JP2717760B2 - Oiling method of vulcanized rubber - Google Patents
Oiling method of vulcanized rubberInfo
- Publication number
- JP2717760B2 JP2717760B2 JP10040493A JP10040493A JP2717760B2 JP 2717760 B2 JP2717760 B2 JP 2717760B2 JP 10040493 A JP10040493 A JP 10040493A JP 10040493 A JP10040493 A JP 10040493A JP 2717760 B2 JP2717760 B2 JP 2717760B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber
- reaction
- vulcanized rubber
- reaction time
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- 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
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ゴムを主原料として製
造されたタイヤ・ホース等の加硫ゴム製品を再資源化す
るための油化反応の反応速度を高め、反応時間を短縮さ
せる加硫ゴムの油化方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention increases the reaction rate of an oiling reaction for recycling vulcanized rubber products such as tires and hoses made from rubber as a main raw material and shortens the reaction time. The present invention relates to a method for oiling vulcanized rubber.
【０００２】[0002]
【従来の技術】例えば、ＥＰＤＭ １００重量部に対し
て、ジキシルジスルフィド ３重量部、酸化亜鉛 ５重
量部、硫黄 ２重量部、促進剤ＤＭ ２重量部 よりな
る加硫ゴムを、裁断もしくは粉砕し、１Ｎ−ＮａＯＨ水
溶液中に加え試料ゴム重量百分率３０％、充填率 ３０
％、温度 ４２０℃迄昇温速度４０℃／分で昇温し、分
解・油化を行い、反応時間の油収率に及ぼす影響を求め
ると、図１に示す結果が得られる。なお、その際、誘導
式加熱炉・小型オートクレーブ等を使った。また、反応
時間・試料ゴム重量百分率・充填率・油収率はそれぞれ
次のように定義される。 反応時間：所定反応温度（４２０±１０℃）到達後の保持時間 試料ゴム重量百分率＝（ゴム重量／ゴム重量及び溶媒重量の和）×１００ 充填率＝（ゴム体積及び溶媒体積の和／高圧容器内容積）×１００ 油収率＝（生成油重量／ゴム重量）×１００2. Description of the Related Art For example, a vulcanized rubber comprising 3 parts by weight of dixyl disulfide, 5 parts by weight of zinc oxide, 2 parts by weight of sulfur, and 2 parts by weight of a promoter DM is cut or crushed with respect to 100 parts by weight of EPDM. 1% NaOH aqueous solution, sample rubber weight percentage 30%, filling rate 30
%, The temperature was raised to 420 ° C. at a temperature rising rate of 40 ° C./min to perform decomposition / oiling, and to determine the effect of the reaction time on the oil yield, the result shown in FIG. 1 was obtained. At that time, an induction heating furnace, a small autoclave and the like were used. The reaction time, the percentage by weight of the sample rubber, the filling rate, and the oil yield are defined as follows. Reaction time: Retention time after reaching a predetermined reaction temperature (420 ± 10 ° C.) Percentage of rubber weight of sample = (Rubber weight / sum of rubber weight and solvent weight) × 100 Filling rate = (sum of rubber volume and solvent volume / high pressure vessel) Internal volume) x 100 Oil yield = (weight of produced oil / weight of rubber) x 100
【０００３】しかしながら、上記従来の加硫ゴム製品の
油化反応は、油収率はともかく、○印で示されるよう
に、油中に未分解ゴムが残留し（油収率にはこの未分解
ゴムを含む）、●印で示されるように、それがなくなる
迄には１５分を要すると言う問題点がある。[0003] However, in the oiling reaction of the conventional vulcanized rubber product, undecomposed rubber remains in the oil as indicated by a circle, regardless of the oil yield. There is a problem that it takes 15 minutes for it to disappear, as indicated by the mark ●.
【０００４】[0004]
【発明が解決しようとする課題】解決しようとする問題
点は、上記従来の加硫ゴムの油化反応の速度は、油収率
はともかく、油中に未分解ゴムが残留し、それがなくな
る迄には１５分を要する程度に遅いことである。The problem to be solved is that the speed of the conventional oil conversion reaction of the vulcanized rubber is not limited to the oil yield, but the undecomposed rubber remains in the oil and disappears. It takes as long as 15 minutes to complete.
【０００５】[0005]
【課題を解決するための手段】この発明に係る加硫ゴム
の油化方法は、加硫ゴムに対して、溶媒として、水溶液
を用いて、超臨界域下（温度６４７Ｋ以上且つ圧力２２
ＭＰａ以上）にて反応させるに当り、金属塩好ましくは
金属酸化物を５重量％以上添加することを特徴とするも
のである。According to the present invention, there is provided a method for converting a vulcanized rubber into an oil by using an aqueous solution as a solvent in a supercritical region (at a temperature of 647K or more and a pressure of 22
(Mpa or more), characterized in that a metal salt, preferably a metal oxide, is added in an amount of 5% by weight or more.
【０００６】[0006]
【実施例】実施例について図によって説明すると、上記
従来例と同様、ＥＰＤＭ １００重量部に対して、ジキ
シルジスルフィド ３重量部、酸化亜鉛 ５重量部、硫
黄２重量部、促進剤ＤＭ ２重量部 よりなる加硫ゴム
を、裁断もしくは粉砕し、触媒としてＺｎＯ ３０ｗｔ
％添加した上、１Ｎ−ＮａＯＨ水溶液中に加え、試料ゴ
ム重量百分率３０％、充填率３０％に設定し、温度４２
０℃、圧力約３０ＭＰａ迄昇温速度４０℃／分で昇温
し、超臨界域下で分解・油化を行い、図２に示す結果を
得た。なお、その際、誘導式加熱炉・小型オートクレー
ブ等を使った。また、反応時間・試料ゴム重量百分率・
充填率・油収率はそれぞれ次のように定義される。 反応時間：所定反応温度（４２０±１０℃）到達後の保持時間 試料ゴム重量百分率＝（ゴム重量／ゴム重量及び溶媒重量の和）×１００ 充填率＝（ゴム体積及び溶媒体積の和／高圧容器内容積）×１００ 油収率＝（生成油重量／ゴム重量）×１００Examples will be described with reference to the drawings. Similar to the above-mentioned conventional example, 3 parts by weight of dixyl disulfide, 5 parts by weight of zinc oxide, 2 parts by weight of sulfur, and 2 parts by weight of an accelerator are added to 100 parts by weight of EPDM. Vulcanized rubber is cut or pulverized, and ZnO 30 wt.
% Of the sample rubber, and the filling rate was set to 30% and the filling rate was set to 30%.
The temperature was increased to 0 ° C. and a pressure of about 30 MPa at a rate of temperature increase of 40 ° C./min, and decomposition and oiling were performed in a supercritical range, and the results shown in FIG. 2 were obtained. At that time, an induction heating furnace, a small autoclave and the like were used. Also, the reaction time, sample rubber weight percentage,
The filling rate and the oil yield are defined as follows. Reaction time: Retention time after reaching a predetermined reaction temperature (420 ± 10 ° C.) Percentage of rubber weight of sample = (Rubber weight / sum of rubber weight and solvent weight) × 100 Filling rate = (sum of rubber volume and solvent volume / high pressure vessel) Internal volume) x 100 Oil yield = (weight of produced oil / weight of rubber) x 100
【０００７】また、上記加硫ゴムについて、他の反応条
件は同一にして、反応時間を２分と一定にし、それぞれ
触媒としてのＺｎＯの添加量を変化させた場合の油収率
への影響をを調べ、次の表１の結果を得た。[0007] Further, with respect to the above-mentioned vulcanized rubber, the other reaction conditions were the same, the reaction time was kept constant at 2 minutes, and the effect on the oil yield when the addition amount of ZnO as a catalyst was changed was examined. And the results in Table 1 below were obtained.
【０００８】[0008]
【表１】 [Table 1]
【０００９】系中の全亜鉛モル数とは試料ゴム中に含ま
れる亜鉛と添加した亜鉛のモル数の和のことである。The total number of moles of zinc in the system is the sum of the number of moles of zinc contained in the sample rubber and the added zinc.
【００１０】更に複合触媒について、金属酸化物を含む
触媒の種類と反応完結までの時間との関係を調べ次の表
２の結果を得た。Further, for the composite catalyst, the relationship between the type of the catalyst containing the metal oxide and the time until the completion of the reaction was examined, and the results shown in Table 2 below were obtained.
【００１１】[0011]
【表２】 [Table 2]
【００１２】作用について説明すると、図２に示すよう
に、反応時間２分で既に油中に未分解ゴムが残留せず、
触媒を加えないものに比較して、反応時間が著しく短縮
される。さらに、Ｃ０Ｏ，Ｍ０Ｏ３等の複合触媒を添加
することにより、さらに高い油収率９５％を得るための
反応時間が短縮され、反応時間は秒オーダーになる。表
１によれば、ＺｎＯ量は０．０５８ｇ（Ｓ：ＺｎＯ＝
１：１）が最適量であることがわかる。The operation will be described. As shown in FIG. 2, the undecomposed rubber does not remain in the oil in the reaction time of 2 minutes.
The reaction time is significantly reduced as compared to the case without a catalyst. Furthermore, by adding a composite catalyst such as C 0 O and M 0 O 3 , the reaction time for obtaining a higher oil yield of 95% is reduced, and the reaction time is on the order of seconds. According to Table 1, the amount of ZnO is 0.058 g (S: ZnO =
1: 1) is the optimum amount.
【００１３】表２によれば、市販の金属酸化物を含むＣ
ＤＳ−Ｄ２１ＴＨＴ−Ｄ３ＴおよびＺｎＯの混合物を用
いれば、反応時問を３０秒にまで短縮可能であることが
わかる。According to Table 2, C containing commercially available metal oxides
It can be seen that the reaction time can be reduced to 30 seconds by using a mixture of DS-D21THT-D3T and ZnO.
【００１４】このように、触媒としては、ＺｎＯに限ら
ず、金属塩好ましくは金属酸化物を処理加硫ゴムに対し
て５重量％以上添加すればよい。金属酸化物が、加水分
解による架橋鎖の切断の際に生成した硫化水素を取り除
くことによって、加水分解を助長させ、次の段階の油化
反応をも促進させるものと推察される。As described above, the catalyst is not limited to ZnO, and a metal salt, preferably a metal oxide, may be added in an amount of 5% by weight or more based on the treated vulcanized rubber. It is presumed that the metal oxide promotes hydrolysis by removing hydrogen sulfide generated at the time of cleavage of the crosslinked chain by hydrolysis, and also promotes the next step of oiling reaction.
【００１５】脱硫の反応機構は図３に、油化反応は図４
にそれぞれ従うものと考えられる。FIG. 3 shows the desulfurization reaction mechanism, and FIG.
Respectively.
【００１６】[0016]
【発明の効果】本発明は以上のように構成されるため、
安価な触媒によって、ゴムを主原料として製造されたタ
イヤ・ホース等の加硫ゴム製品を再資源化するための油
化反応の反応速度を高められ、反応時間が著しく短縮さ
れる。Since the present invention is configured as described above,
An inexpensive catalyst can increase the reaction rate of an oiling reaction for recycling vulcanized rubber products such as tires and hoses manufactured using rubber as a main raw material, thereby significantly reducing the reaction time.
【図１】従来例の反応時間と油収率との関係を示す特性
図である。FIG. 1 is a characteristic diagram showing a relationship between a reaction time and an oil yield in a conventional example.
【図２】本発明の実施例の反応時間と油収率との関係を
示す特性図である。FIG. 2 is a characteristic diagram showing a relationship between a reaction time and an oil yield in an example of the present invention.
【図３】本発明の脱硫の反応機構を示す化学式の図であ
る。FIG. 3 is a diagram of a chemical formula showing a reaction mechanism of desulfurization of the present invention.
【図４】本発明の油化反応を示す模式図である。FIG. 4 is a schematic diagram showing an oiling reaction of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 天王 俊成 広島市西区三篠町２丁目２番８号 西川 ゴム工業株式会社内 (56)参考文献 特開 昭50−35101（ＪＰ，Ａ) 特開 平５−287281（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Toshinari Tenno 2-5-2-8, Mishino-cho, Nishi-ku, Hiroshima-shi Inside Nishikawa Rubber Industries Co., Ltd. (56) References 5-287281 (JP, A)
Claims (1)
を用いて、超臨界域下（温度６４７Ｋ以上且つ圧力２２
ＭＰａ以上）にて反応させるに当り、金属塩好ましくは
金属酸化物を５重量％以上添加することを特徴とする加
硫ゴムの油化方法。An aqueous solution is used as a solvent for a vulcanized rubber in a supercritical region (at a temperature of 647K or more and a pressure of 22
Per the reaction is effected under MPa or more), the metal salt preferably Yuka method that pressurized <br/> vulcanized rubber be characterized by the addition of metal oxide 5 wt% or more.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10040493A JP2717760B2 (en) | 1993-04-01 | 1993-04-01 | Oiling method of vulcanized rubber |
| DE4411483A DE4411483C2 (en) | 1993-04-01 | 1994-03-29 | Process for the desulfurization of sulfur-containing compositions by hydrothermal reaction |
| DE4447937A DE4447937C2 (en) | 1993-04-01 | 1994-03-29 | Desulphurising sulphur-contg. compsns., esp. vulcanised rubber |
| US08/219,104 US5502262A (en) | 1993-04-01 | 1994-03-29 | Process for the conversion of vulcanized rubbers into oils by use of supercritical aqueous fluids |
| FR9403815A FR2703360B1 (en) | 1993-04-01 | 1994-03-31 | Process for the desulfurization of compositions containing sulfur and process for the conversion into oils of vulcanized rubbers. |
| FR9409627A FR2706168B1 (en) | 1993-04-01 | 1994-08-03 | Process for the conversion of vulcanized rubber oils. |
| NL9401326A NL194762C (en) | 1993-04-01 | 1994-08-17 | Process for desulphurizing sulfur-containing compositions by means of a hydrothermal reaction. |
| US08/563,364 US5639934A (en) | 1993-04-01 | 1995-11-28 | Process for the desulfurization of sulfur-containing compositions by hydrothermal reaction |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10040493A JP2717760B2 (en) | 1993-04-01 | 1993-04-01 | Oiling method of vulcanized rubber |
| NL9401326A NL194762C (en) | 1993-04-01 | 1994-08-17 | Process for desulphurizing sulfur-containing compositions by means of a hydrothermal reaction. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287351A JPH06287351A (en) | 1994-10-11 |
| JP2717760B2 true JP2717760B2 (en) | 1998-02-25 |
Family
ID=26441440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10040493A Expired - Fee Related JP2717760B2 (en) | 1993-04-01 | 1993-04-01 | Oiling method of vulcanized rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2717760B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894377A (en) * | 2003-12-19 | 2007-01-10 | 国际壳牌研究有限公司 | Systems, methods, and catalysts for producing a crude product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7406620A (en) * | 1973-05-21 | 1974-11-25 | ||
| JPH05287281A (en) * | 1992-02-10 | 1993-11-02 | Mazda Motor Corp | Method for producing low-boiling hydrocarbon oil from waste plastic or rubber material and equipment therefor |
-
1993
- 1993-04-01 JP JP10040493A patent/JP2717760B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06287351A (en) | 1994-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2717760B2 (en) | Oiling method of vulcanized rubber | |
| JPH03212405A (en) | Removal of bf3 from olefinoligomer by bf3 catalyst | |
| EP0404178B1 (en) | Process for producing over-based sulfurized alkaline earth metal phenate type detergent | |
| CA2459579A1 (en) | Method of producing silicon metal particulates of reduced average size | |
| JP4046209B2 (en) | Recycled vulcanized rubber | |
| TWI308144B (en) | High yield cyclohexyl hydroperoxide decomposition process | |
| CA1245010A (en) | Reclaiming of vulcanized rubber | |
| EP2918551A1 (en) | Method for treating waste water containing fluorine component | |
| DE69506792T2 (en) | Suppression of dioxane formation when glycols are obtained from polyester resins | |
| WO2008135777A1 (en) | Treatment of epoxidized natural rubber latex | |
| EP0640682A1 (en) | Over-based sulfurized alkaline earth metal phenate and process for producing the same | |
| US4911758A (en) | Disposal of waste aqueous boron trifluoride solutions | |
| JP4841099B2 (en) | Compositions of polysulfides having reduced odor levels | |
| KR910007846A (en) | Method for producing 1,1-dichlorotetrafluoroethane | |
| US4751326A (en) | Process for producing benzophenone-azine | |
| EP4105299A1 (en) | Method for removing chlorine from waste oil fractions containing high content of chlorine using solid acid material | |
| US5430165A (en) | Method of oxidizing aluminum alkyls | |
| EP0558021A2 (en) | Process for producing over-based alkaline earth metal phenate | |
| US1967319A (en) | Treatment of fats to produce fatty acids | |
| JPH09286744A (en) | Method for recovering terephthalic acid and ethylene glycol from polyethylene terephthalate | |
| CN114981233B (en) | Method for increasing the rate of preformation of a hydroformylation catalyst | |
| EP0404379B1 (en) | Method for recovering solid molybdenum compounds | |
| GB1590958A (en) | Oxidation of cyclohexane | |
| CN1219553A (en) | Vulcanization acceralator for rare earth rubber and its preparation method | |
| JP2000063386A (en) | Manufacture of carboxylate of lanthanide metal, and its use as catalyst for polymerization of dienic monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |