JPH0848511A - Removal of zinc from waste tire carbonization char and production of active carbon - Google Patents
Removal of zinc from waste tire carbonization char and production of active carbonInfo
- Publication number
- JPH0848511A JPH0848511A JP6208118A JP20811894A JPH0848511A JP H0848511 A JPH0848511 A JP H0848511A JP 6208118 A JP6208118 A JP 6208118A JP 20811894 A JP20811894 A JP 20811894A JP H0848511 A JPH0848511 A JP H0848511A
- Authority
- JP
- Japan
- Prior art keywords
- char
- zinc
- carbonization
- furnace
- reducing
- 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.)
- Pending
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 68
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000010920 waste tyre Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000003763 carbonization Methods 0.000 title abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000011787 zinc oxide Substances 0.000 claims abstract description 39
- 230000004913 activation Effects 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 238000000197 pyrolysis Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 235000014692 zinc oxide Nutrition 0.000 description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000002939 deleterious effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
Landscapes
- Processing Of Solid Wastes (AREA)
- Carbon And Carbon Compounds (AREA)
- Coke Industry (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、廃タイヤを乾留処理す
る過程で回収される乾留チャーに含まれている亜鉛を除
去する方法に係り、特に廃タイヤ乾留チャーから活性炭
を製造するのに好適な廃タイヤ乾留チャーの亜鉛除去方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing zinc contained in a dry-distilled char recovered during a dry-distillation treatment of a waste tire, and particularly suitable for producing activated carbon from a waste tire dry-distilled char. Method for removing zinc from various waste tire carbonization chars.
【０００２】[0002]
【従来の技術】近年、自動車の普及に伴い使用済のゴム
タイヤ、いわゆる廃タイヤが激増し、廃タイヤの処分方
法が大きな問題となっており、廃タイヤを有効に利用す
る方法が種々検討されている。そして、廃タイヤの有効
利用法の１つとして、廃タイヤを乾留して油成分を抽出
するとともに、チャーとして残ったゴム中のカーボンブ
ラックを活性炭として利用することが検討されている。2. Description of the Related Art In recent years, with the widespread use of automobiles, the number of used rubber tires, so-called waste tires, has dramatically increased, and the disposal method of waste tires has become a big problem. Various methods for effectively using the waste tires have been studied. There is. Then, as one of the effective utilization methods of the waste tire, it is considered to dry-distill the waste tire to extract an oil component and to use the carbon black in the rubber remaining as char as the activated carbon.
【０００３】ところが、ゴムタイヤには、酸化亜鉛（亜
鉛華＝ＺｎＯ）が数％含まれており、タイヤを乾留する
と乾留チャー中に５〜７重量％程度残留する。この酸化
亜鉛は、それ自体安定であって、ｐＨが中性域の通常の
雰囲気ではチャーから溶出することがないので特に問題
を生じない。しかし、酸化亜鉛は、酸性またはアルカリ
性の液に対して容易に溶出し、廃タイヤ乾留チャーを水
処理用の活性炭として使用した場合に、活性炭から溶出
して重金属汚染の問題を引き起こす可能性がある。この
ため、廃タイヤ乾留チャーをそのまま賦活化して得た活
性炭は、用途が限定されており、その用途を広げるため
に乾留チャーから酸化亜鉛を除去する方法の開発が強く
望まれていた。However, rubber tires contain zinc oxide (zinc white = ZnO) of several percent, and when the tire is carbonized, about 5 to 7% by weight remains in the carbonized char. This zinc oxide is stable in itself and does not elute from the char in a normal atmosphere having a neutral pH, so that it does not cause a problem. However, zinc oxide easily elutes into acidic or alkaline liquids, and when waste tire carbonization char is used as activated carbon for water treatment, it may elute from activated carbon and cause a problem of heavy metal contamination. . Therefore, the activated carbon obtained by directly activating the waste tire dry-distilled char has limited uses, and development of a method for removing zinc oxide from the dry-distilled char has been strongly desired in order to expand the use.
【０００４】そこで、廃タイヤ乾留チャーから酸化亜鉛
を除去する方法として、乾留チャーの吸着能力を高める
ための賦活処理をしたのち、濃度が１〜１０％程度の塩
酸にチャーを浸して酸化亜鉛ＺｎＯを塩酸中に塩化亜鉛
ＺｎＣｌ2 として溶出分離し、その後、乾留チャーを水
洗することが提案されている（特開平６−１４４８１９
号公報）。Therefore, as a method for removing zinc oxide from waste tire dry-distilled char, an activation treatment for enhancing the adsorption capacity of dry-distilled char is performed, and then the char is immersed in hydrochloric acid having a concentration of about 1 to 10% to form zinc oxide ZnO. It has been proposed to elute and separate carbon dioxide as zinc chloride ZnCl 2 in hydrochloric acid, and then wash the dry distillation char with water (JP-A-6-144819).
Issue).
【０００５】[0005]
【発明が解決しようとする課題】しかし、上記公報に記
載の酸化亜鉛の除去方法は、酸化亜鉛を溶出させる溶液
として腐食性の強い塩酸を使用しており、取扱いに充分
な注意が必要である。しかも、溶出されたＺｎＣｌ2 自
体が毒物及び劇物取締法第２条別表２の劇物に該当す
る。このため、脱亜鉛処理後の廃液からＺｎＣｌ2 を回
収するにあたり、公害防止上の観点からも高価な処理設
備を必要とし、大きな処理コストを要する。また、上記
の方法は、塩酸処理後に水洗、乾燥を行う必要があり、
多くの工程とコストを必要とする。However, in the method for removing zinc oxide described in the above publication, hydrochloric acid having a strong corrosive property is used as a solution for eluting zinc oxide, so that it is necessary to handle it with sufficient care. . Moreover, the eluted ZnCl 2 itself corresponds to the poisonous substance and the deleterious substance listed in Appendix 2 of Article 2 of the Deleterious Substances Control Law. Therefore, in recovering ZnCl 2 from the waste liquid after the dezincification treatment, an expensive treatment facility is required from the viewpoint of pollution prevention, and a large treatment cost is required. Further, the above method requires washing with water and drying after hydrochloric acid treatment,
It requires many steps and costs.
【０００６】一方、酸化亜鉛を安全に除去する方法とし
て、乾留チャーを高温処理して酸化亜鉛を昇華させ、こ
れを回収するとが考えられる。ところが、酸化亜鉛Ｚｎ
Ｏの昇華温度は１９７５°Ｃと極めて高く、ＺｎＯを昇
華させるためには、高温耐火炉を必要とし、実用的でな
い。また、乾留チャーを水分（Ｈ2Ｏ）や炭酸ガス（Ｃ
Ｏ2 ）などの酸化雰囲気のもとで脱亜鉛することが考え
られるが、１３００°Ｃ以上の高温でないと亜鉛を除去
することができないし、残留亜鉛濃度を低下させるにも
限界がある。しかも、１３００°Ｃ以上の高温において
処理するため、運転コストもかかり、炉の痛みも激しく
て寿命も短い。On the other hand, as a method for safely removing zinc oxide, it is considered that dry distillation char is subjected to high temperature treatment to sublimate zinc oxide and recover it. However, zinc oxide Zn
The sublimation temperature of O is extremely high at 1975 ° C., and a high temperature refractory furnace is required to sublime ZnO, which is not practical. In addition, dry distillation char is treated with water (H 2 O) or carbon dioxide (C
It is considered that dezincification is carried out in an oxidizing atmosphere such as O 2 ), but zinc cannot be removed unless the temperature is higher than 1300 ° C, and there is a limit in reducing the residual zinc concentration. Moreover, since the treatment is performed at a high temperature of 1300 ° C. or higher, the operating cost is high, the pain of the furnace is severe, and the life is short.
【０００７】本発明は、前記従来技術の欠点を解消する
ためになされたもので、強腐食性の物質を用いることな
く乾留チャー中の亜鉛を除去できるようにすることを目
的としている。また、本発明は、劇物を発生させること
なく乾留チャー中の亜鉛を除去できるようにすることを
目的としている。さらに、本発明は、乾留チャー中の亜
鉛を除去するためのコストを低減することを目的として
いる。また、本発明は、乾留チャー中の残留亜鉛を除去
するための加熱温度を低くすることを目的としている。The present invention has been made to solve the above-mentioned drawbacks of the prior art, and an object thereof is to enable removal of zinc in carbonization char without the use of a strongly corrosive substance. Another object of the present invention is to enable removal of zinc in carbonization char without generating deleterious substances. Further, the present invention aims to reduce the cost for removing zinc in carbonization char. Another object of the present invention is to lower the heating temperature for removing the residual zinc in the carbonization char.
【０００８】[0008]
【課題を解決するための手段および作用】本発明は、金
属亜鉛の沸点が図３に示されるように９０７°Ｃと、酸
化亜鉛の昇華温度より大幅に低いことに注目してなされ
たもので、上記の目的を達成するために、本発明に係る
廃タイヤ乾留チャーの亜鉛除去方法は、乾留して得た廃
タイヤ乾留チャー中の酸化亜鉛を還元ガスによって亜鉛
に還元し、この亜鉛を蒸発させるようにしてある。The present invention has been made paying attention to the fact that the boiling point of metallic zinc is 907 ° C., which is much lower than the sublimation temperature of zinc oxide, as shown in FIG. In order to achieve the above object, the method for removing zinc from a waste tire carbonization char according to the present invention reduces zinc oxide in a waste tire carbonization char obtained by carbonization to zinc with a reducing gas and evaporates the zinc. I am allowed to do it.
【０００９】また、本発明に係る活性炭の製造方法は、
廃タイヤを乾留して得た乾留チャーを賦活処理して活性
炭にする活性炭の製造方法において、前記賦活処理前ま
たは賦活処理後の前記乾留チャーを還元ガスに接触させ
て乾留チャー中の酸化亜鉛を亜鉛に還元し、この亜鉛を
蒸発させる構成となっている。The method for producing activated carbon according to the present invention is
In the method for producing activated carbon that activates the dry-distilled char obtained by dry-distilling a waste tire into activated carbon, the dry-distilled char before the activation treatment or after the activation treatment is contacted with a reducing gas to remove zinc oxide in the dry-distilled char. The structure is such that it is reduced to zinc and this zinc is evaporated.
【００１０】このように、ＺｎＯをＺｎに還元して蒸発
させると、腐食性の強い物質を用いることなく、チャー
中の残留亜鉛を極めて少なくすることができる。そし
て、ＺｎＣｌ2 のような劇物の発生がないので、処理施
設の簡素化を図ることができ、処理コストの低減を図る
ことができる。しかも、Ｚｎにして蒸発させるため、Ｚ
ｎＯを昇華させたり、酸化雰囲気で脱亜鉛処理する場合
に比較して処理温度を大幅に低くすることができ、設備
費を軽減することができるとともに、処理炉の寿命を大
幅に延ばすことができ、ランニングコストの低減が図れ
る。As described above, when ZnO is reduced to Zn and evaporated, the amount of residual zinc in the char can be extremely reduced without using a highly corrosive substance. Since no deleterious substance such as ZnCl 2 is generated, the processing facility can be simplified and the processing cost can be reduced. Moreover, since it is converted to Zn and evaporated, Z
Compared with the case of subliming nO or dezincing in an oxidizing atmosphere, the processing temperature can be significantly reduced, the facility cost can be reduced, and the life of the processing furnace can be greatly extended. The running cost can be reduced.
【００１１】還元ガスとしては、ＺｎＯと反応して亜鉛
Ｚｎが得られるものであればよく、例えば一酸化炭素Ｃ
Ｏや水素ガスＨ2 を用いることができる。還元ガスとし
てＣＯを使用した場合、次の〔化１〕の反応が生じ、Ｚ
ｎＯをＺｎに還元することができる。Any reducing gas may be used as long as it can react with ZnO to obtain zinc Zn. For example, carbon monoxide C
O or hydrogen gas H 2 can be used. When CO is used as the reducing gas, the following reaction of [Chemical formula 1] occurs and Z
nO can be reduced to Zn.
【化１】 また、還元ガスとしてＨ2 を使用した場合、Embedded image When H 2 is used as the reducing gas,
【化２】 の式によりＺｎＯをＺｎに還元することができる。そし
て、上記の〔化１〕、〔化２〕の反応によるＺｎ、Ｚｎ
Ｏ、ＣＯ、ＣＯ2 、Ｈ2 、Ｈ2Ｏ系の反応平衡線図は、
図４のようになる。Embedded image ZnO can be reduced to Zn by the following formula. Then, Zn and Zn produced by the reactions of [Chemical Formula 1] and [Chemical Formula 2] above
The reaction equilibrium diagram of O, CO, CO 2 , H 2 , H 2 O system is
It becomes like FIG.
【００１２】ただし、横軸は温度を示しており、１０4
／絶対温度Ｔで表しており、縦軸はＣＯ2 の分圧とＣＯ
の分圧との比の対数を示している。また、図中の線分
Ａ、Ｂは、ＣＯ2 の分圧とＣＯの分圧との比の処理温度
に対する変化を対数で示したものであり、いずれも文献
値である。また、線分Ｃは、Ｈ2Ｏの分圧とＨ2 の分圧
との比の処理温度に対する変化を対数で示したもので、
計算値によっている。However, the horizontal axis indicates the temperature, and 10 4
/ Absolute temperature T, where the vertical axis is the partial pressure of CO 2 and CO
The logarithm of the ratio with the partial pressure of is shown. Further, line segments A and B in the figure are logarithmic changes in the ratio of the partial pressure of CO 2 and the partial pressure of CO with respect to the processing temperature, and both are literature values. The line segment C is a logarithmic change in the ratio of the partial pressure of H 2 O and the partial pressure of H 2 with respect to the processing temperature.
It depends on the calculated value.
【００１３】ＺｎＯのＺｎへの還元は、還元ガスとして
ＣＯ2 を含んだＣＯを用いる場合、線分Ａ、Ｂの下方の
運転条件によって行い、還元ガスがＨ2Ｏを含んだＨ2
である場合、線分Ｃの下方の運転条件によって行う。還
元処理温度は、還元ガスがＣＯである場合、９５０〜１
３００°Ｃ程度、望ましくは１１００〜１２００°Ｃで
ある。一方、還元ガスがＨ2 である場合、処理温度は８
００〜１２００°Ｃ程度であり、特に９５０°Ｃ前後に
おいて行うのがよい。還元雰囲気は、還元ガスＨ2 が５
〜２０％、残余は不活性の窒素ガスであってよい。そし
て、チャーをロータリキルンなどの還元炉（脱亜鉛炉）
によって連続的に処理する場合、還元ガスの供給量は、
乾留チャー１００ｋｇ／ｈの処理量に対して８０〜１３
０Ｎｍ3／ｈであって、処理時間は残留亜鉛濃度が０．
１重量％以下になるように、０．５〜４時間、好ましく
は１〜２時間である。[0013] reduction of Zn in ZnO, when using CO containing CO 2 as a reducing gas, the line segment A, carried by the lower operating conditions of B, reducing gas containing H 2 O H 2
If it is, the operation is performed under the operating condition below the line segment C. The reducing treatment temperature is 950 to 1 when the reducing gas is CO.
The temperature is about 300 ° C, preferably 1100 to 1200 ° C. On the other hand, when the reducing gas is H 2 , the processing temperature is 8
The temperature is about 00 to 1200 ° C, and it is particularly preferable to perform it at about 950 ° C. The reducing atmosphere is such that the reducing gas H 2 is 5
-20%, the balance may be inert nitrogen gas. Then, the char is reduced to a rotary kiln or other reduction furnace (dezincification furnace).
In the case of continuous treatment by
80 to 13 per 100 kg / h of dry distillation char
A 0 nm 3 / h, the processing time is remaining zinc concentration 0.
It is 0.5 to 4 hours, preferably 1 to 2 hours so as to be 1% by weight or less.
【００１４】なお、還元炉に供給する廃タイヤ乾留チャ
ーチャーは、予め粉砕機などにより適宜の粒径に粉砕
し、タイヤに埋め込まれているピアノ線などの金属成分
をふるいに掛けたり磁力を利用した磁選機により除去し
ておくとともに、水洗して不純物を除去したのち、乾燥
して洗浄した際に吸着した水分を取り除いておくとよ
い。また、還元炉としては、ロータリキルンの他、流動
床炉等の他の形式の炉を用いてもよいし、バッチ処理を
してもよい。The waste tire carbonization charture supplied to the reduction furnace is crushed in advance to a proper particle size by a crusher or the like, and the metal component such as piano wire embedded in the tire is sieved or the magnetic force is used. It is advisable to remove the impurities by washing with a magnetic separator, remove impurities by washing with water, and then remove water adsorbed during drying and washing. Further, as the reduction furnace, other types of furnaces such as a fluidized bed furnace other than the rotary kiln may be used, or batch processing may be performed.
【００１５】還元炉におけるＺｎＯのＺｎへの還元は、
Ｚｎの沸点以上において行うことが望ましい。Ｚｎの沸
点以上においてＺｎＯの還元を行えば、ＺｎＯから還元
されたＺｎはそのまま蒸発するため、乾留チャーへの残
留を非常に少なくできる。そして、蒸発したＺｎは、冷
却して金属亜鉛の状態で回収したり、再度酸化してＺｎ
Ｏの状態にして回収する。The reduction of ZnO to Zn in a reduction furnace is
It is desirable to carry out at the boiling point of Zn or higher. If ZnO is reduced at a temperature equal to or higher than the boiling point of Zn, the Zn reduced from ZnO evaporates as it is, and therefore the residue on the carbonization char can be extremely reduced. Then, the evaporated Zn is cooled and recovered in the state of metallic zinc, or is oxidized again to produce Zn.
Collect in the O state.
【００１６】廃タイヤの乾留処理は、従来から一般に行
われている通常の方法、例えば常圧の不活性ガス雰囲気
（例えば窒素ガス雰囲気）において、廃タイヤを温度４
５０〜５５０°Ｃに加熱して熱分解する。乾留して得た
チャーは、粉砕・除鉄したのちに水洗して不純物を除
き、４００°Ｃ程度の温度で１〜３時間乾燥して水分を
除去する。そして、ＺｎＯのＺｎへの還元は、乾留チャ
ーを活性炭として利用する場合、乾燥直後の乾留チャー
に対して行ってもよいし、吸着性を高めるための賦活処
理をしたのちに行ってもよい。乾燥直後に脱亜鉛処理を
行った場合、その後、乾留チャーの賦活処理をし、冷却
して製品（活性炭）にする。また、賦活化処理後に脱亜
鉛処理（Ｚｎへの還元、蒸発）を行う場合、脱亜鉛処理
後に直ちにチャーを冷却して製品にすることができる。The dry distillation treatment of a waste tire is carried out by a conventional method generally used, for example, in an inert gas atmosphere (for example, nitrogen gas atmosphere) under normal pressure, the waste tire is heated to a temperature of 4 ° C.
It is heated to 50 to 550 ° C to be pyrolyzed. The char obtained by dry distillation is crushed and iron-removed, then washed with water to remove impurities, and dried at a temperature of about 400 ° C. for 1 to 3 hours to remove water. The reduction of ZnO to Zn may be performed on the dry-distilled char immediately after drying when using the dry-distilled char as activated carbon, or may be performed after the activation treatment for enhancing the adsorptivity. When the dezincing treatment is performed immediately after drying, the dry distillation char is then activated and cooled to obtain a product (activated carbon). Further, when the dezincification treatment (reduction to Zn, evaporation) is performed after the activation treatment, the char can be cooled immediately after the dezincification treatment to obtain a product.
【００１７】賦活処理は、通常の方法によって行うこと
ができる。例えば、温度７００〜１０００°Ｃ、不活性
ガスの雰囲気にしたロータリキルンなどの賦活炉に乾燥
直後のチャーまたは脱亜鉛処理を終了したチャーを投入
し、水蒸気を供給して行うことができる。処理時間は、
１〜４時間程度でよい。The activation treatment can be carried out by a usual method. For example, the char after the drying or the char after the dezincification treatment is put into an activation furnace such as a rotary kiln in the atmosphere of an inert gas atmosphere at a temperature of 700 to 1000 ° C., and steam can be supplied. The processing time is
It may be about 1 to 4 hours.
【００１８】[0018]
【実施例】本発明の好ましい実施例を、添付図面に基づ
いて詳細に説明する。図１は、実施例に係る亜鉛除去方
法を利用して、廃タイヤから活性炭を製造する活性炭製
造設備の例を示したものである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 shows an example of an activated carbon production facility for producing activated carbon from waste tires by using the zinc removal method according to the embodiment.
【００１９】廃タイヤは、乾留炉１０において油成分と
乾留チャーとに熱分解される。気化した油成分は、凝縮
器１２において液化し、油回収装置１４により回収油と
して回収する。そして、凝縮器１２において液化できな
いガス成分は、２次燃焼炉１６において導いて燃焼した
のち、排ガス処理装置１８によって排ガス処理をし、大
気中に放出される。The waste tire is pyrolyzed in the carbonization furnace 10 into oil components and carbonization char. The vaporized oil component is liquefied in the condenser 12 and is recovered by the oil recovery device 14 as recovered oil. Then, the gas component that cannot be liquefied in the condenser 12 is introduced into the secondary combustion furnace 16 and burned, and then is subjected to exhaust gas treatment by the exhaust gas treatment device 18 and is discharged into the atmosphere.
【００２０】一方、乾留して得た廃タイヤ乾留チャー
は、粉砕・除鉄装置２０によって所定の粒度に粉砕する
とともに、ピアノ線などの金属成分を除去して水洗し、
その後、さらに乾燥器２２によって乾燥する。この乾燥
したチャーは、還元ガス雰囲気にしてあるロータリキル
ンからなる脱亜鉛炉（還元炉）２４に投入される。脱亜
鉛炉２４は、チャー中に残留しているＺｎＯをＣＯやＨ
2 などの還元ガスによってＺｎに還元したのち、Ｚｎを
蒸発してチャーの脱亜鉛処理をする。そして、亜鉛を除
去された乾留チャーは、ロータリキルンからなる賦活炉
２６において賦活処理されたのち、冷却器２８によって
冷却され、製品の活性炭となる。なお、脱亜鉛炉２４に
おいてＺｎＯから還元され、蒸発したＺｎは、２次燃焼
炉（図示せず）において再び酸化されてＺｎＯとなり、
冷却されたのち、酸化亜鉛ＺｎＯとして回収される。On the other hand, the waste tire dry distillation char obtained by dry distillation is crushed to a predetermined particle size by a crushing / iron removing device 20, and metal components such as piano wire are removed and washed with water.
Then, it is further dried by the dryer 22. The dried char is put into a dezincification furnace (reduction furnace) 24 made of a rotary kiln in a reducing gas atmosphere. The dezincification furnace 24 removes ZnO remaining in the char into CO and H.
After reducing to Zn with a reducing gas such as 2 , Zn is evaporated to dezinc the char. Then, the carbonization char from which zinc has been removed is subjected to activation treatment in an activation furnace 26 made of a rotary kiln and then cooled by a cooler 28 to become activated carbon of the product. The Zn reduced and evaporated from ZnO in the dezincification furnace 24 is oxidized again in a secondary combustion furnace (not shown) to become ZnO,
After cooling, it is recovered as zinc oxide ZnO.
【００２１】以下に、乾留チャーからの亜鉛除去方法の
具体的実施例を示す。通常の方法により廃タイヤを乾留
して得た廃タイヤ乾留チャーを粒径１〜２ｍｍ程度の大
きさに粉砕して除鉄を行ったのち水洗し、この水洗した
チャーをロータリキルンからなる乾燥器２２において乾
燥した。この乾燥は、従来行われている通常の方法によ
って行われ、４００°Ｃ程度の温度において１〜３時間
程度、炉を回転させながら乾燥させた。Specific examples of the method for removing zinc from carbonization char will be shown below. The waste tire dry distillation char obtained by dry distillation of the waste tire by a usual method is crushed to a particle size of about 1 to 2 mm to remove iron, and then washed with water, and the washed char is a dryer composed of a rotary kiln. Dried at 22. This drying was performed by a conventional method which has been conventionally performed, and was dried at a temperature of about 400 ° C. for about 1 to 3 hours while rotating the furnace.
【００２２】乾燥した乾留チャーを還元ガス雰囲気にし
たロータリキルンからなる脱亜鉛炉２４に投入し、炉を
回転させながらＺｎＯをＺｎに還元して蒸発させた。還
元条件は、実施例１の場合、還元ガスとしてＨ2 を使用
し、炉内温度を９００〜１０００°Ｃに保持し、脱亜鉛
炉２４にＨ2 を１０％、Ｎ2 を９０％を供給して還元雰
囲気にし、１〜２時間処理をした。また、実施例２にお
いては、還元ガスとしてＨ2 とＣＯとを用い、Ｈ2 ＋Ｃ
Ｏを３０％、ＣＯ2 、Ｈ2Ｏ、Ｎ2 存在下で脱亜鉛炉に
供給し、炉内の雰囲気を反応によって生ずるＣＯ2 、Ｈ
2Ｏを存在させたＣＯ、ＣＯ2 、Ｈ2 、Ｈ2Ｏ、Ｎ2 の混
合ガス雰囲気にし、処理温度を１１００〜１２００°Ｃ
に保持して１〜２時間の処理を行った。なお、還元ガス
の供給量は、いずれの場合も乾留チャーの処理量が１０
０ｋｇ／ｈのとき、１００Ｎｍ3 ／ｈにした。The dried carbonization char was put into a dezincification furnace 24 made of a rotary kiln in a reducing gas atmosphere, and ZnO was reduced to Zn while the furnace was rotated to evaporate. Regarding the reducing conditions, in the case of Example 1, H 2 was used as a reducing gas, the furnace temperature was kept at 900 to 1000 ° C., and H 2 10% and N 2 90% were supplied to the dezincification furnace 24. To a reducing atmosphere and treated for 1 to 2 hours. Further, in Example 2, H 2 and CO were used as the reducing gas, and H 2 + C
O is supplied to a dezincification furnace in the presence of 30% of CO 2 , H 2 O and N 2 , and the atmosphere in the furnace is CO 2 and H generated by the reaction.
A mixed gas atmosphere of CO, CO 2 , H 2 , H 2 O and N 2 in which 2 O is present is used, and the treatment temperature is 1100 to 1200 ° C.
The treatment was carried out for 1 to 2 hours. In addition, as for the supply amount of the reducing gas, the treatment amount of the dry distillation char is 10 in each case.
When it was 0 kg / h, it was 100 Nm 3 / h.
【００２３】上記のように還元処理をした後の乾留チャ
ー中を適宜の濃度の酸（例えば１０％塩酸）中に浸漬
し、チャー中の亜鉛を酸によって溶出し、比色分析を行
ってチャー中の残留亜鉛量を測定した。その結果、還元
処理前のチャー中の残留亜鉛量が５〜７重量％であった
ものが、図２に示したように、脱亜鉛処理後の実施例１
においては残留亜鉛量が０．１重量％、実施例２におい
ては０．０３〜０．０８重量％となり、チャー中の残留
亜鉛量を極めて少なくすることができた。そして、この
ようにして脱亜鉛処理を行ったチャーをロータリキルン
からなる賦活炉２６において賦活処理を行って得た活性
炭は、ヨウ素吸着能力が７００ｍｇ／ｇ、活性炭の比表
面積が５２０ｍ2 ／ｇであった。After the reduction treatment as described above, the dry-distilled char is immersed in an acid having an appropriate concentration (for example, 10% hydrochloric acid), zinc in the char is eluted with the acid, and colorimetric analysis is performed to perform char. The amount of residual zinc therein was measured. As a result, the amount of residual zinc in the char before the reduction treatment was 5 to 7% by weight. However, as shown in FIG.
In Example 2, the amount of residual zinc was 0.1% by weight, and in Example 2, it was 0.03 to 0.08% by weight, and the amount of residual zinc in the char could be extremely reduced. The activated carbon obtained by activating the dezincified char in the activation furnace 26 made of a rotary kiln has an iodine adsorption capacity of 700 mg / g and a specific surface area of activated carbon of 520 m 2 / g. there were.
【００２４】なお、乾燥した乾留チャーを吸着力を高め
る賦活処理したのち、前記と同様の処理条件において脱
亜鉛処理を行った結果、残留亜鉛の量を上記実施例１、
２とほぼ同じにすることができた。しかも、これのヨウ
素吸着性能、比表面積も実施例１、２と同様の値を得る
ことができた。The dried carbonized char was subjected to an activation treatment for enhancing the adsorptive power and then dezincification treatment under the same treatment conditions as described above. As a result, the amount of residual zinc was determined as in Example 1 above.
It could be almost the same as 2. Moreover, the iodine adsorption performance and the specific surface area of these were able to obtain the same values as in Examples 1 and 2.
【００２５】前記実施例においては、脱亜鉛炉や賦活
炉、乾燥器としてロータリキルンを使用した場合につい
て説明したが、ロータリキルンに代えて流動床等の他の
形式の炉を用いてもよい。また、前記実施例において
は、チャーを連続処理する場合について説明したが、バ
ッチ処理をしてもよい。そして、前記実施例において
は、廃タイヤ乾留チャーを活性炭にする場合について説
明したが、土壌改良剤などに使用してもよい。In the above embodiments, the case where the dezincification furnace, the activation furnace, and the rotary kiln are used as the dryer has been described, but other types of furnaces such as a fluidized bed may be used instead of the rotary kiln. Further, in the above-described embodiment, the case where char is continuously processed has been described, but batch processing may be performed. Further, in the above-mentioned embodiment, the case where the waste tire dry distillation char is made of activated carbon has been described, but it may be used as a soil improving agent or the like.
【００２６】[0026]
【発明の効果】以上に説明したように、本発明によれ
ば、廃タイヤ乾留チャーを還元ガス雰囲気において酸化
亜鉛を亜鉛に還元したのち、亜鉛を蒸発させるようにし
たことにより、腐食性の強い物質を使用したり、劇物を
発生させることなく、チャー中に存在する残留亜鉛の量
を極めて少なくすることができ、廃タイヤ乾留チャーを
水処理用の活性炭として利用することができる。また、
酸化亜鉛を亜鉛に還元して蒸発させるため、チャー中の
亜鉛を除去するための処理温度を大幅に下げることが可
能となって、設備費用の軽減と処理コストの軽減を図る
ことができる。As described above, according to the present invention, since zinc oxide is reduced to zinc in a waste gas dry distillation char in a reducing gas atmosphere, and then zinc is evaporated, the corrosiveness is high. The amount of residual zinc present in the char can be extremely reduced without using substances or generating deleterious substances, and the waste tire carbonization char can be used as activated carbon for water treatment. Also,
Since zinc oxide is reduced to zinc and evaporated, the treatment temperature for removing zinc in char can be significantly lowered, and the facility cost and the treatment cost can be reduced.
【図１】本発明の亜鉛除去方法を適用した廃タイヤから
活性炭を製造する設備の構成説明図である。FIG. 1 is a structural explanatory view of equipment for producing activated carbon from a waste tire to which a zinc removing method of the present invention is applied.
【図２】実施例の残留亜鉛量を示す図である。FIG. 2 is a diagram showing the amount of residual zinc in Examples.
【図３】亜鉛の温度と蒸気圧との関係を示す図である。FIG. 3 is a diagram showing a relationship between zinc temperature and vapor pressure.
【図４】Ｚｎ、ＺｎＯ、ＣＯ、ＣＯ2 、Ｈ2 、Ｈ2Ｏ系
反応平衡線図である。FIG. 4 is a reaction equilibrium diagram for Zn, ZnO, CO, CO 2 , H 2 , and H 2 O systems.
１０ 乾留炉 ２２ 乾燥器 ２４ 脱亜鉛炉 ２６ 賦活炉 ２８ 冷却器 10 Dry distillation furnace 22 Dryer 24 Dezincification furnace 26 Activation furnace 28 Cooler
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｂ 53/00 Ｂ // Ｃ０１Ｇ 9/03 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C10B 53/00 B // C01G 9/03
Claims (2)
化亜鉛を還元ガスによって亜鉛に還元し、この亜鉛を蒸
発させることを特徴とする廃タイヤ乾留チャーの亜鉛除
去方法。1. A method for removing zinc from a waste tire dry-distilled char, which comprises reducing zinc oxide in the waste tire dry-distilled char obtained by dry distillation to zinc with a reducing gas and evaporating the zinc.
活処理して活性炭にする活性炭の製造方法において、前
記賦活処理前または賦活処理後の前記乾留チャーを還元
ガスに接触させて乾留チャー中の酸化亜鉛を亜鉛に還元
し、この亜鉛を蒸発させることを特徴とする活性炭の製
造方法。2. A dry-distilled char obtained by subjecting a dry-distilled char obtained by dry-distilling a waste tire to activation treatment to obtain activated carbon, wherein the dry-distilled char before or after the activation treatment is brought into contact with a reducing gas. A method for producing activated carbon, which comprises reducing the zinc oxide therein to zinc and evaporating the zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6208118A JPH0848511A (en) | 1994-08-09 | 1994-08-09 | Removal of zinc from waste tire carbonization char and production of active carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6208118A JPH0848511A (en) | 1994-08-09 | 1994-08-09 | Removal of zinc from waste tire carbonization char and production of active carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0848511A true JPH0848511A (en) | 1996-02-20 |
Family
ID=16550939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6208118A Pending JPH0848511A (en) | 1994-08-09 | 1994-08-09 | Removal of zinc from waste tire carbonization char and production of active carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0848511A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913360A1 (en) * | 1997-09-23 | 1999-05-06 | Chien-Lang Teng | Intermittent continuous method for recovering refined activated carbon from waste tyres and the like and the device therefor |
| JP2002523552A (en) * | 1998-08-21 | 2002-07-30 | − スツレ エルシャグ、ベングト | Method for recovering carbon and hydrocarbon mixtures from polymers by pyrolysis in a pyrolysis reactor, preferably in the form of waste tires |
| WO2019152288A1 (en) * | 2018-02-03 | 2019-08-08 | Magnum Group International, Inc. | Non-polluting biomass waste processor, components and processes for use by a municipality, industrial, forestry and/or agricultural facility |
| CN113501519A (en) * | 2021-08-02 | 2021-10-15 | 江苏龙腾城矿环境技术有限公司 | Method for preparing activated carbon and recovering zinc by utilizing waste tire rubber pyrolytic carbon |
| CN115558796A (en) * | 2022-11-04 | 2023-01-03 | 昆明理工大学 | Method for resource extraction of zinc oxide from waste tire coupled blast furnace ash |
| CN115591911A (en) * | 2022-10-12 | 2023-01-13 | 昆明理工大学（Cn） | Treatment method for recycling whole waste tires |
-
1994
- 1994-08-09 JP JP6208118A patent/JPH0848511A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913360A1 (en) * | 1997-09-23 | 1999-05-06 | Chien-Lang Teng | Intermittent continuous method for recovering refined activated carbon from waste tyres and the like and the device therefor |
| JP2002523552A (en) * | 1998-08-21 | 2002-07-30 | − スツレ エルシャグ、ベングト | Method for recovering carbon and hydrocarbon mixtures from polymers by pyrolysis in a pyrolysis reactor, preferably in the form of waste tires |
| WO2019152288A1 (en) * | 2018-02-03 | 2019-08-08 | Magnum Group International, Inc. | Non-polluting biomass waste processor, components and processes for use by a municipality, industrial, forestry and/or agricultural facility |
| US20210031250A1 (en) * | 2018-02-03 | 2021-02-04 | Magnum Group International, Inc. | Non-polluting Biomass Waste Processor, Components and Processes for Use by a Municipality, Industrial, Forestry and/or Agricultural Facility |
| CN113501519A (en) * | 2021-08-02 | 2021-10-15 | 江苏龙腾城矿环境技术有限公司 | Method for preparing activated carbon and recovering zinc by utilizing waste tire rubber pyrolytic carbon |
| CN115591911A (en) * | 2022-10-12 | 2023-01-13 | 昆明理工大学（Cn） | Treatment method for recycling whole waste tires |
| CN115591911B (en) * | 2022-10-12 | 2024-05-28 | 昆明理工大学 | Full-recycling treatment method for waste tires |
| CN115558796A (en) * | 2022-11-04 | 2023-01-03 | 昆明理工大学 | Method for resource extraction of zinc oxide from waste tire coupled blast furnace ash |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2102510C1 (en) | Method of raising titanium dioxide content in titanium-containing ore or concentrate | |
| US4689154A (en) | Process for removing phosphorus from industrial waste water | |
| US4804390A (en) | Process for removing mineral impurities from coals and oil shales | |
| EP0776246B1 (en) | Process for regenerating nitrogen-treated carbonaceous chars used for hydrogen sulfide removal | |
| JP2001516395A (en) | Fluidized bed treatment of EAF dust | |
| JPH0848511A (en) | Removal of zinc from waste tire carbonization char and production of active carbon | |
| US5094012A (en) | Process for decontaminating contaminated soils | |
| JPS6225735B2 (en) | ||
| US3180706A (en) | Method for the recovery of metal values from a spent hydrocarbon conversion catalyst | |
| JPH10501208A (en) | Method for extracting metals from metal-containing materials by high-temperature hydrolysis | |
| CN116832777A (en) | Carbon-based material, preparation method and application thereof, and uranium-containing wastewater purification method | |
| IE49580B1 (en) | Process for recovering metals from catalysts for the hydrodesulfurization of hydrocarbons | |
| JP3132962B2 (en) | Method for producing modified activated carbon | |
| EP0663370B1 (en) | Method of producing active carbon from waste tires | |
| US2927063A (en) | Process for maintaining high level of activity for supported manganese oxide acceptors for hydrogen sulfide | |
| JP2000263031A (en) | Method for restoring polluted soil | |
| JPH06174383A (en) | Treating method of electric furnace dust | |
| CA1072325A (en) | Method of treating wet-washed silica dust | |
| JPH08126839A (en) | Treatment of waste clay and adsorbent composed of its treated material | |
| CA1109637A (en) | Purification of titanium trichloride | |
| JPH0633158A (en) | Treatment of zinc-and tin-containing scrap | |
| JP3027763B2 (en) | Activated carbon for recovery of organic halogenated solvents | |
| ATE105204T1 (en) | METHOD AND DEVICE FOR PROCESSING OF ACTIVATED CARBON LOADED WITH HEAVY METAL. | |
| JP4003084B2 (en) | Detoxification method for dredged soil | |
| Van Deventer et al. | Kinetics of the thermal regeneration of spent activated carbon in a fluidized bed |