で作成し、アルミナ単体でのデータも示し
た。鉛、スズは明らかに他の３種より炭素除去性能に優
れることがわかる。Table 2 shows oxides of lead and tin and oxides of zinc, iron and antimony, and a comparison was made under the same conditions as in Table 1. Data was also shown for alumina alone, which was prepared by coating a nitrate with a porous alumina cylindrical tube as a carrier and firing. It can be seen that lead and tin are clearly superior to the other three in carbon removal performance.
【００１５】[0015]
【表２】 [Table 2]
【００１６】ここでプロセスとして使用することを考え
ると、酸化剤としては酸素よりも空気の方が安価で入手
しやすいため妥当であると考えられ、将来的にはボイラ
ー燃焼排ガスや焼却炉ガス等の塵芥を含み水分の多いダ
ーティな酸素含有ガスから熱と酸素を使用する手段とし
て期待できるため、酸素濃度が低くても応用できるよう
に酸素透過膜の膜厚を薄くするなどの方向が好ましいと
考える。Considering its use as a process here, air is considered to be appropriate as an oxidizer because it is cheaper and more readily available than oxygen, and in the future, it will be appropriate to use boiler combustion exhaust gas, incinerator gas, etc. Since it can be expected as a means of using heat and oxygen from a dirty oxygen-containing gas that contains dust and contains a lot of water, it is preferable to reduce the thickness of the oxygen permeable film so that it can be applied even if the oxygen concentration is low. Think
【００１７】[0017]
【発明の効果】酸素透過膜を介して酸素を酸化物内イオ
ンの形で供給することにより、熱分解反応系内に酸素が
流出すること無しに析出、付着炭素分を除去できた。Effects of the Invention By supplying oxygen in the form of ions in the oxide through the oxygen permeable membrane, it was possible to remove the deposited and adhered carbon content without flowing oxygen into the thermal decomposition reaction system.
【図１】は、本発明に関わる酸素透過概念を示す酸素透
過膜の断面図、FIG. 1 is a sectional view of an oxygen permeable membrane showing the concept of oxygen permeation according to the present invention,
【図２】は、円筒状酸素透過膜型熱分解部の概略図、FIG. 2 is a schematic view of a cylindrical oxygen permeable membrane type pyrolysis unit,
【図３】は、絞り込み式酸素透過膜型熱分解部の概略
図、FIG. 3 is a schematic view of a narrowing-down type oxygen permeable membrane type thermal decomposition unit,
【図４】は、石炭急速熱分解装置における工程の概要図
である。FIG. 4 is a schematic view of steps in a coal rapid thermal decomposition apparatus.
Ａ…熱分解反応部、 Ｂ…酸化剤供給部、
Ｃ…酸素透過膜、１…炭素分、 ２
…一酸化炭素、３…酸素イオン、 ４…
酸化剤、５…イオン移動方向、 ６…二層構
造外層部、７…熱分解部、 ８…高温
ガス供給装置、９…石炭供給装置、 １０…
固体分離装置、１１…気液分離装置。A ... Pyrolysis reaction section, B ... Oxidizing agent supply section,
C ... Oxygen permeable membrane, 1 ... Carbon content, 2
… Carbon monoxide, 3… Oxygen ions, 4…
Oxidizer, 5 ... Ion migration direction, 6 ... Two-layer structure outer layer part, 7 ... Pyrolysis part, 8 ... High temperature gas supply device, 9 ... Coal supply device, 10 ...
Solid separation device, 11 ... Gas-liquid separation device.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小水流 広行 千葉県富津市新富20−１ 新日本製鐵株式 会社技術開発本部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Komizu, 20-1 Shintomi, Futtsu City, Chiba Shin Nippon Steel Co., Ltd.
Claims (8)
熱分解させる石炭急速熱分解装置において、析出または
付着した炭素分を、６００℃から１０００℃の温度範囲
で、酸素透過膜を介して含酸素ガスから供給した酸素で
酸化することを特徴とする炭素分除去方法。1. A rapid coal pyrolysis apparatus for blowing coal into a high-temperature gas stream for rapid thermal decomposition, in which a deposited or adhering carbon content is contained in a temperature range of 600 ° C. to 1000 ° C. through an oxygen permeable membrane. A method for removing carbon, comprising oxidizing with oxygen supplied from oxygen gas.
解部が酸素透過膜よりなる内層部と、熱分解部外壁であ
る外層部からなる二層構造であることを特徴とする炭素
分除去装置。2. The carbon content removing device in the rapid coal pyrolysis apparatus, wherein the pyrolysis section has a two-layer structure including an inner layer section made of an oxygen permeable membrane and an outer layer section which is an outer wall of the pyrolysis section. .
の酸化物であることを特徴とする請求項１に記載の炭素
分除去方法。3. The carbon content removing method according to claim 1, wherein the oxygen permeable film is an oxide of a metal having a plurality of ionic valences.
の酸化物であることを特徴とする請求項２に記載の炭素
分除去装置。4. The carbon content removing device according to claim 2, wherein the oxygen permeable film is an oxide of a metal having a plurality of ionic valences.
あることを特徴とする請求項１に記載の炭素分除去方
法。5. The carbon content removing method according to claim 1, wherein the oxygen permeable film is an oxide of Pb or Sn.
あることを特徴とする請求項２に記載の炭素分除去装
置。6. The carbon content removing device according to claim 2, wherein the oxygen permeable film is an oxide of Pb or Sn.
ＣＯ2 、ＮＯ、ＮＯ2 、Ｎ2 Ｏ、ＳＯ2 、ＳＯ3 、ＣＨ
3 ＯＨ、Ｃ2 Ｈ5 ＯＨのいずれか１種類のガスまたは２
種類以上の組み合せで混合した含酸素ガスを使用し、含
酸素ガス中の酸素原子数が、前記熱分解部へ供給する石
炭中の炭素原子数の５％以上の速度で供給されることを
特徴とする請求項１、３または５のいずれかに記載の炭
素分除去方法。7. The oxygen-containing gas is O 2 , air, CO,
CO 2 , NO, NO 2 , N 2 O, SO 2 , SO 3 , CH
Any one gas of 3 OH and C 2 H 5 OH or 2
An oxygen-containing gas mixed in a combination of more than one kind is used, and the number of oxygen atoms in the oxygen-containing gas is supplied at a rate of 5% or more of the number of carbon atoms in the coal supplied to the thermal decomposition section. The method for removing carbon according to claim 1, 3, or 5.
ＣＯ2 、ＮＯ、ＮＯ2 、Ｎ2 Ｏ、ＳＯ2 、ＳＯ3 、ＣＨ
3 ＯＨ、Ｃ2 Ｈ5 ＯＨのいずれか１種類のガスまたは２
種類以上の組み合せで混合した含酸素ガスを使用し、含
酸素ガス中の酸素原子数が、前記熱分解部へ供給する石
炭中の炭素原子数の５％以上の速度で供給されることを
特徴とする請求項２、４または６のいずれかに記載の炭
素分除去方法。8. The oxygen-containing gas is O 2 , air, CO,
CO 2 , NO, NO 2 , N 2 O, SO 2 , SO 3 , CH
Any one gas of 3 OH and C 2 H 5 OH or 2
An oxygen-containing gas mixed in a combination of more than one kind is used, and the number of oxygen atoms in the oxygen-containing gas is supplied at a rate of 5% or more of the number of carbon atoms in the coal supplied to the thermal decomposition section. The method for removing carbon according to claim 2, 4, or 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33469192A JPH06179882A (en) | 1992-12-15 | 1992-12-15 | Method and apparatus for eliminating carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33469192A JPH06179882A (en) | 1992-12-15 | 1992-12-15 | Method and apparatus for eliminating carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06179882A true JPH06179882A (en) | 1994-06-28 |
Family
ID=18280150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33469192A Withdrawn JPH06179882A (en) | 1992-12-15 | 1992-12-15 | Method and apparatus for eliminating carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06179882A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009298632A (en) * | 2008-06-12 | 2009-12-24 | Ihi Corp | Separation method of hydrogen and carbon dioxide and separation device of hydrogen and carbon dioxide |
-
1992
- 1992-12-15 JP JP33469192A patent/JPH06179882A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009298632A (en) * | 2008-06-12 | 2009-12-24 | Ihi Corp | Separation method of hydrogen and carbon dioxide and separation device of hydrogen and carbon dioxide |
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