JP3159133B2 - Method for removing chlorine from chlorine-containing polymer resin - Google Patents
Method for removing chlorine from chlorine-containing polymer resinInfo
- Publication number
- JP3159133B2 JP3159133B2 JP18929197A JP18929197A JP3159133B2 JP 3159133 B2 JP3159133 B2 JP 3159133B2 JP 18929197 A JP18929197 A JP 18929197A JP 18929197 A JP18929197 A JP 18929197A JP 3159133 B2 JP3159133 B2 JP 3159133B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- treated
- resin
- resin material
- containing polymer
- 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 - Fee Related
Links
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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Fire-Extinguishing Compositions (AREA)
- Incineration Of Waste (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化ビニル等の含
塩素高分子樹脂から塩素を除去するための含塩素高分子
樹脂の脱塩素方法に関する。BACKGROUND OF THE INVENTION The present invention provides a chlorine-containing polymer to remove chlorine from the chlorine-containing polymer resin such as vinyl chloride
The present invention relates to a method for dechlorinating a resin .
【０００２】[0002]
【従来の技術】近年、産業廃棄物や一般廃棄物としてプ
ラスチック等の合成樹脂類が急増しており、その処理が
大きな問題となっている。なかでも高分子系の炭化水素
化合物であるプラスチックは燃焼時に発生する熱量が高
く、焼却処理した場合に焼却炉を傷めるために大量処理
が困難であり、その多くがごみ埋立地等に投棄されてい
るのが現状である。しかし、プラスチック等の投棄は環
境対策上好ましくなく、また昨今では埋立用の用地不足
が社会問題となりつつあり、このため投棄によらない合
成樹脂類の大量処理方法の開発が切望されている。2. Description of the Related Art In recent years, synthetic resins such as plastics have rapidly increased as industrial wastes and general wastes, and their disposal has become a major problem. Among these, plastics, which are high-molecular hydrocarbon compounds, generate a large amount of heat during combustion, and when incinerated, damage to the incinerator makes mass treatment difficult, and most of them are dumped in landfills. That is the current situation. However, dumping of plastics and the like is not preferable in terms of environmental measures, and in recent years, the shortage of land for landfill has become a social problem. For this reason, development of a method for mass processing of synthetic resins without dumping has been desired.
【０００３】このような背景の下、プラスチック等の合
成樹脂類を高炉等の補助燃料或いは鉄源の還元剤として
用いる方法が、例えば欧州特許公開公報第０６２２４６
５Ａ１号や特公昭５１−３３４９３号公報に示されてい
る。しかし、廃棄合成樹脂類中には塩化ビニル樹脂等の
含塩素高分子樹脂が平均して約１５％も含まれると言わ
れており、このような合成樹脂類を高炉等に供給した場
合には、含塩素高分子樹脂の熱分解や燃焼により多量の
有害ガス（ＨＣｌ）が発生し、著しい環境汚染を生じさ
せる。したがって、このような有害ガスの発生を防止す
るためには、事前に合成樹脂類から含塩素高分子樹脂を
分離除去し、この分離除去された含塩素高分子樹脂から
塩素分を除去する必要がある。Against this background, a method of using synthetic resins such as plastics as an auxiliary fuel for a blast furnace or the like or a reducing agent for an iron source has been proposed, for example, in EP-A-0 622 246.
5A1 and JP-B-51-33493. However, it is said that waste synthetic resins contain about 15% of chlorine-containing polymer resin such as vinyl chloride resin on average, and when such synthetic resins are supplied to a blast furnace or the like, In addition, a large amount of harmful gas (HCl) is generated due to thermal decomposition and combustion of the chlorine-containing polymer resin, causing significant environmental pollution. Therefore, in order to prevent the generation of such harmful gases, it is necessary to separate and remove the chlorine-containing polymer resin from the synthetic resins in advance, and to remove chlorine from the separated and removed chlorine-containing polymer resin. is there.
【０００４】従来、含塩素高分子樹脂を脱塩素処理する
ための方法として、図８に示すようなロータリーキルン
を用いる方法が知られている。この方法はロータリーキ
ルンＢの内部に含塩素高分子樹脂材と熱媒体である砂を
供給するとともに、熱源として加熱ガスを供給するもの
で、含塩素高分子樹脂はキルンの回転により砂と混合さ
れつつ約２５０〜３５０℃程度に加熱され、この加熱に
よって樹脂中の塩素分が塩化水素として脱離する脱離反
応が生じ、塩化水素ガスが発生する。この塩化水素ガス
は加熱ガスとともにキルン外に排出され、また、脱塩素
処理が完了した含塩素高分子樹脂の残渣（樹脂の残留固
形物）も熱媒体である砂とともにキルン外に排出され
る。Conventionally, as a method for dechlorinating a chlorine-containing polymer resin, a method using a rotary kiln as shown in FIG. 8 is known. In this method, a chlorine-containing polymer resin material and sand as a heat medium are supplied into the rotary kiln B, and a heating gas is supplied as a heat source. The chlorine-containing polymer resin is mixed with the sand by the rotation of the kiln. The resin is heated to about 250 to 350 ° C., and this heating causes a elimination reaction in which chlorine in the resin is eliminated as hydrogen chloride, and hydrogen chloride gas is generated. This hydrogen chloride gas is discharged to the outside of the kiln together with the heating gas, and the residue of the chlorine-containing polymer resin (residual solid matter of the resin) after the dechlorination treatment is also discharged to the outside of the kiln together with sand as a heat medium.
【０００５】[0005]
【発明が解決しようとする課題】しかし、このようなロ
ータリーキルンを用いた従来の塩素除去方法では、発生
した塩化水素が加熱ガスと混合した状態で炉外に排出さ
れ、しかもこの排出ガスは膨大な量であるため、排出ガ
スから塩化水素を分離除去するための大規模な設備が必
要であり、またその処理自体にも多大なコストがかか
る。また、塩化水素は３５０℃を超えるような高温域以
外に１５０℃以下の温度域でも高い腐食性を示すという
特徴がある。そして、図８に示すような従来使用されて
いるロータリーキルンでは、壁体を構成する耐火物の内
壁面の温度は処理温度と略同等であるが、壁体の外側は
常温であるため耐火物の厚さ方向で温度勾配が生じ、鉄
皮内面付近が露点（１５０℃）以下となる。このため、
耐火物内部に浸透した塩化水素により鉄皮等が腐食する
という大きな問題がある。However, in the conventional chlorine removing method using such a rotary kiln, the generated hydrogen chloride is discharged outside the furnace in a state of being mixed with a heating gas, and the discharged gas is enormous. Because of the volume, a large-scale facility for separating and removing hydrogen chloride from the exhaust gas is required, and the treatment itself is very costly. Further, hydrogen chloride is characterized in that it exhibits high corrosiveness even in a temperature range of 150 ° C. or less, in addition to a high temperature range exceeding 350 ° C. In a conventional rotary kiln as shown in FIG. 8, the temperature of the inner wall surface of the refractory constituting the wall is substantially equal to the treatment temperature, but the temperature of the outside of the wall is room temperature, so A temperature gradient occurs in the thickness direction, and the temperature near the inner surface of the steel shell becomes lower than the dew point (150 ° C.). For this reason,
There is a major problem that hydrogen chloride and the like are corroded by the hydrogen chloride that has penetrated inside the refractory.
【０００６】また、従来の方法では樹脂材とともにキル
ンに装入する熱媒体として主に砂が用いられているが、
砂は樹脂材と粒度や比重が大きく異なるためキルン内で
偏析し易く、このため熱媒体として有効に機能せず、処
理効率が低いという問題がある。また、脱塩素処理され
た樹脂材の残渣を高炉等の溶解炉の吹き込み若しくは装
入原料（主として、鉄源の還元剤や燃料）として用いる
ことを前提とした場合、熱媒体として砂を用いる従来技
術では脱塩素処理が完了した樹脂材の残渣から砂を分離
する必要があり、この処理のために設備コストや処理コ
ストの増大を招くという問題もある。In the conventional method, sand is mainly used as a heat medium to be charged into the kiln together with the resin material.
Sand has a problem that it tends to segregate in the kiln because it has a large difference in particle size and specific gravity from the resin material, and thus does not function effectively as a heat medium and has a low treatment efficiency. In addition, when it is assumed that the residue of the dechlorinated resin material is blown into a melting furnace such as a blast furnace or used as a charging material (mainly a reducing agent or fuel for an iron source), a conventional method using sand as a heat medium is used. In the technology, it is necessary to separate sand from the residue of the resin material after the dechlorination treatment is completed, and there is a problem that this treatment causes an increase in equipment cost and treatment cost.
【０００７】したがって本発明の目的は、このような従
来技術の問題を解決し、ロータリーキルン方式による塩
素除去装置を用いた含塩素高分子樹脂の塩素除去方法に
おいて、発生した塩化水素を加熱ガスと混合させること
なく取り出すことができること、塩化水素による腐食等
の問題を生じないこと、さらに、脱塩素処理後の樹脂材
の残渣から熱媒体を分離することなく、そのまま炉用の
原料として用いることを可能とする含塩素高分子樹脂の
塩素除去方法を提供することにある。Accordingly, an object of the present invention is to solve such a problem of the prior art, and to solve the problem by using a rotary kiln system .
Removal method for chlorine-containing polymer resin using element removal equipment
That the generated hydrogen chloride can be taken out without mixing with the heating gas, corrosion by hydrogen chloride, etc.
It does not cause problems, further, without separating the heating medium from the residue of the resin material after dechlorination, provide chlorine removal process of chlorine-containing polymer resin which enables to use it as a raw material for the furnace Is to do.
【０００８】[0008]
【課題を解決するための手段】このような課題を解決す
るための本発明の特徴は以下の通りである。 [1] 装置本体を外管とその内部に配置される内管とから
構成し、内管内を被処理樹脂材用の通路とするととも
に、内管と外管間の空間を加熱ガス用の通路としたロー
タリーキルン方式の塩素除去装置を用い、被処理樹脂材
および熱媒体と加熱ガスを装置本体の一端側から前記被
処理樹脂材用の通路と加熱ガス用の通路にそれぞれ供給
し、装置本体の前記一端側から他端側方向に移送される
被処理樹脂材および熱媒体を、装置本体の前記一端側か
ら他端側方向に流れる加熱ガスにより内管の管壁を通じ
て加熱して樹脂中の塩素分を塩化水素ガスとして脱離さ
せることにより被処理樹脂材を脱塩素処理し、溶解炉供
給用の脱塩素処理された樹脂残渣を得る含塩素高分子樹
脂の塩素除去方法であって、脱塩素処理された樹脂残渣
とともに塩素除去装置外に取り出される熱媒体として、
溶解炉用の原料又は燃料として使用可能な材料である、
粉鉱石、焼結粉、溶解炉用の鉄源還元剤の粉粒物、溶解
炉用の燃料の粉粒物、溶解炉用の副原料の粉粒物の中か
ら選ばれる１種以上を用い、被処理樹脂材用の通路内で
の被処理樹脂材の加熱温度を２５０〜３５０℃とするこ
とを特徴とする含塩素高分子樹脂の塩素除去方法。The features of the present invention for solving such a problem are as follows. [1] The apparatus body is composed of an outer tube and an inner tube disposed inside the inner tube, and the inside of the inner tube is used as a passage for the resin material to be treated, and the space between the inner tube and the outer tube is used as a passage for the heating gas. Using a rotary kiln type chlorine removing device, a resin material to be treated and a heating medium and a heating gas are supplied from one end side of the device body to a passage for the resin material to be treated and a passage for heating gas, respectively. The resin material to be processed and the heat medium transferred from the one end side to the other end side are heated through the inner wall of the inner tube by a heating gas flowing from the one end side to the other end side of the apparatus main body, and chlorine in the resin is heated. min a treated resin material to dechlorination, melting furnace dechlorination treated chlorine removal process of chlorine-containing polymer resin to obtain a resin residue for supply by desorbed as hydrogen chloride gas, dechlorination Processed resin residue
As the heat medium to be taken out of the chlorine removal device with,
It is a material that can be used as a raw material or fuel for melting furnaces.
Using at least one selected from powder ore, sintered powder, powder of iron source reducing agent for melting furnace, powder of fuel for melting furnace, and powder of auxiliary material for melting furnace A method for removing chlorine from a chlorine-containing polymer resin, wherein the heating temperature of the resin material to be treated in the passage for the resin material to be treated is 250 to 350 ° C.
【０００９】[2] 上記[1]の方法において、被処理樹脂
材用の通路内にキャリアガスを通気させることを特徴と
する含塩素高分子樹脂の塩素除去方法。 [3] 上記[1]または[2]の方法において、熱媒体が、粉コ
ークス、粉鉱石、焼結粉および粉粒状熱硬化性樹脂の中
から選ばれる１種以上の粉粒物であることを特徴とする
含塩素高分子樹脂の塩素除去方法。 [4] 上記[3]の方法において、熱媒体が、粉コークスお
よび粉粒状熱硬化性樹脂の中から選ばれる１種以上の粉
粒物であることを特徴とする含塩素高分子樹脂の塩素除
去方法。 [2] In the method of the above [1], the resin to be treated
Characterized by venting carrier gas into the material passage
To remove chlorine from chlorine-containing polymer resin. [3] The method according to the above [1] or [2], wherein the heat medium is a powder core.
Ore, ore, sinter powder and powdery thermosetting resin
Characterized in that it is at least one kind of powdery material selected from
Method for removing chlorine from chlorine-containing polymer resin. [4] In the method of the above [3], the heat medium is coke breeze or coke breeze.
And one or more powders selected from thermosetting resins and powdery granules
Chlorine removal of chlorine-containing polymer resin characterized by being granular
How to leave.
【００１０】[5] 上記[1]〜[4]のいずれかの方法におい
て、装置本体が、外管とその内部に配置される単一の内
管とから構成された塩素除去装置を用いて被処理樹脂材
の脱塩素処理を行うことを特徴とする含塩素高分子樹脂
の塩素除去方法。 [6] 上記[1]〜[4]のいずれかの方法において、装置本体
が、外管とその内部に配置される複数の内管とから構成
された塩素除去装置を用いて被処理樹脂材の脱塩素処理
を行うことを特徴とする含塩素高分子樹脂の塩素除去方
法。 [7] 上記[1]〜[6]のいずれかの方法において、内管の内
部に加熱ガス用のガス導管が配置された塩素除去装置を
用いて被処理樹脂材の脱塩素処理を行うことを特徴とす
る含塩素高分子樹脂の塩素除去方法。 [5] The method according to any one of the above [1] to [4]
The main body of the device is an outer tube and a single
Resin material to be treated using a chlorine removal device composed of pipes
-Containing polymer resin characterized by dechlorination
Chlorine removal method. [6] The method according to any one of [1] to [4] above,
Consists of an outer tube and multiple inner tubes
Treatment of the resin material to be treated using the chlorine removal equipment
For removing chlorine from chlorine-containing polymer resin
Law. [7] The method according to any one of [1] to [6] above, wherein
A chlorine removal device with a gas conduit for heating gas
Dechlorination treatment of the resin material to be treated by using
For removing chlorine from chlorine-containing polymer resins.
【００１１】[8] 上記[1]〜[7]のいずれかの方法におい
て、外管および内管が一体に回転するように構成された
塩素除去装置を用いて被処理樹脂材の脱塩素処理を行う
ことを特徴とする含塩素高分子樹脂の塩素除去方法。 [9] 上記[1]〜[7]のいずれかの方法において、内管のみ
が回転するように構成された塩素除去装置を用いて被処
理樹脂材の脱塩素処理を行うことを特徴とする含塩素高
分子樹脂の塩素除去方法。 本発明法では、 被処理材に塩
素含有樹脂以外の樹脂類、塩素含有樹脂と他の素材との
複合材、樹脂以外の素材が含まれることを妨げない。 [8] The method according to any one of the above [1] to [7]
And the outer tube and the inner tube are configured to rotate integrally.
Dechlorinating the resin material to be treated using a chlorine removal device
A method for removing chlorine from a chlorine-containing polymer resin. [9] In any of the above methods [1] to [7], only the inner tube is used.
Treated using a chlorine removal device configured to rotate
High chlorine content characterized by dechlorination of resin
Method for removing chlorine from molecular resin. The method of the present invention does not prevent the target material from containing a resin other than the chlorine-containing resin, a composite material of the chlorine-containing resin and another material, and a material other than the resin.
【００１２】[0012]
【発明の実施の形態】図１および図２は本発明法に使用
される塩素除去装置の一実施形態を示すもので、Ａは装
置本体、１はこれを構成する外管、２は同じく内管であ
り、この内管２は外管１の内部長手方向に外管１と略同
芯状に配置されている。そして、内管２の内部が被処理
材（以下、被処理材が実質的に樹脂材のみからなる場合
を例に述べる）の通路３（処理用空間）を構成し、また
外管１と内管２の間の空間が加熱ガスの通路４を構成し
ている。1 and 2 are used in the method of the present invention .
1 shows an embodiment of a chlorine removing apparatus to be used, wherein A is an apparatus main body, 1 is an outer tube constituting the same, 2 is also an inner tube, and the inner tube 2 is formed in the inner longitudinal direction of the outer tube 1. It is arranged substantially concentrically with the outer tube 1. The inside of the inner tube 2 constitutes a passage 3 (processing space) for a material to be treated (hereinafter, a case where the material to be treated is substantially composed of only a resin material). The space between the tubes 2 forms a passage 4 for the heating gas.
【００１３】図３および図４は塩素除去装置の他の実施
形態を示すもので、図１および図２では外管内に単一の
内管を配置した構造としたのに対し、外管１内に複数の
内管２ａ〜２ｃを設けたものである。なお、外管１内に
配置する内管２の数は任意である。このような構造で
は、内管を複数本設けるためにそれだけ伝熱面積が大き
くなり、このため通路４を流れる加熱ガスから内管内へ
の熱伝達が効率的に行える利点があり、また、処理すべ
き樹脂材と熱媒体の配合比や種類を各内管毎に変えるこ
とができるため、例えば、粒径が大きく処理効率の劣る
樹脂材については熱媒体の配合比を多くし、一方、粒径
が小さく処理効率が高い樹脂材については熱媒体の配合
比を少なくした上で、それぞれを別々の内管に供給して
処理する、というような操業も可能である。FIGS. 3 and 4 show another embodiment of the chlorine removing apparatus . In FIGS. 1 and 2, a single inner pipe is arranged in the outer pipe. Are provided with a plurality of inner tubes 2a to 2c. In addition, the number of the inner tubes 2 arranged in the outer tube 1 is arbitrary. In such a structure, since a plurality of inner pipes are provided, the heat transfer area becomes larger accordingly, and therefore, there is an advantage that heat can be efficiently transferred from the heating gas flowing through the passage 4 into the inner pipes. Since the mixing ratio and type of the resin material to be heated and the heating medium can be changed for each inner tube, for example, the mixing ratio of the heating medium is increased for a resin material having a large particle size and inferior processing efficiency, while the particle size is increased. For a resin material having a small processing efficiency and a high processing efficiency, it is possible to reduce the mixing ratio of the heat medium, and then supply each to a separate inner tube for processing.
【００１４】図５は、塩素除去装置の他の実施形態を示
したもので、内管２の内部にガス導管５を配置し、被処
理樹脂材の加熱効率をさらに高めることができるように
したものである。なお、このようなガス導管は図３およ
び図４の装置の内管２ａ〜２ｃ内にも配置することがで
きる。FIG. 5 shows another embodiment of the chlorine removing apparatus , in which a gas conduit 5 is arranged inside the inner pipe 2 so that the heating efficiency of the resin material to be treated can be further increased. Things. Note that such a gas conduit can also be arranged in the inner pipes 2a to 2c of the apparatus shown in FIGS.
【００１５】図６は、図１および図２の構造を有するロ
ータリーキルンのより具体的な実施形態を示すもので、
内管２の一端側は外管１の外方に延出し、この内管２の
一端側にはスクリューフィーダ７を備えた定量供給装置
６が接続されている。そして、この定量供給装置６を通
じて内管内部の通路３に塩素含有樹脂を含む被処理材と
熱媒体が供給される。このような構造のロータリーキル
ンでは、図示しない回転駆動装置により内管２のみが回
転する。また、外管１の両端部は回転する内管２に対し
てシールされるとともに、外管１の一端側には外管１と
内管２との間に形成される通路４に加熱ガス（熱風）を
供給するための供給口８が、また他端側には加熱ガスの
排出口９がそれぞれ設けられている。FIG. 6 shows a more specific embodiment of the rotary kiln having the structure shown in FIGS. 1 and 2.
One end of the inner tube 2 extends outside the outer tube 1, and a fixed-quantity supply device 6 having a screw feeder 7 is connected to one end of the inner tube 2. Then, the material to be treated containing the chlorine-containing resin is supplied to the passage 3 inside the inner pipe through the fixed amount supply device 6.
A heating medium is supplied. In the rotary kiln having such a structure, only the inner tube 2 is rotated by a rotation driving device (not shown). Both ends of the outer tube 1 are sealed with respect to the rotating inner tube 2, and one end of the outer tube 1 is connected to a passage 4 formed between the outer tube 1 and the inner tube 2 by heating gas ( A supply port 8 for supplying hot air) is provided, and a discharge port 9 for heating gas is provided on the other end side.
【００１６】本発明法が使用する装置はロータリーキル
ン方式の塩素除去装置であるが、実質的には内管２，２
ａ〜２ｃがその周方向で回転しさえすれば、被処理樹脂
材の脱塩素処理を何ら支障なく行うことができる。した
がって、塩素除去装置は、外管１を含めた装置本体Ａの
全体をその周方向で回転可能に構成してもよいが、内管
２，２ａ〜２ｃのみをその周方向で回転可能に構成して
もよい。また、図３および図４の装置の場合には、内管
２ａ〜２ｃを一体的に回転（したがって、この場合には
装置本体Ａを回転させる場合と同様、個々の内管は偏心
回転する）させてもよいし、また、各内管２ａ〜２ｃを
個別に回転させてもよい。The apparatus used in the method of the present invention is a rotary kiln type chlorine removing apparatus.
As long as a to 2c rotate in the circumferential direction, dechlorination of the resin material to be processed can be performed without any trouble. Therefore, the chlorine removing apparatus may be configured such that the entire apparatus main body A including the outer pipe 1 can be rotated in the circumferential direction, but only the inner pipes 2, 2a to 2c are configured to be rotatable in the circumferential direction. May be. In the case of the apparatus shown in FIGS. 3 and 4, the inner pipes 2a to 2c are integrally rotated (in this case, the individual inner pipes are eccentrically rotated as in the case of rotating the apparatus main body A). Alternatively, the inner tubes 2a to 2c may be individually rotated.
【００１７】次に、上述した塩素除去装置を用いた本発
明法について説明する。被処理樹脂材および熱媒体（粉
粒物）と加熱ガスは、装置本体Ａの一端側から図示しな
い供給機構を通じて通路３および通路４に供給される。
通路４に供給された加熱ガスは、内管２，２ａ〜２ｃの
全体を加熱し、その管壁を通じて被処理樹脂材および熱
媒体が加熱される。通路４を流れた加熱ガスは装置本体
Ａの他端側から排出される。Next, the present invention using the above-described chlorine removing apparatus
The light method will be described. The resin material to be processed, the heating medium (granules), and the heating gas are supplied to the passage 3 and the passage 4 from one end of the apparatus main body A through a supply mechanism (not shown).
The heating gas supplied to the passage 4 heats the entire inner pipes 2, 2a to 2c, and the resin material to be processed and the heat medium are heated through the pipe walls. The heated gas flowing through the passage 4 is discharged from the other end of the apparatus main body A.
【００１８】一方、内管２，２ａ〜２ｃ内部の通路３に
供給された被処理樹脂材は、内管２，２ａ〜２ｃの回転
によって熱媒体と混合され、且つ通路３を移送されつつ
加熱され、この加熱によって樹脂中の塩素分が塩化水素
として脱離し、塩化水素が発生する。なお、固体熱媒体
は被処理樹脂材を加熱するだけでなく、被処理樹脂材中
に分散して被処理樹脂材どうしの融着、塊状化を抑制
し、これらにより脱塩素効率を向上させる。このように
して脱塩素処理が完了した樹脂材（熱分解後の樹脂の残
渣）は熱媒体とともに装置本体Ａの他端側から排出さ
れ、同時に塩化水素も排出される。したがって、含塩素
高分子樹脂材の加熱によって発生した塩化水素は加熱ガ
スと混合することなく回収される。なお、被処理樹脂材
と熱媒体を通路３内で円滑に移動させるため、通路３内
に少量のキャリアガス（エア等）を通気させることがで
きる。On the other hand, the resin material to be processed supplied to the passage 3 inside the inner tubes 2, 2a to 2c is mixed with the heat medium by the rotation of the inner tubes 2, 2a to 2c, and heated while being transferred through the passage 3. This heating causes the chlorine content in the resin to be eliminated as hydrogen chloride, generating hydrogen chloride. In addition, the solid heat medium not only heats the resin material to be treated, but also disperses in the resin material to be treated, thereby suppressing fusion and agglomeration of the resin materials to be treated, thereby improving the dechlorination efficiency. The resin material (residue of the resin after thermal decomposition) that has been thus dechlorinated is discharged from the other end of the apparatus main body A together with the heat medium, and hydrogen chloride is also discharged at the same time. Therefore, hydrogen chloride generated by heating the chlorine-containing polymer resin material is recovered without mixing with the heated gas. In order to smoothly move the resin material to be processed and the heat medium in the passage 3, a small amount of carrier gas (such as air) can be passed through the passage 3.
【００１９】通路３内における含塩素高分子樹脂材の加
熱温度は２５０〜３５０℃、望ましくは３００℃前後と
することが好ましい。加熱温度が２５０℃未満では塩化
水素の脱離反応が効率的に行われず、一方、３５０℃を
超えると常温で液状またはガス状となる炭化水素への熱
分解が起こり始める。塩素除去装置では、内部で塩化水
素が発生する内管の外側を加熱ガスが流れ、したがって
内管全体が上述した２５０〜３５０℃程度の温度となる
ため、塩化水素が接触する部分には、塩化水素による腐
食作用が大きい１５０℃以下の温度領域は存在しない。
したがって、塩化水素による装置の腐食、特に内管各部
の腐食が適切に防止される。The heating temperature of the chlorine-containing polymer resin material in the passage 3 is preferably 250 to 350 ° C., more preferably about 300 ° C. If the heating temperature is lower than 250 ° C., the elimination reaction of hydrogen chloride is not efficiently performed. On the other hand, if the heating temperature is higher than 350 ° C., thermal decomposition into hydrocarbon which becomes liquid or gaseous at normal temperature starts to occur. In the chlorine removal device, the heating gas flows outside the inner tube in which hydrogen chloride is generated. Therefore, the temperature of the entire inner tube is about 250 to 350 ° C. There is no temperature region of 150 ° C. or less where the corrosive action by hydrogen is large.
Therefore, corrosion of the apparatus due to hydrogen chloride, particularly corrosion of each part of the inner pipe, is appropriately prevented.
【００２０】被処理樹脂材とともに通路３内に供給され
る熱媒体（粉粒物）としては、従来法のように砂等の粒
状物を用いることもできるが、脱塩素処理された樹脂材
の残渣を熱媒体と分離することなくそのまま高炉等の炉
（特に、溶解炉）に供給する場合には、熱媒体としては
炉用の原材料として使用可能なもの、具体的には炉の鉄
源、鉄源還元剤、燃料、副原料等として使用可能な粉粒
物を用いることが好ましい。これによって、脱塩素処理
を終えた樹脂材の残渣を熱媒体と分離することなく、そ
のまま溶解炉等に鉄源の還元剤や燃料として供給するこ
とができる。As the heating medium (powder and granule) supplied into the passage 3 together with the resin material to be treated, a granular material such as sand can be used as in the conventional method. When the residue is directly supplied to a furnace such as a blast furnace (particularly, a melting furnace) without being separated from the heating medium, a heating medium that can be used as a raw material for the furnace, specifically, an iron source of the furnace, It is preferable to use powders and granules that can be used as an iron source reducing agent, fuel, auxiliary raw material, and the like. Thus, the residue of the resin material after the dechlorination treatment can be supplied as it is to the melting furnace or the like as a reducing agent or fuel of the iron source without being separated from the heat medium.
【００２１】そのような熱媒体に適した粉粒物として
は、粉コークス、粉鉱石、焼結粉（焼結鉱の粉粒物）、
粉粒状熱硬化性樹脂（例えば、フェノール樹脂、ユリア
樹脂、ウレタン樹脂等）等が挙げられ、これらの１種以
上を熱媒体として使用することができる。また、通路３
内での熱媒体の偏析を防止して加熱効率を向上させるた
めには、熱媒体の粒径や比重が樹脂材になるべく近い方
が好ましく、このような観点からは熱媒体として粉コー
クスおよび／または粉粒状熱硬化性樹脂を使用すること
が最も好ましい。また、熱媒体として粉コークス、粉粒
状熱硬化性樹脂を用いることにより熱媒体の偏析が防止
される結果、樹脂材の低級炭化水素への分解も抑制され
る。Examples of the fine particles suitable for such a heat medium include coke breeze, fine ore, sintered powder (sinter ore fine particles),
Pulverized thermosetting resin (for example, phenol resin, urea resin, urethane resin, and the like) and the like can be used, and one or more of these can be used as a heat medium. Passage 3
In order to prevent the segregation of the heating medium in the inside and to improve the heating efficiency, it is preferable that the particle size and specific gravity of the heating medium be as close as possible to the resin material. From such a viewpoint, coke breeze and / or Alternatively, it is most preferable to use a particulate thermosetting resin. In addition, the use of coke breeze or a particulate thermosetting resin as a heat medium prevents segregation of the heat medium, thereby suppressing decomposition of the resin material into lower hydrocarbons.
【００２２】[0022]
【実施例】図７に示す塩素除去装置を用い、塩化ビニル
樹脂材の脱塩素処理を実施した。装置構成の概略は以下
の通りである。 ［装置構成］ キルン寸法（外管内径Ｄ２×全長Ｌ）：６００ｍｍφ×
３０００ｍｍ 内管寸法（内管内径Ｄ１×全長Ｌ）：４００ｍｍφ×３
０００ｍｍ 装置本体の傾斜角θ：５° 本実施例では塩素含有率：３５％、灰分：１．５％、粒
径１０〜２０ｍｍの塩化ビニル樹脂材の処理を行い、ま
た固体の熱媒体としては粉コークス（粒径１０ｍｍ以
下）を用いた。EXAMPLE A vinyl chloride resin material was dechlorinated using a chlorine removing apparatus shown in FIG. The outline of the device configuration is as follows. [Device Configuration] kiln dimensions (outer tube inner diameter D 2 × total length L): 600mmφ ×
3000mm in tube dimensions (inner tube inner diameter D 1 × total length L): 400mmφ × 3
In this embodiment, a vinyl chloride resin material having a chlorine content of 35%, an ash content of 1.5%, and a particle size of 10 to 20 mm is treated. Coke powder (particle size 10 mm or less) was used.
【００２３】脱塩素処理は塩化ビニル樹脂材供給量：５
０ｋｇ／ｈ，粉コークス供給量２０ｋｇ／ｈ（以上、実
施例１）と塩化ビニル樹脂材供給量：７０ｋｇ／ｈ，粉
コークス供給量：１０ｋｇ／ｈ（以上、実施例２）の２
水準で行い、塩化ビニル樹脂材と熱媒体（粉コークス）
のキルン内滞留時間が１５分程度となるようキルン回転
数等を調整した。また、内管内の通路には塩化ビニル樹
脂材と熱媒体の移動を円滑にするため少量のキャリアガ
スを通気させた。各実施例の処理条件と処理の結果を表
１に示す。これによれば、本発明法により塩化ビニル樹
脂材から塩素を高効率で除去することができ、また、排
ガス中には微量の低級炭化水素ガスが含まれていたもの
の、高濃度の塩化水素ガスを回収することができた。In the dechlorination treatment, supply amount of vinyl chloride resin material: 5
0 kg / h, coke breeze supply 20 kg / h (above, Example 1) and vinyl chloride resin material supply: 70 kg / h, coke breeze supply: 10 kg / h (above, Example 2)
Performed at the level, vinyl chloride resin material and heat medium (coke powder)
The kiln rotation speed and the like were adjusted so that the residence time in the kiln was about 15 minutes. In addition, a small amount of carrier gas was passed through the passage in the inner tube in order to smoothly move the vinyl chloride resin material and the heat medium. Table 1 shows the processing conditions and processing results of each embodiment. According to the method, chlorine can be removed from the vinyl chloride resin material with high efficiency by the method of the present invention. Also, although a small amount of lower hydrocarbon gas is contained in the exhaust gas, the concentration of hydrogen chloride gas is high. Could be recovered.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】以上述べた本発明の塩素除去方法によれ
ば、発生した塩化水素を加熱ガスと混合させることなく
取り出すため、排出ガスの処理に要する設備コストや処
理コストを従来法に較べて大幅に低減させることができ
る。また、塩化水素が発生する内管全体を加熱ガスで加
熱するため、内管全体の温度を、塩化水素が強い腐食性
を示す１５０℃以下の温度域よりも高い温度域に維持す
ることができ、このため発生した塩化水素による装置、
特に内管各部の腐食を適切に防止することができる。According to the chlorine removing method of the present invention described above, the generated hydrogen chloride can be mixed with the heating gas without mixing.
Since it is taken out , equipment costs and processing costs required for processing the exhaust gas can be significantly reduced as compared with the conventional method. Furthermore, pressure to the entire inner tube hydrogen chloride generated by heating the gas
Because of heating , the temperature of the entire inner tube can be maintained in a temperature range higher than the temperature range of 150 ° C. or less, at which hydrogen chloride exhibits strong corrosiveness.
In particular, corrosion of each part of the inner pipe can be appropriately prevented.
【００２６】また、熱媒体として炉の原材料として使用
することができる粉粒物を使用するため、脱塩素処理完
了後の樹脂の残渣を熱媒体と分離することなく、そのま
ま高炉等をはじめとする各種の溶解炉に鉄源、燃料、鉄
源の還元剤等として供給することができる。また、特に
熱媒体として粉コークスおよび／または粉粒状熱硬化性
樹脂を用いることにより熱媒体の偏析等が防止され、こ
のため脱塩素処理の高い処理効率を確保することができ
る。In addition, since a powdery material which can be used as a raw material for a furnace is used as a heat medium, the resin residue after the completion of the dechlorination treatment is not separated from the heat medium, but is directly used in a blast furnace or the like. It can be supplied to various melting furnaces as an iron source, a fuel, a reducing agent for the iron source, and the like. In particular, by using coke breeze and / or granular thermosetting resin as the heat medium, segregation of the heat medium and the like can be prevented, and therefore, high processing efficiency of the dechlorination treatment can be secured.
【図１】本発明法に使用される塩素除去装置の一実施形
態を示す縦断面図FIG. 1 is a longitudinal sectional view showing one embodiment of a chlorine removing apparatus used in the method of the present invention .
【図２】図１に示す装置の横断面図2 is a cross-sectional view of the device shown in FIG.
【図３】本発明法に使用される塩素除去装置の他の実施
形態を示す縦断面図FIG. 3 is a longitudinal sectional view showing another embodiment of the chlorine removing apparatus used in the method of the present invention .
【図４】図３に示す装置の横断面図FIG. 4 is a cross-sectional view of the device shown in FIG.
【図５】本発明法に使用される塩素除去装置の他の実施
形態を示す横断面図FIG. 5 is a cross-sectional view showing another embodiment of the chlorine removing apparatus used in the method of the present invention .
【図６】本発明法に使用される塩素除去装置の他の実施
形態を示す縦断面図FIG. 6 is a longitudinal sectional view showing another embodiment of the chlorine removing apparatus used in the method of the present invention .
【図７】実施例で用いた塩素除去装置を模式的に示す説
明図FIG. 7 is an explanatory view schematically showing a chlorine removing apparatus used in the embodiment.
【図８】ロータリーキルン方式の従来装置およびこれに
よる脱塩素方法を示すもので、（ａ）は装置の横断面
図、（ｂ）は装置の縦断面図8A and 8B show a conventional apparatus of a rotary kiln system and a dechlorination method using the apparatus, wherein FIG. 8A is a cross-sectional view of the apparatus, and FIG.
Ａ…装置本体、１…外管、２，２ａ〜２ｃ…内管、３，
４…通路、５…ガス導管、６…定量供給装置、７…スク
リューフィーダ、８…供給口、９…排出口A: apparatus main body, 1: outer tube, 2, 2a to 2c: inner tube, 3,
4 ... passage, 5 ... gas conduit, 6 ... fixed amount supply device, 7 ... screw feeder, 8 ... supply port, 9 ... discharge port
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｊ 11/12 ＺＡＢ Ｆ２３Ｇ 5/20 Ａ Ｆ２３Ｇ 5/20 Ｂ０９Ｂ 3/00 ＺＡＢ (56)参考文献 特開 昭53−60974（ＪＰ，Ａ) 特開 昭48−65280（ＪＰ，Ａ) 特開 平５−215320（ＪＰ，Ａ) 特開 昭52−127471（ＪＰ，Ａ) 特開 平８−33882（ＪＰ，Ａ) 特開 平７−180820（ＪＰ，Ａ) 特開 平７−150150（ＪＰ，Ａ) 実開 昭52−80046（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) B09B 3/00 A62D 3/00 B29B 17/00 C08J 11/12 F23G 5/20 F27B 7/30 ────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI C08J 11/12 ZAB F23G 5/20 A F23G 5/20 B09B 3/00 ZAB (56) References JP-A-53-60974 (JP) JP-A-48-65280 (JP, A) JP-A-5-215320 (JP, A) JP-A-52-127471 (JP, A) JP-A-8-33882 (JP, A) 7-180820 (JP, A) JP-A-7-150150 (JP, A) Japanese Utility Model Application Laid-open No. 52-80046 (JP, U) (58) Fields investigated (Int. Cl. 7 , DB name) B09B 3/00 A62D 3/00 B29B 17/00 C08J 11/12 F23G 5/20 F27B 7/30
Claims (9)
内管とから構成し、内管内を被処理樹脂材用の通路とす
るとともに、内管と外管間の空間を加熱ガス用の通路と
したロータリーキルン方式の塩素除去装置を用い、被処
理樹脂材および熱媒体と加熱ガスを装置本体の一端側か
ら前記被処理樹脂材用の通路と加熱ガス用の通路にそれ
ぞれ供給し、装置本体の前記一端側から他端側方向に移
送される被処理樹脂材および熱媒体を、装置本体の前記
一端側から他端側方向に流れる加熱ガスにより内管の管
壁を通じて加熱して樹脂中の塩素分を塩化水素ガスとし
て脱離させることにより被処理樹脂材を脱塩素処理し、
溶解炉供給用の脱塩素処理された樹脂残渣を得る含塩素
高分子樹脂の塩素除去方法であって、脱塩素処理された樹脂残渣とともに塩素除去装置外に取
り出される 熱媒体として、溶解炉用の原料又は燃料とし
て使用可能な材料である、粉鉱石、焼結粉、溶解炉用の
鉄源還元剤の粉粒物、溶解炉用の燃料の粉粒物、溶解炉
用の副原料の粉粒物の中から選ばれる１種以上を用い、
被処理樹脂材用の通路内での被処理樹脂材の加熱温度を
２５０〜３５０℃とすることを特徴とする含塩素高分子
樹脂の塩素除去方法。1. An apparatus main body comprising an outer tube and an inner tube disposed therein, wherein the inner tube serves as a passage for a resin material to be treated, and a space between the inner tube and the outer tube serves as a heating gas. A rotary kiln-type chlorine removing device was used as the passage, and the resin material to be treated, the heating medium, and the heating gas were supplied from one end side of the device body to the passage for the resin material to be treated and the passage for the heating gas, respectively. The resin material to be processed and the heat medium transferred from the one end side to the other end side of the main body are heated through the inner wall of the inner pipe by a heating gas flowing from the one end side to the other end side of the apparatus main body, thereby forming a resin. Dechlorinating the resin material to be treated by desorbing the chlorine content as hydrogen chloride gas,
A chlorine removal process of chlorine-containing polymer resin to obtain a dechlorination treated resin residue for dissolution furnace feed, taken out of the chlorine removal device with dechlorination treated resin residue
The heat medium discharged is used as a raw material or fuel for the melting furnace.
Is a material that can be used Te, fine ore, Shoyuiko, granular product of the iron source reducing agent for melting furnaces, granular product of fuel for furnaces, in the granular product of the auxiliary raw material for a melting furnace Using one or more kinds selected from
A method for removing chlorine from a chlorine-containing polymer resin, wherein the heating temperature of the resin material to be treated in the passage for the resin material to be treated is 250 to 350 ° C.
を通気させることを特徴とする請求項１に記載の含塩素
高分子樹脂の塩素除去方法。2. The method for removing chlorine from a chlorine-containing polymer resin according to claim 1, wherein a carrier gas is passed through the passage for the resin material to be treated.
および粉粒状熱硬化性樹脂の中から選ばれる１種以上の
粉粒物であることを特徴とする請求項１または２に記載
の含塩素高分子樹脂の塩素除去方法。3. The method according to claim 1, wherein the heating medium is at least one kind of powdery material selected from coke breeze, fine ore, sintered powder, and particulate thermosetting resin. The method for removing chlorine from a chlorine-containing polymer resin described in the above.
化性樹脂の中から選ばれる１種以上の粉粒物であること
を特徴とする請求項３に記載の含塩素高分子樹脂の塩素
除去方法。4. The chlorine in the chlorine-containing polymer resin according to claim 3, wherein the heat medium is at least one powdery substance selected from coke breeze and a particulate thermosetting resin. Removal method.
る単一の内管とから構成された塩素除去装置を用いて被
処理樹脂材の脱塩素処理を行うことを特徴とする請求項
１、２、３または４に記載の含塩素高分子樹脂の塩素除
去方法。5. The apparatus according to claim 1, wherein the apparatus main body performs a dechlorination treatment of the resin material to be treated by using a chlorine removing apparatus composed of an outer tube and a single inner tube disposed therein. Item 6. The method for removing chlorine from a chlorine-containing polymer resin according to Item 1, 2, 3, or 4.
る複数の内管とから構成された塩素除去装置を用いて被
処理樹脂材の脱塩素処理を行うことを特徴とする請求項
１、２、３または４に記載の含塩素高分子樹脂の塩素除
去方法。6. The apparatus according to claim 1, wherein the apparatus body performs a dechlorination treatment of the resin material to be treated by using a chlorine removing apparatus composed of an outer tube and a plurality of inner tubes disposed therein. The method for removing chlorine from a chlorine-containing polymer resin according to 1, 2, 3 or 4.
置された塩素除去装置を用いて被処理樹脂材の脱塩素処
理を行うことを特徴とする請求項１、２、３、４、５ま
たは６に記載の含塩素高分子樹脂の塩素除去方法。 7. A dechlorination process for a resin material to be treated by using a chlorine removing device in which a gas conduit for a heating gas is disposed inside an inner tube.
The method of claim 1, 2, 3, 4, 5, or
Or a method for removing chlorine from a chlorine-containing polymer resin according to item 6.
構成された塩素除去装置を用いて被処理樹脂材の脱塩素Dechlorination of resin material to be treated using the configured chlorine removal device
処理を行うことを特徴とする請求項１、２、３、４、A process is performed, wherein:
５、６または７に記載の含塩素高分子樹脂の塩素除去方5. A method for removing chlorine from a chlorine-containing polymer resin according to 5, 6, or 7.
法。Law.
素除去装置を用いて被処理樹脂材の脱塩素処理を行うこDechlorination of the resin material to be treated
とを特徴とする請求項１、２、３、４、５、６または７The method according to claim 1, 2, 3, 4, 5, 6, or 7.
に記載の含塩素高分子樹脂の塩素除去方法。3. The method for removing chlorine from a chlorine-containing polymer resin according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18929197A JP3159133B2 (en) | 1996-07-02 | 1997-06-30 | Method for removing chlorine from chlorine-containing polymer resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-191363 | 1996-07-02 | ||
| JP19136396 | 1996-07-02 | ||
| JP18929197A JP3159133B2 (en) | 1996-07-02 | 1997-06-30 | Method for removing chlorine from chlorine-containing polymer resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2409099A Division JP3353730B2 (en) | 1996-07-02 | 1999-02-01 | Chlorine removal equipment for chlorine-containing polymer resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1071384A JPH1071384A (en) | 1998-03-17 |
| JP3159133B2 true JP3159133B2 (en) | 2001-04-23 |
Family
ID=26505397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18929197A Expired - Fee Related JP3159133B2 (en) | 1996-07-02 | 1997-06-30 | Method for removing chlorine from chlorine-containing polymer resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3159133B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5582685B2 (en) * | 2008-03-27 | 2014-09-03 | 宇部興産株式会社 | Solid fuel and method for producing solid fuel |
-
1997
- 1997-06-30 JP JP18929197A patent/JP3159133B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1071384A (en) | 1998-03-17 |
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