JP3266856B2 - Dechlorination method of chlorine-containing polymer composition - Google Patents
Dechlorination method of chlorine-containing polymer compositionInfo
- Publication number
- JP3266856B2 JP3266856B2 JP14352598A JP14352598A JP3266856B2 JP 3266856 B2 JP3266856 B2 JP 3266856B2 JP 14352598 A JP14352598 A JP 14352598A JP 14352598 A JP14352598 A JP 14352598A JP 3266856 B2 JP3266856 B2 JP 3266856B2
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- containing polymer
- polymer composition
- organic solvent
- reaction
- 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
- 239000000460 chlorine Substances 0.000 title claims description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052801 chlorine Inorganic materials 0.000 title claims description 34
- 239000000203 mixture Substances 0.000 title claims description 30
- 229920000642 polymer Polymers 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 18
- 238000006298 dechlorination reaction Methods 0.000 title claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 7
- 230000000382 dechlorinating effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 229920003023 plastic Polymers 0.000 description 24
- 239000004033 plastic Substances 0.000 description 24
- 239000002699 waste material Substances 0.000 description 16
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 229920000915 polyvinyl chloride Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリ塩化ビニルの
ような含塩素重合体組成物の脱塩素法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dechlorinating a chlorine-containing polymer composition such as polyvinyl chloride.
【０００２】[0002]
【従来の技術】プラスチックは軽くて耐久性に富み、成
形性がよく化学的にも比較的安定で他の材料にない優れ
た特性があり、しかも安価であるため、日用品等に広く
使用されている。2. Description of the Related Art Plastics are widely used in daily necessities because plastics are light, durable, have good moldability, are relatively stable chemically, have excellent properties not found in other materials, and are inexpensive. I have.
【０００３】しかしながら、その反面廃棄物となったと
きはこの特性が裏目となり、一般家庭、各種事業所、製
造関連産業から廃棄される使用済み廃プラスチックは腐
らず嵩ばり、燃やすと混入しているポリ塩化ビニル等か
ら有害な塩素系化合物を発生し、このことに起因して焼
却炉を腐食させたり環境を汚染させたりする厄介な問題
を惹起する。[0003] On the other hand, when it is turned into waste, this property is a backfire, and the used waste plastic discarded from ordinary households, various business establishments, and manufacturing-related industries is bulky without rot and is mixed when burned. Harmful chlorine-based compounds are generated from polyvinyl chloride and the like, which causes troublesome problems of corroding incinerators and polluting the environment.
【０００４】ところが、廃棄プラスチックを焼却処分す
る際に発生する塩素系化合物による焼却炉の腐食を防止
する実用上有効な技術は確立しておらず、都市系廃棄プ
ラスチックの処理に際しては、ポリ塩化ビニル等の含塩
素プラスチックを分別除去し、その量を少なくして焼却
していた。However, no practically effective technology has been established for preventing incinerators from being corroded by chlorine compounds generated when incinerating waste plastics. Such chlorine-containing plastics were separated and removed, and the amount was reduced and incinerated.
【０００５】しかし、多量の廃棄プラスチックから含塩
素プラスチックをほぼ完全に分別除去することが大変で
あることにも起因して、大部分が埋め立て処分されてい
るのが現状である。However, at present, most of the waste plastics are landfilled because it is difficult to completely and completely separate and remove chlorine-containing plastics from a large amount of waste plastics.
【０００６】廃プラスチックの利用を考えるとき、ブラ
スチックの発熱量は１０，０００ｋｃａ１／ｋｇと高
く、塩素を除去すれば良質な重油代替燃料となるほか、
製銑高炉における還元剤或いは熱源として微粉炭を代替
できる。高炉への利用法としては、廃プラスチックを直
径６ｍｍ程度の粒状にし、熱風とともに高炉内へ吹き込
む方法があり、炉内の高温によってプラスチックが瞬時
にガス化し、これを鉄鉱石の還元剤としてまた、熱源と
して利用する途がある。高炉で溶銑を１トン造るのに微
粉炭を１５０ｋｇ使っているが、廃プラスチックを利用
できれば、５０ｋｇの微粉炭を廃プラスチックで代替で
きる。このことは、日産５，０００ｔの高炉１基で２５
０ｔ／日（８万ｔ／年）の廃プラスチックを利用できる
ことになる。When considering the use of waste plastics, the calorific value of plastics is as high as 10,000 kca1 / kg, and if chlorine is removed, it becomes a high-quality fuel oil alternative fuel.
Pulverized coal can be used as a reducing agent or heat source in the ironmaking blast furnace. As a method of using the blast furnace, there is a method in which the waste plastic is granulated to a diameter of about 6 mm and blown into the blast furnace together with hot air. The high temperature in the furnace instantaneously gasifies the plastic, and this is used as a reducing agent for iron ore. There is a way to use it as a heat source. 150 kg of pulverized coal is used to make 1 ton of hot metal in a blast furnace, but if waste plastic can be used, 50 kg of pulverized coal can be replaced with waste plastic. This means that a 5,000 ton / day blast furnace has a
0 t / day (80,000 t / year) of waste plastic can be used.
【０００７】ところが、廃プラスチックを燃焼させる
と、その中に含有されているポリ塩化ビニルから腐食性
の強い塩素系化合物およびダイオキシンなどの人体に有
害な塩素系化合物が発生するので、燃焼に際しては前も
って脱塩素処理が必要となる。However, when waste plastics are burned, highly corrosive chlorine-based compounds and dioxins and other harmful chlorine-based compounds are generated from the polyvinyl chloride contained in the waste plastics. Dechlorination is required.
【０００８】廃プラスチックからの脱塩素処理法とし
て、通常、熱分解法が用いられているが、熱分解を効率
よく進行させるためには２００℃〜４５０℃程度の高温
領域で反応を行う必要があり、実用化が非常に困難であ
った。[0008] Pyrolysis is generally used as a method for dechlorination of waste plastics, but it is necessary to carry out the reaction in a high temperature range of about 200 ° C to 450 ° C in order to make the pyrolysis proceed efficiently. Yes, it was very difficult to put it to practical use.
【０００９】これを解決するために、出願人は先に特願
平９−１４６９４９号において、可塑剤を配合したポリ
塩化ビニルを有機溶媒で溶解し、この溶液をアルカリ水
溶液と６０℃〜２００℃の温度域で加水分解することに
よって、反応率を十分にした含塩素重合体組成物の脱塩
素法を提案している。In order to solve this problem, the applicant has previously disclosed in Japanese Patent Application No. 9-146949 a method in which polyvinyl chloride containing a plasticizer is dissolved in an organic solvent, and this solution is mixed with an alkaline aqueous solution at 60 to 200 ° C. A method for dechlorinating a chlorinated polymer composition which has a sufficient conversion by hydrolyzing in the temperature range described above has been proposed.
【００１０】[0010]
【発明が解決しようとする課題】しかし、前記脱塩素法
では沸点以上の高温条件下で加水分解反応を進行せしめ
る必要があり、必然的に耐圧容器中加圧下でのバッチ式
となり、また、エネルギーコスト上の問題もある。However, in the above-described dechlorination method, it is necessary to allow the hydrolysis reaction to proceed under a high temperature condition not lower than the boiling point. There are also cost issues.
【００１１】そこで、本発明は、含塩素重合体組成物の
脱塩素を工業的規模で、常圧下で、かつ比較的低温域
で、高い反応率で含塩素重合体組成物の脱塩素反応を進
行せしめる方法を確立することにある。Accordingly, the present invention provides a process for dechlorination of a chlorine-containing polymer composition on an industrial scale under normal pressure and in a relatively low temperature range at a high reaction rate. The goal is to establish a way to get it going.
【００１２】[0012]
【課題を解決するための手段】本発明は、高沸点でしか
もポリ塩化ビニル等をよく溶かす特性を有する有機溶媒
を用いることによって、溶媒の種類によって反応率は異
なるにしても、常圧下で、しかも、比較的低温域でも十
分に反応が進行することを知見したことに基づく。SUMMARY OF THE INVENTION The present invention uses an organic solvent having a high boiling point and a property of dissolving polyvinyl chloride or the like well. Moreover, it is based on the finding that the reaction sufficiently proceeds even in a relatively low temperature range.
【００１３】すなわち、本発明の含塩素重合体組成物の
脱塩素法は、含塩素重合体組成物を有機溶媒に溶解せし
め、常圧下で、常温から前記有機溶媒の沸点までの温度
域で加水分解することを特徴とする。That is, in the method for dechlorinating a chlorine-containing polymer composition of the present invention, the chlorine-containing polymer composition is dissolved in an organic solvent, and the solution is hydrolyzed under normal pressure at a temperature range from normal temperature to the boiling point of the organic solvent. It is characterized by decomposing.
【００１４】本発明は、処理する含塩素重合体組成物に
可塑剤その他の添加剤を含有したものであっても適用で
きる。The present invention is applicable even if the chlorine-containing polymer composition to be treated contains a plasticizer and other additives.
【００１５】本発明において使用する有機溶媒として
は、水と自由に混和し、ポリ塩化ビニルのような含塩素
重合体組成物を溶解し液状物にするもので、しかも沸点
がかなり高いものが好ましい。The organic solvent used in the present invention is preferably one which is freely miscible with water, dissolves a chlorine-containing polymer composition such as polyvinyl chloride to form a liquid, and has a considerably high boiling point. .
【００１６】有機溶媒で含塩素重合体組成物を溶解する
過程では、ポリ塩化ビニルのような含塩素重合体組成物
が選択的に溶解されるから、有機溶媒に容易に溶解され
ない他のプラスチック例えばＰＥＴ等と含塩素重合体組
成物を容易かつ確実に濾別することができる。In the process of dissolving the chlorine-containing polymer composition in an organic solvent, since the chlorine-containing polymer composition such as polyvinyl chloride is selectively dissolved, other plastics which are not easily dissolved in the organic solvent, for example, PET and the like and the chlorine-containing polymer composition can be easily and reliably filtered off.
【００１７】本発明で使用する有機溶媒としては、水と
自由に混和する非プロトン性極性溶媒を用いることがで
きる。非プロトン性極性溶媒として、例えばジメチルス
ルホキシド（ＤＭＳＯ）〔Ｏ＝Ｓ（ＣＨ3）2）〕或いは
ジメチルイミダゾリジノン（ＤＭＩ）As the organic solvent used in the present invention, an aprotic polar solvent that is freely miscible with water can be used. As the aprotic polar solvent, for example, dimethyl sulfoxide (DMSO) [O = S (CH 3 ) 2 )] or dimethyl imidazolidinone (DMI)
【化１】 （ＨＭＰＡ）〔Ｏ＝Ｐ〔Ｎ（ＣＨ3）2〕3〕があるが、
ジメチルスル ホキシド（ＤＭＳＯ）が、常温から低温
域でもよく反応し、工業的な反応プロセスに用いるのに
好ましい。Embedded image (HMPA) [O = P [N (CH 3 ) 2 ] 3 ]
Dimethyl sulfoxide (DMSO) reacts well in the range from room temperature to low temperature, and is preferable for use in industrial reaction processes.
【００１８】このような有機溶媒を使用することで、常
圧下であっても、常温から有機溶媒の沸点以下の温度域
で脱塩素反応は十分に反応が進行する。By using such an organic solvent, the dechlorination reaction sufficiently proceeds in a temperature range from normal temperature to the boiling point of the organic solvent or lower even under normal pressure.
【００１９】[0019]
【発明の実施の形態】図１は本発明の含塩素重合体組成
物の脱塩素処理工程を示すフロー図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a flow chart showing a step of dechlorination of a chlorine-containing polymer composition of the present invention.
【００２０】同図に示すように、集められた廃プラスチ
ックは破砕された後、分別される。分別手段としては、
比重を溶媒と溶質の種類および量の組合せによって種々
に変えて、プラスチックの化学的組成に応じた比重によ
る分別する比重差を利用した分別法を適用できる。As shown in the figure, the collected waste plastic is crushed and then separated. As a separation method,
The specific gravity is variously changed depending on the combination of the type and amount of the solvent and the solute, and a fractionation method utilizing a specific gravity difference based on the specific gravity according to the chemical composition of the plastic can be applied.
【００２１】これによって、塩素を含まないプラスチッ
クの群と、ポリ塩化ビニル（ＰＶＣ）のような含塩素重
合体組成物およびポリエチレンテレフタレート（ＰＥ
Ｔ）のような塩素を含まないものが混在する群との２つ
の群に分別し、塩素を含まない群はそのまま燃料或いは
原料として利用する。Thus, a group of chlorine-free plastics, a chlorine-containing polymer composition such as polyvinyl chloride (PVC) and polyethylene terephthalate (PE)
T) is separated into two groups: a group containing chlorine-free materials such as T), and a group containing no chlorine is used as it is as a fuel or a raw material.
【００２２】一方、含塩素重合体組成物と塩素を含まな
いものとが混在する群は、有機溶媒によって含塩素重合
体組成物が選択的に溶解され液状物とされる。この際、
塩素を含まないものは難溶性であるために、その殆どが
固体のまま残存するから、これを濾別することによって
容易かつ確実に分別できる。On the other hand, in a group in which the chlorine-containing polymer composition and the chlorine-free polymer composition are mixed, the chlorine-containing polymer composition is selectively dissolved by an organic solvent to be a liquid. On this occasion,
Since those containing no chlorine are hardly soluble, most of them remain as solids, so that they can be easily and reliably separated by filtration.
【００２３】次いで、同図において、溶剤処理分離工程
で得られた液状物にアルカリ水溶液を加えて、常温乃至
使用する有機溶媒の沸点以下の温度域で加水分解し、塩
素を除去する。Next, in the same figure, an alkaline aqueous solution is added to the liquid obtained in the solvent treatment separation step, and the mixture is hydrolyzed at a temperature range from room temperature to the boiling point of the organic solvent to be used to remove chlorine.
【００２４】加水分解反応は、示性式 (−ＣＨ2ＣＨＣｌ−)n＋ｎＮａＯＨ→(−ＣＨ2ＣＨＯＨ
−)n＋ｎＮａＣｌ で示される。The hydrolysis reaction is represented by the chemical formula (—CH 2 CHCl—) n + n NaOH → (—CH 2 CHOH)
−) Indicated by n + nNaCl.
【００２５】このようにして脱塩素化された、例えばＰ
ＶＣが脱塩素化されポリビニルアルコール（ＰＶＡ）
は、燃料或いは他の原料として利用される。The thus dechlorinated, for example, P
VC is dechlorinated and polyvinyl alcohol (PVA)
Is used as a fuel or other raw material.
【００２６】このように、加水分解によって脱塩素化物
が生成し、食塩（ＮａＣｌ）が副生し可塑剤が分離され
る。食塩および可塑剤は系外に取り出され可塑剤はリサ
イクル等有効利用されることになる。As described above, a dechlorinated product is produced by the hydrolysis, and salt (NaCl) is by-produced to separate the plasticizer. The salt and the plasticizer are taken out of the system, and the plasticizer is effectively used for recycling or the like.
【００２７】[0027]
【実施例】実施例１ ポリ塩化ビニル５ｇを１００ｍｌのジメチルスルホキシ
ドに８０℃で溶かし常温まで冷却した後、ＮａＯＨ：
６．６ｇを水１０ｍｌに溶解したアルカリ水溶液を仕込
み、そのまま常温（３０℃）で５時間加水分解反応させ
た。Example 1 5 g of polyvinyl chloride was dissolved in 100 ml of dimethyl sulfoxide at 80 ° C. and cooled to room temperature.
An aqueous alkaline solution in which 6.6 g was dissolved in 10 ml of water was charged, and the mixture was subjected to a hydrolysis reaction at room temperature (30 ° C.) for 5 hours.
【００２８】反応生成物は、アルコール等の、反応後の
ポリマーを溶かさないメタノール４００ｍｌで処理し、
ポリマーを取り除いた後の液から消費ＮａＯＨ量を分析
し、原料ポリ塩化ビニルのＣｌ含有量で消費ＮａＯＨ量
を除して反応率を求めた。また、反応により生成するＮ
ａＣｌをイオンクロマト法で分析することにより反応率
を求めることもできる。その際、有機溶媒自体のＮａＯ
Ｈ消費もあるので、ブランクテストとしてポリ塩化ビニ
ルを仕込まない状態での加水分解を行い、そのときのＮ
ａＯＨ消費を差引いた。また、イオンクロマト法による
分析値を差引いて実質のポリ塩化ビニルのみの反応率を
求めることもできる。このときの脱塩素化率即ち反応率
は７８．８％であった。The reaction product is treated with 400 ml of methanol which does not dissolve the polymer after the reaction, such as alcohol,
The amount of NaOH consumed was analyzed from the liquid after removing the polymer, and the reaction rate was determined by dividing the amount of NaOH consumed by the Cl content of the starting polyvinyl chloride. In addition, N generated by the reaction
The reaction rate can also be determined by analyzing aCl by ion chromatography. At that time, NaO of the organic solvent itself
As there is also consumption of H, as a blank test, hydrolysis was carried out without charging polyvinyl chloride.
aOH consumption was deducted. Also, the reaction rate of the substantial polyvinyl chloride alone can be obtained by subtracting the analysis value by the ion chromatography method. At this time, the dechlorination rate, that is, the reaction rate, was 78.8%.
【００２９】実施例２ 加水分解反応をそれそれ５０℃、８０℃、１００℃およ
び１３０℃の温度で進行させた他は、実施例１と同じ条
件で実施した。反応率はそれぞれ９８．８％、９９．０
％、１００％および９９．２％であった。Example 2 The reaction was carried out under the same conditions as in Example 1 except that the hydrolysis reaction was carried out at 50 ° C., 80 ° C., 100 ° C. and 130 ° C., respectively. The reaction rates were 98.8% and 99.0, respectively.
%, 100% and 99.2%.
【００３０】比較例１ ポリ塩化ビニル５ｇを３００ｍｌ三つ口フラスコでそれ
ぞれ１００ｍｌのジオキサンおよびテトラヒドロフラン
に溶かした後、ＮａＯＨ：６．６ｇを水１０ｍｌに溶解
したアルカリ水溶液を仕込み、常圧下に、ジオキサンの
場合は８０℃で、テトラヒドロフランの場合は６０℃で
それぞれ５時間加水分解反応させた。同時に、ブランク
テストも実施例１と同一反応条件で行い、分析も実施例
１と同様な方法で行って反応率を求めた。その結果、反
応率は、有機溶媒をジオキサンとした場合は８．７％で
あり、テトラヒドロフランとした場合は、３．３％であ
った。COMPARATIVE EXAMPLE 1 5 g of polyvinyl chloride was dissolved in 100 ml of dioxane and tetrahydrofuran in a 300 ml three-necked flask, and an alkaline aqueous solution in which 6.6 g of NaOH was dissolved in 10 ml of water was charged. The hydrolysis reaction was carried out at 80 ° C. for 5 hours and at 60 ° C. for tetrahydrofuran for 5 hours. At the same time, a blank test was performed under the same reaction conditions as in Example 1, and an analysis was performed in the same manner as in Example 1 to determine a reaction rate. As a result, the reaction rate was 8.7% when the organic solvent was dioxane, and was 3.3% when the organic solvent was tetrahydrofuran.
【００３１】比較例２ 加水分解反応をオートクレーブ中加圧下に、１２０℃で
５時間進行させた他は、比較例１と同じ条件で実施し
た。その結果、反応率は、有機溶媒をジオキサンとした
場合は５２．８％であり、テトラヒドロフランとした場
合は、６８．６％であった。Comparative Example 2 The same procedure as in Comparative Example 1 was carried out except that the hydrolysis reaction was allowed to proceed at 120 ° C. for 5 hours under pressure in an autoclave. As a result, the reaction rate was 52.8% when dioxane was used as the organic solvent and 68.6% when tetrahydrofuran was used.
【００３２】図２は、本発明における脱塩素反応プロセ
ス即ち、可塑剤を配合された含塩素重合体組成物を、有
機溶媒としてジメチルスルホキシド（ＤＭＳＯ）を用い
て溶解し溶液状態にしたものを加水分解したときの、反
応温度と反応率の関係を示す。 比較のために、先に挙
げた特願平９−１４６９４９号に開示した、ジオキサン
或いはテトラヒドロフランを有機溶媒としてボリ塩化ビ
ニルを溶解し得られた液状物を、オートクレーブ中６０
℃〜２００℃の温度域で加水分解したときの反応温度と
反応率の関係を併せて示す。FIG. 2 shows a dechlorination reaction process according to the present invention, that is, a solution obtained by dissolving a chlorine-containing polymer composition containing a plasticizer using dimethyl sulfoxide (DMSO) as an organic solvent to form a solution. The relationship between the reaction temperature and the reaction rate when decomposed is shown. For comparison, a liquid obtained by dissolving polyvinyl chloride using dioxane or tetrahydrofuran as an organic solvent and disclosed in Japanese Patent Application No. 9-146949 mentioned above was used in an autoclave.
The relationship between the reaction temperature and the reaction rate when hydrolyzed in a temperature range of ℃ to 200 ℃ is also shown.
【００３３】同図から、含塩素重合体組成物をジメチル
スルホキシド（ＤＭＳＯ）といった水と混和する非プロ
トン性極性溶媒で溶解し液状物とするプロセスを採るこ
とによって、次の加水分解反応を常圧下に格段に低い温
度域で高い反応率下に進行させ得ることが分かる。From the figure, it can be seen that the following hydrolysis reaction is carried out at normal pressure by dissolving the chlorine-containing polymer composition in a water-miscible aprotic polar solvent such as dimethylsulfoxide (DMSO) to form a liquid. It can be seen that the reaction can proceed at a significantly lower temperature range and a higher reaction rate.
【００３４】[0034]
【発明の効果】本発明によれば、工業的規模で、可塑剤
を配合した含塩素重合体組成物の脱塩素を従来技術にお
けるような高温、高圧下で行う必要はなく、格段に低い
温度域で、しかも常圧下に高い効率で行うことができ
る。According to the present invention, it is not necessary to carry out dechlorination of a chlorine-containing polymer composition containing a plasticizer at a high temperature and a high pressure as in the prior art on an industrial scale. And at high efficiency under normal pressure.
【００３５】従って、低いエネルギーコストで含塩素重
合体組成物の脱塩素が可能となり、廃プラスチックを重
油代替燃料として活用することができ埋め立て処分が不
要になるほか、一例として高炉操業における還元剤或い
は熱源として利用でき、微粉炭の使用量を大きく減少さ
せることができる等、プラスチック廃棄物の再資源化に
資することができる。Therefore, the chlorine-containing polymer composition can be dechlorinated at a low energy cost, the waste plastic can be used as an alternative fuel for heavy oil, and no landfill disposal is required. For example, a reducing agent or a reducing agent for blast furnace operation is used. It can be used as a heat source and can greatly reduce the amount of pulverized coal used, contributing to the recycling of plastic waste.
【図１】 本発明プロセスにおける廃棄プラスチックの
分別から含塩素重合体組成物の脱塩素処理工程までのフ
ローを示す。FIG. 1 shows a flow from the separation of waste plastic to the step of dechlorinating a chlorine-containing polymer composition in the process of the present invention.
【図２】 本発明のプロセスにおける加水分解反応温度
と反応率の関係を従来例と対比して示す。FIG. 2 shows the relationship between the hydrolysis reaction temperature and the conversion in the process of the present invention in comparison with a conventional example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 武藤 光明 福岡県北九州市戸畑区牧山一丁目１番36 号 濱田重工株式会社内 (56)参考文献 特開 平７−11026（ＪＰ，Ａ) 特開 昭48−64160（ＪＰ，Ａ) 特開 平８−325407（ＪＰ，Ａ) 特開 平７−179651（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 11/00 - 11/28 B09B 3/00 304 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Mitsuaki Mutoh 1-36 Makiyama, Tobata-ku, Kitakyushu-shi, Fukuoka Hamada Heavy Industries, Ltd. (56) References JP-A-7-111026 (JP, A) 48-64160 (JP, A) JP-A-8-325407 (JP, A) JP-A-7-179651 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 11 / 00-11/28 B09B 3/00 304
Claims (3)
し、得られた溶液を常圧下に、常温から前記有機溶媒の
沸点までの温度域で加水分解することを特徴とする含塩
素重合体組成物の脱塩素法。1. A chlorine-containing polymer comprising dissolving a chlorine-containing polymer composition in an organic solvent, and hydrolyzing the resulting solution under normal pressure in a temperature range from room temperature to the boiling point of the organic solvent. Dechlorination of coalescing composition.
が、水と自由に混和する非プロトン性極性溶媒である請
求項１に記載の含塩素重合体組成物の脱塩素法。2. The method for dechlorinating a chlorine-containing polymer composition according to claim 1, wherein the organic solvent dissolving the chlorine-containing polymer composition is an aprotic polar solvent that is freely miscible with water.
が、ジメチルスルホキシドである請求項２に記載の含塩
素重合体組成物の脱塩素法。3. The method for dechlorinating a chlorine-containing polymer composition according to claim 2, wherein the organic solvent for dissolving the chlorine-containing polymer composition is dimethyl sulfoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14352598A JP3266856B2 (en) | 1998-05-25 | 1998-05-25 | Dechlorination method of chlorine-containing polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14352598A JP3266856B2 (en) | 1998-05-25 | 1998-05-25 | Dechlorination method of chlorine-containing polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11335484A JPH11335484A (en) | 1999-12-07 |
| JP3266856B2 true JP3266856B2 (en) | 2002-03-18 |
Family
ID=15340775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14352598A Expired - Fee Related JP3266856B2 (en) | 1998-05-25 | 1998-05-25 | Dechlorination method of chlorine-containing polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3266856B2 (en) |
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1998
- 1998-05-25 JP JP14352598A patent/JP3266856B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11335484A (en) | 1999-12-07 |
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