JP2005307007A - Method for pyrolyzing waste plastic - Google Patents
Method for pyrolyzing waste plastic Download PDFInfo
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- JP2005307007A JP2005307007A JP2004126000A JP2004126000A JP2005307007A JP 2005307007 A JP2005307007 A JP 2005307007A JP 2004126000 A JP2004126000 A JP 2004126000A JP 2004126000 A JP2004126000 A JP 2004126000A JP 2005307007 A JP2005307007 A JP 2005307007A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 51
- 239000004033 plastic Substances 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 87
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000008187 granular material Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009826 distribution Methods 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims description 77
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 10
- 238000010298 pulverizing process Methods 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 2
- 238000007688 edging Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 abstract 3
- 239000000741 silica gel Substances 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 6
- 229920013716 polyethylene resin Polymers 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、廃プラスチックの分解方法に関し、詳しくは、酸化チタン又はその混合物の顆粒体の存在下に廃プラスチックを加熱し、ガス化する廃プラスチックの分解方法に関する。 The present invention relates to a method for decomposing waste plastics, and more particularly to a method for decomposing waste plastics by heating and plasticizing waste plastics in the presence of granules of titanium oxide or a mixture thereof.
近年、廃プラスチックを処理し、又は再利用する方法として、種々のものが提案され、また、一部は実用化されている。このような廃プラスチックの再利用、資源化の一つの有力な方法として、廃プラスチック片を光触媒として知られている酸化チタンからなる分解触媒の存在下に紫外線を照射しながら、加熱して、廃プラスチックをガス化する方法が提案されている（特許文献１参照）。 In recent years, various methods for treating or reusing waste plastic have been proposed, and some of them have been put into practical use. As one effective method for recycling and recycling such waste plastics, waste plastic pieces are heated while being irradiated with ultraviolet rays in the presence of a decomposition catalyst made of titanium oxide, which is known as a photocatalyst. A method of gasifying plastic has been proposed (see Patent Document 1).
しかし、このように、酸化チタンを分解触媒として用いて廃プラスチックを熱分解する方法は、廃プラスチックの熱分解によるガス化を促進するために、通常、容器中に担体ガスを流通させながら、酸化チタンと廃プラスチック片とを攪拌下に加熱し、廃プラスチックを熱分解して、熱分解生成物である分解ガスを容器外に排出させるものである。従って、触媒として用いられる酸化チタン粒子は摩耗し、微粉化し、廃プラスチックの熱分解生成ガスと同伴して容器外に失われるので、時間の経過と共に、熱分解効率が低下する。また、酸化チタン粒子の微粉化に伴って、その粒度分布が変化し、この点からも、廃プラスチックの熱分解効率が低下する。 However, in this way, the method of thermally decomposing waste plastics using titanium oxide as a decomposition catalyst usually promotes oxidation while circulating the carrier gas in the container in order to promote gasification by thermal decomposition of the waste plastics. Titanium and the waste plastic piece are heated with stirring to thermally decompose the waste plastic, and the decomposition gas as the pyrolysis product is discharged out of the container. Accordingly, the titanium oxide particles used as a catalyst are worn, pulverized, and lost to the outside of the container along with the thermal decomposition product gas of the waste plastic, so that the thermal decomposition efficiency decreases with the passage of time. In addition, as the titanium oxide particles are pulverized, the particle size distribution changes, and also from this point, the thermal decomposition efficiency of the waste plastic is lowered.
そこで、容器から熱分解ガスを排出させるための管路にフィルターを取付ければ、微粉化した酸化チタンを回収することはできるが、フィルターが容易に目詰まりを起こすので、廃プラスチックの熱分解効率の低下を招く。他方、酸化チタンの微粉化を避けるために、徒に粒径を大きいもののみを用いても、廃プラスチックの熱分解効率に劣る。
本発明は、酸化チタンの粒子を熱分解触媒として用いる廃プラスチックの熱分解における上述した問題を解決するためになされたものであって、廃プラスチックの熱分解効率を高く保ちながら、しかも、触媒の微粉化による損失を最小限に抑えた廃プラスチックの熱分解方法を提供することを目的とする。 The present invention has been made in order to solve the above-mentioned problems in the thermal decomposition of waste plastics using titanium oxide particles as a thermal decomposition catalyst, and while maintaining high thermal decomposition efficiency of the waste plastics, An object of the present invention is to provide a method for thermally decomposing waste plastic in which loss due to pulverization is minimized.
本発明によれば、第１の方法として、担体ガスの流通下に酸化チタンの顆粒体からなる触媒と共に廃プラスチック片を加熱しながら攪拌して、上記プラスチックをガス化する廃プラスチックの分解方法において、上記酸化チタンの顆粒体がチタン酸化物のゾルを乾燥して酸化チタンゲルとし、この酸化チタンゲルを４５０〜８５０℃の範囲の温度で焼成し、この焼成物を破砕し、エッジ処理して得られるものであって、０．５〜１．１８ｍｍの粒径を有する粒子の割合が５０〜９５重量％の範囲にあり、１．１８〜１．７ｍｍの粒径を有する粒子の割合が５〜５０重量％の範囲にある粒度分布を有すると共に、２．０％以下の摩耗率を有するものであることを特徴とする方法が提供される。 According to the present invention, as a first method, in the method for decomposing waste plastics, the plastic waste is gasified by stirring while heating the waste plastic pieces together with a catalyst comprising titanium oxide granules under the flow of a carrier gas. The titanium oxide granules are obtained by drying a titanium oxide sol to form a titanium oxide gel, firing the titanium oxide gel at a temperature in the range of 450 to 850 ° C., crushing the fired product, and subjecting it to an edge treatment. The ratio of particles having a particle diameter of 0.5 to 1.18 mm is in the range of 50 to 95% by weight, and the ratio of particles having a particle diameter of 1.18 to 1.7 mm is 5 to 50 A method is provided that has a particle size distribution in the range of weight percent and has a wear rate of 2.0% or less.
更に、本発明によれば、第２の方法として、担体ガスの流通下にアルミナとシリカから選ばれる少なくとも１種と酸化チタンとの混合物の顆粒体からなる触媒と共に廃プラスチック片を加熱しながら攪拌して、上記プラスチックをガス化する廃プラスチックの分解方法において、上記アルミナとシリカから選ばれる少なくとも１種と酸化チタンとの混合物の顆粒体がアルミナゾルとシリカゾルから選ばれる少なくとも１種のゾルとチタン酸化物のゾルとを混合し、乾燥してゲルとし、このゲルを４５０〜８５０℃の範囲の温度で焼成し、この焼成物を破砕し、エッジ処理して得られるものであって、０．５〜１．１８ｍｍの粒径を有する粒子の割合が５０〜９５重量％の範囲にあり、１．１８〜１．７ｍｍの粒径を有する粒子の割合が５〜５０重量％の範囲にある粒度分布を有すると共に、２．０％以下の摩耗率を有するものであることを特徴とする方法が提供される。 Furthermore, according to the present invention, as a second method, the waste plastic piece is stirred while heating the catalyst together with a catalyst comprising granules of a mixture of at least one selected from alumina and silica and titanium oxide under a carrier gas flow. Then, in the method for decomposing waste plastics for gasifying the plastic, the granule of a mixture of at least one selected from alumina and silica and titanium oxide is oxidized with at least one sol selected from alumina sol and silica sol and titanium oxide. It is obtained by mixing with a sol of a product, drying to obtain a gel, firing the gel at a temperature in the range of 450 to 850 ° C., crushing the fired product, and performing edge treatment. The proportion of particles having a particle size of ˜1.18 mm is in the range of 50 to 95% by weight and the proportion of particles having a particle size of 1.18 to 1.7 mm is 5 to 5 And it has a particle size distribution in the range of weight%, wherein the one having 2.0% or less of the wear rate is provided.
本発明の方法によれば、酸化チタン又はこれを含む混合物のゲルの焼成物を破砕し、エッジ処理して、所定の粒度分布と摩耗率とを有する顆粒体を熱分解触媒として用いるので、廃プラスチックの熱分解効率を高く保ちながら、しかも、上記顆粒体からなる触媒の微粉化による損失を最小限に抑えることができる。 According to the method of the present invention, the burned product of the gel of titanium oxide or a mixture containing the same is crushed, edge-treated, and granules having a predetermined particle size distribution and wear rate are used as the pyrolysis catalyst. While keeping the thermal decomposition efficiency of the plastic high, it is possible to minimize the loss due to the pulverization of the catalyst composed of the granules.
本発明に従って、廃プラスチックを熱分解するための装置構成の一例を図１に示す。反応容器１は、廃プラスチック片をこの反応容器に投入するための投入口２と、担体ガス３を反応容器に導入し、生成する熱分解ガスを反応容器から搬出するための担体ガス管４を備えており、更に、反応容器中の熱分解触媒５と廃プラスチック片６を攪拌するための攪拌機７を備えている。また、反応容器中の熱分解触媒と廃プラスチック片を加熱するための加熱装置８を備えている。図示した装置においては、この加熱装置は反応容器外に配設されているが、反応容器内に配設されていてもよい。上記担体ガスとしては、通常、空気が用いられるが、必要に応じて、不活性ガスを用いてもよい。しかし、本発明に従って、廃プラスチックを熱分解するに際して、用いる装置は上記例示に限定されるものではなく、例えば、ロータリーキルンや流動床装置を用いることもできる。 An example of an apparatus configuration for thermally decomposing waste plastic according to the present invention is shown in FIG. The reaction vessel 1 has an inlet 2 for introducing waste plastic pieces into the reaction vessel, and a carrier gas pipe 4 for introducing the carrier gas 3 into the reaction vessel and carrying out the pyrolysis gas to be generated from the reaction vessel. And a stirrer 7 for stirring the thermal decomposition catalyst 5 and the waste plastic piece 6 in the reaction vessel. Moreover, the heating apparatus 8 for heating the thermal decomposition catalyst and waste plastic piece in a reaction container is provided. In the illustrated apparatus, the heating device is disposed outside the reaction container, but may be disposed within the reaction container. As the carrier gas, air is usually used, but an inert gas may be used if necessary. However, when pyrolyzing waste plastic according to the present invention, the apparatus to be used is not limited to the above example, and for example, a rotary kiln or a fluidized bed apparatus can be used.
本発明によれば、熱分解触媒として、第１の方法においては、酸化チタンの顆粒体が用いられ、第２の方法においては、アルミナとシリカから選ばれる少なくとも１種と酸化チタンとの混合物（以下、簡単のため、酸化チタン混合物という。）の顆粒体が用いられる。既に知られているように、酸化チタンは光触媒としての機能も有しているので、上記いずれかの触媒を用いて、廃プラスチックを熱分解するに際して、必要に応じて、紫外線の照射の下に、触媒と廃プラスチックとを加熱攪拌してもよい。 According to the present invention, as the pyrolysis catalyst, granules of titanium oxide are used in the first method, and in the second method, a mixture of at least one selected from alumina and silica and titanium oxide ( Hereinafter, for simplicity, a granule of a titanium oxide mixture) is used. As already known, since titanium oxide also has a function as a photocatalyst, when any of the above catalysts is used to thermally decompose waste plastic, it may be irradiated under ultraviolet rays as necessary. The catalyst and waste plastic may be heated and stirred.
本発明によれば、第１の方法において上記熱分解触媒として用いられる酸化チタンの顆粒体は、チタン酸化物のゾルを乾燥して酸化チタンゲルとし、この酸化チタンゲルを４５０〜８５０℃の範囲の温度で焼成し、この焼成物を破砕し、エッジ処理して得られものであって、０．５〜１．１８ｍｍの粒径を有する粒子の割合が５０〜９５重量％の範囲にあり、１．１８〜１．７ｍｍの粒径を有する粒子の割合が５〜５０重量％の範囲にある粒度分布を有すると共に、２．０％以下の摩耗率を有するものである。 According to the present invention, the titanium oxide granules used as the thermal decomposition catalyst in the first method are obtained by drying a titanium oxide sol into a titanium oxide gel, and the titanium oxide gel has a temperature in the range of 450 to 850 ° C. 1 and obtained by crushing and edging the fired product, and the proportion of particles having a particle size of 0.5 to 1.18 mm is in the range of 50 to 95% by weight. It has a particle size distribution in which the proportion of particles having a particle size of 18 to 1.7 mm is in the range of 5 to 50% by weight, and has a wear rate of 2.0% or less.
また、本発明によれば、第２の方法において上記熱分解触媒として用いられる酸化チタン混合物の顆粒体は、アルミナゾルとシリカゾルから選ばれる少なくとも１種のゾルとチタン酸化物のゾルとを混合し、乾燥してゲルとし、このゲルを４５０〜８５０℃の範囲の温度で焼成し、この焼成物を破砕し、エッジ処理して得られるものであって、０．５〜１．１８ｍｍの粒径を有する粒子の割合が５０〜９５重量％の範囲にあり、１．１８〜１．７ｍｍの粒径を有する粒子の割合が５〜５０重量％の範囲にある粒度分布を有すると共に、２．０％以下の摩耗率を有するものである。 According to the present invention, the granule of the titanium oxide mixture used as the thermal decomposition catalyst in the second method is a mixture of at least one sol selected from alumina sol and silica sol and a titanium oxide sol, It is dried to obtain a gel, which is obtained by baking the gel at a temperature in the range of 450 to 850 ° C., crushing the fired product, and subjecting it to an edge treatment, and having a particle size of 0.5 to 1.18 mm. Having a particle size distribution in which the proportion of particles having is in the range of 50-95 wt%, the proportion of particles having a particle size of 1.18-1.7 mm in the range of 5-50 wt%, and 2.0% It has the following wear rate.
本発明において用いる熱分解触媒は、このように、酸化チタンの顆粒体か、又は酸化チタン混合物の顆粒体からなり、上記粒度分布を有すると共に、エッジ処理の結果、２．０％以下の摩耗率を有するものであるので、廃プラスチック片と加熱下に攪拌混合しても、長期間にわたって、上記粒度分布を保つことができる。従って、本発明によれば、上述したような熱分解触媒を用いることによって、長時間にわたって廃プラスチックを高い熱分解効率にて分解することができる。但し、本発明において、顆粒体の摩耗率とは、後述するように、所定の装置を用いて所定の条件下に測定して得られる値をいうものとする。 Thus, the thermal decomposition catalyst used in the present invention is composed of titanium oxide granules or titanium oxide mixture granules, and has the above particle size distribution and, as a result of edge treatment, wear rate of 2.0% or less. Therefore, even if it stirs and mixes with a waste plastic piece under heating, the said particle size distribution can be maintained over a long period of time. Therefore, according to the present invention, waste plastic can be decomposed with high thermal decomposition efficiency over a long period of time by using the thermal decomposition catalyst as described above. However, in the present invention, the wear rate of the granule means a value obtained by measurement under a predetermined condition using a predetermined apparatus, as will be described later.
熱分解触媒として、種々の製法による酸化チタンのなかでも、上述したように、チタン酸化物のゾルを乾燥して酸化チタンゲルとし、この酸化チタンゲルを４５０〜８５０℃の範囲の温度で焼成して得られる酸化チタンが廃プラスチックの熱分解触媒としてすぐれた性能を有するが、破砕物のままでは、容易に摩耗し、微粉を生じて、失われる部分が多くなる。 As described above, among the titanium oxides produced by various production methods as the thermal decomposition catalyst, the titanium oxide sol is dried to form a titanium oxide gel, and the titanium oxide gel is obtained by firing at a temperature in the range of 450 to 850 ° C. Titanium oxide obtained has excellent performance as a thermal decomposition catalyst for waste plastics, but if it is crushed, it will be easily worn out, resulting in fine powder, and more parts will be lost.
そこで、本発明に従って、そのような酸化チタンゲルの焼成物の破砕物をエッジ処理して、いわば、予め、角を取ることによって、摩耗率を著しく低減し、かくして、廃プラスチックを高い熱分解効率で熱分解することができるのみならず、望ましい粒度分布を保って、その高い熱分解効率を長時間にわたって維持することができる。酸化チタン混合物の顆粒体からなる触媒についても同様である。このようなエッジ処理は、例えば、酸化チタンのゲルや、アルミナとシリカから選ばれる少なくとも１種のゲルと酸化チタンのゲルとの混合ゲルを破砕し、これを造粒装置の一つとしてよく知られている転動造粒装置にて処理することによって行うことができる。 Therefore, according to the present invention, such a crushed product of the titanium oxide gel is edge-treated, so to speak, the wear rate is remarkably reduced by removing the corners in advance, and thus the waste plastic can be decomposed with high thermal decomposition efficiency. Not only can it be pyrolyzed, it can maintain its high thermal decomposition efficiency over a long period of time while maintaining the desired particle size distribution. The same applies to a catalyst made of granules of a titanium oxide mixture. Such edge treatment is well known as one of granulating devices, for example, by crushing a gel of titanium oxide or a mixed gel of at least one gel selected from alumina and silica and a gel of titanium oxide. It can carry out by processing with the rolling granulation apparatus currently used.
特に、本発明によれば、触媒として用いる酸化チタンの顆粒体又は酸化チタン混合物の顆粒体は、０．５〜１．１８ｍｍの粒径を有する粒子の割合が６０〜９０重量％の範囲にあり、１．１８〜１．７ｍｍの粒径を有する粒子の割合が１０〜４０重量％の範囲にある粒度分布を有する共に、１．０％以下の摩耗率を有するものであることが好ましい。 In particular, according to the present invention, the titanium oxide granules or titanium oxide mixture granules used as the catalyst have a ratio of particles having a particle size of 0.5 to 1.18 mm in the range of 60 to 90% by weight. It is preferable that the ratio of the particles having a particle size of 1.18 to 1.7 mm has a particle size distribution in the range of 10 to 40% by weight and has a wear rate of 1.0% or less.
本発明において、上述した粒度分布を有する顆粒体を得る方法は特に限定されるものではない。例えば、前述したように、ゲルを焼成し、得られた焼成物を破砕し、エッジ処理した後、分級して、上記粒度分布を有する顆粒体を得てもよく、また、エッジ処理した後、分級し、得られた分級物を適宜、混合して、上記粒度分布を有する顆粒体を得てもよい。 In the present invention, the method for obtaining the granule having the particle size distribution described above is not particularly limited. For example, as described above, the gel is fired, and the obtained fired product is crushed and subjected to an edge treatment, followed by classification to obtain granules having the above particle size distribution, and after the edge treatment, Classification may be performed, and the obtained classified product may be appropriately mixed to obtain granules having the above particle size distribution.
本発明によれば、熱分解触媒として、上述した酸化チタンの顆粒体又は酸化チタン混合物の顆粒体と共に、無機酸化物又は水酸化物を併用してもよい。このような酸化物や水酸化物として、例えば、アルカリ金属又はアルカリ土類金属の酸化物や水酸化物が好ましく、例えば、酸化ナトリウム、酸化カリウム、酸化カルシウム、酸化マグネシウム等を挙げることができる。しかし、これら以外にも、例えば、酸化アルミニウム、酸化ケイ素、酸化鉄等も用いることができる。更に、これらの酸化物の一つの形態として、セメントも無機酸化物として用いることができる。 According to the present invention, an inorganic oxide or a hydroxide may be used in combination with the above-described titanium oxide granules or titanium oxide mixture granules as a thermal decomposition catalyst. As such an oxide or hydroxide, for example, an alkali metal or alkaline earth metal oxide or hydroxide is preferable, and examples thereof include sodium oxide, potassium oxide, calcium oxide, and magnesium oxide. However, besides these, for example, aluminum oxide, silicon oxide, iron oxide, and the like can be used. Furthermore, cement can also be used as an inorganic oxide as one form of these oxides.
このような無機酸化物や水酸化物も、酸化チタンや酸化チタン混合物と同じく、プラスチックの熱分解触媒として有効であるが、上記酸化チタンや酸化チタン混合物とは、好適な反応温度や生成する熱分解ガスが異なるので、酸化チタンや酸化チタン混合物と上述した無機酸化物や水酸化物を併用することによって、熱分解温度の範囲を拡大や最適化、生成ガスの種類の制御等を行うことができる。また、上述した無機酸化物や水酸化物以外にも、炭酸塩も用いることができる。 Such inorganic oxides and hydroxides are also effective as a thermal decomposition catalyst for plastics like titanium oxides and titanium oxide mixtures. However, the above-mentioned titanium oxides and titanium oxide mixtures are suitable for reaction temperatures and heat generated. Since the cracked gas is different, the combined use of titanium oxide or a titanium oxide mixture and the above-mentioned inorganic oxides or hydroxides can expand or optimize the thermal decomposition temperature range, control the type of product gas, etc. it can. In addition to the inorganic oxides and hydroxides described above, carbonates can also be used.
本発明において、熱分解触媒と廃プラスチックの加熱温度は、プラスチックの種類にもよるが、少なくとも、２００℃は必要であり、好ましくは、３００℃以上であり、特に好ましくは、４００〜６００℃の範囲である。 In the present invention, the heating temperature of the pyrolysis catalyst and the waste plastic depends on the kind of plastic, but at least 200 ° C. is necessary, preferably 300 ° C. or more, and particularly preferably 400 to 600 ° C. It is a range.
本発明の方法を適用することができるプラスチックは、特に限定されるものではなく、ポリエチレン、ポリプロピレン等の汎用の熱可塑性プラスチックのほか、熱硬化性プラスチックも本発明の方法によって熱分解し、ガス化することができる。必要に応じて、廃プラスチックを軟化点近くまで予熱した後、反応容器に投入してもよい。また、廃プラスチックは、破砕して、数ｍｍ角程度の大きさにしたものが好ましいが、特に、限定されるものではない。 The plastic to which the method of the present invention can be applied is not particularly limited. In addition to general-purpose thermoplastics such as polyethylene and polypropylene, thermosetting plastics are also thermally decomposed and gasified by the method of the present invention. can do. If necessary, the waste plastic may be preheated to near the softening point and then charged into the reaction vessel. The waste plastic is preferably crushed to a size of about several square mm, but is not particularly limited.
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
硫酸法による酸化チタン製造工程のうち、加水分解工程から得られたチタン水酸化物のスラリーを濾過、水洗し、これをリパルプしてスラリーとした。このスラリーにゾル化剤として硝酸を加え、チタン酸化物のゾルを得た。このチタン酸化物のゾルを１００℃に加熱、乾燥して、乾燥ゲルとし、これを電気炉中、６５０℃で３時間焼成して、酸化チタンの焼成物を得た。
Example 1
Of the titanium oxide production process by the sulfuric acid method, the titanium hydroxide slurry obtained from the hydrolysis process was filtered, washed with water, and repulped to obtain a slurry. Nitric acid was added to the slurry as a solubilizing agent to obtain a titanium oxide sol. This titanium oxide sol was heated to 100 ° C. and dried to obtain a dried gel, which was baked in an electric furnace at 650 ° C. for 3 hours to obtain a baked product of titanium oxide.
この酸化チタンの焼成物を粗砕し、得られた粗砕物を回転円盤式転動造粒装置（ダルトン社製マルメライザー）にて周速４ｍ／秒で１時間処理して、エッジ処理した後、分級して、酸化チタンの顆粒体を得た。この酸化チタンの顆粒体の粒度分布は粒径０．５〜１．１８ｍｍの粒子が７５重量％であり、粒径１．１８〜１．７ｍｍの粒子が２５重量％であり、比表面積は４３ｍ2／ｇであり、摩耗率は０．３７％であった。 After this titanium oxide fired product is crushed, the resulting crushed product is treated with a rotating disk type rolling granulator (Malmerizer manufactured by Dalton Co., Ltd.) at a peripheral speed of 4 m / sec for 1 hour, and then subjected to edge treatment. To obtain titanium oxide granules. The particle size distribution of the titanium oxide granules is 75% by weight of particles having a particle size of 0.5 to 1.18 mm, 25% by weight of particles having a particle size of 1.18 to 1.7 mm, and a specific surface area of 43 m. 2 / g, and the wear rate was 0.37%.
酸化チタンの顆粒体の摩耗率は図２に示す摩耗率測定装置にて測定した。即ち、この摩耗測定装置は、内径６３ｍｍ、深さ８６ｍｍの試料容器９に攪拌機１０を取付けてなり、この攪拌機は、軸体１１の下端部にそれぞれ長さ２０ｍｍの楕円形状の攪拌羽根１２を３枚、６０゜間隔で軸体から直径方向に延びるように取付けたものであって、攪拌羽根はそれぞれ水平に対して４５゜の角度を有するように傾斜している。この攪拌羽根は、その最下縁が試料容器の底から８ｍｍの距離に位置する。
The wear rate of the titanium oxide granules was measured with a wear rate measuring apparatus shown in FIG. In other words, this wear measuring apparatus has a
試料酸化チタンの顆粒体の摩耗率の測定に際しては、これを１５０ｍＬを２００ｍＬメスシリンダーで計量し、重量を記録した後、試料容器に全量を投入し、３００ｒｐｍで３０分間上記攪拌機を用いて攪拌した後、試料容器から試料を取り出し、全量を目開き０．５ｍｍの篩に移し、この篩を通過した試料の重量を測定した。ここに、試料の摩耗率Ａは、目開き０．５ｍｍの篩を通過した試料の重量をＷとし、測定に供した試料の重量をＷ0 とするとき、Ａ＝（Ｗ／Ｗ0 ）×１００（％）である。 In measuring the wear rate of the titanium oxide granules, 150 mL of this was measured with a 200 mL graduated cylinder, the weight was recorded, the entire amount was put into the sample container, and stirred at 300 rpm for 30 minutes using the above stirrer. Thereafter, the sample was taken out from the sample container, and the entire amount was transferred to a sieve having an opening of 0.5 mm, and the weight of the sample that passed through this sieve was measured. Here, the wear rate A of the sample is A = (W / W 0 ) × where W is the weight of the sample that has passed through the sieve having an aperture of 0.5 mm, and W 0 is the weight of the sample subjected to the measurement. 100 (%).
次に、攪拌機と加熱装置を有する５００ｍＬ容量ビーカーからなる熱分解装置のビーカー内に上で得た酸化チタンの顆粒体５０ｇと約５ｍｍ角に破砕したポリエチレン樹脂５０ｇとを仕込み、攪拌しながら、４００℃に加熱し、上記ポリエチレン樹脂がすべて熱分解されて、ガス化するまでの時間を測定したところ、１３分であった。 Next, 50 g of the titanium oxide granules obtained above and 50 g of polyethylene resin crushed to about 5 mm square were charged into a beaker of a thermal decomposition apparatus comprising a 500 mL capacity beaker having a stirrer and a heating apparatus, and while stirring, 400 g It was 13 minutes when it heated to ° C and the time until all the said polyethylene resins were thermally decomposed and gasified was measured.
実施例２
実施例１において、チタン酸化物の乾燥ゲルを電気炉中、６００℃で３時間焼成した以外は、同様にして、酸化チタンの顆粒体を得た。この酸化チタンの顆粒体の粒度分布は粒径０．５〜１．１８ｍｍの粒子が７９重量％であり、粒径１．１８〜１．７ｍｍの粒子が２１重量％であり、比表面積は６１ｍ2／ｇであり、摩耗率は１．７％であった。
Example 2
Titanium oxide granules were obtained in the same manner as in Example 1 except that the dried gel of titanium oxide was calcined at 600 ° C. for 3 hours in an electric furnace. The particle size distribution of the titanium oxide granules is 79% by weight of particles having a particle size of 0.5 to 1.18 mm, 21% by weight of particles having a particle size of 1.18 to 1.7 mm, and a specific surface area of 61 m. 2 / g, and the wear rate was 1.7%.
この酸化チタンの顆粒体を熱分解触媒として用いて、実施例１と同様にして、上記ポリエチレン樹脂がすべて熱分解されて、ガス化するまでの時間を測定したところ、１３分であった。 Using the titanium oxide granules as a thermal decomposition catalyst, the time until the polyethylene resin was all thermally decomposed and gasified was measured in the same manner as in Example 1. The result was 13 minutes.
実施例３
実施例１で得たチタン酸化物のゾルにアルミナ２０重量％を含有するアルミナゾルを混合し、この混合ゾルを１００℃に加熱、乾燥して、乾燥ゲルとし、これを電気炉中、６５０℃で３時間焼成して、酸化チタンとアルミナとの混合物（酸化チタン／アルミナ重量比１／１）の焼成物を得た。
Example 3
An alumina sol containing 20% by weight of alumina was mixed with the titanium oxide sol obtained in Example 1, and this mixed sol was heated to 100 ° C. and dried to obtain a dried gel, which was then heated at 650 ° C. in an electric furnace. Firing was performed for 3 hours to obtain a fired product of a mixture of titanium oxide and alumina (titanium oxide / alumina weight ratio 1/1).
この酸化チタンとアルミナとの混合物の焼成物を実施例１と同様に粗砕し、エッジ処理した後、分級して、酸化チタンとアルミナとの混合物の顆粒体を得た。この顆粒体の粒度分布は粒径０．５〜１．１８ｍｍの粒子が６５重量％であり、粒径１．１８〜１．７ｍｍの粒子が３５重量％であり、比表面積は９０ｍ2／ｇであり、摩耗率は０．２５％であった。 The fired product of the mixture of titanium oxide and alumina was roughly crushed in the same manner as in Example 1, and after edge treatment, it was classified to obtain granules of a mixture of titanium oxide and alumina. The granule has a particle size distribution of 65% by weight of particles having a particle size of 0.5 to 1.18 mm, 35% by weight of particles having a particle size of 1.18 to 1.7 mm, and a specific surface area of 90 m 2 / g. The wear rate was 0.25%.
この酸化チタンとアルミナとの混合物の顆粒体を熱分解触媒として用いて、実施例１と同様にして、上記ポリエチレン樹脂がすべて熱分解されて、ガス化するまでの時間を測定したところ、１３．５分であった。 Using this granule of a mixture of titanium oxide and alumina as a thermal decomposition catalyst, the time until the polyethylene resin was all thermally decomposed and gasified was measured in the same manner as in Example 1. It was 5 minutes.
実施例４
実施例１で得たチタン酸化物のゾルにシリカ３０重量％を含有するシリカゾルを混合し、この混合ゾルを１００℃に加熱、乾燥して、乾燥ゲルとし、これを電気炉中、６５０℃で３時間焼成して、酸化チタンとシリカとの混合物（酸化チタン／シリカ重量比３５：６５）の焼成物を得た。
Example 4
A silica sol containing 30% by weight of silica was mixed with the titanium oxide sol obtained in Example 1, and this mixed sol was heated to 100 ° C. and dried to obtain a dry gel, which was heated at 650 ° C. in an electric furnace. Firing was performed for 3 hours to obtain a fired product of a mixture of titanium oxide and silica (titanium oxide / silica weight ratio 35:65).
この酸化チタンとシリカとの混合物の焼成物を実施例１と同様に粗砕し、エッジ処理した後、分級して、酸化チタンとシリカとの混合物の顆粒体を得た。この顆粒体の粒度分布は粒径０．５〜１．１８ｍｍの粒子が５５重量％であり、粒径１．１８〜１．７ｍｍの粒子が４５重量％であり、比表面積は７５ｍ2／ｇであり、摩耗率は０．２０％であった。 The fired product of the mixture of titanium oxide and silica was roughly crushed in the same manner as in Example 1, and after edge treatment, it was classified to obtain granules of a mixture of titanium oxide and silica. The granule has a particle size distribution of 55% by weight of particles having a particle size of 0.5 to 1.18 mm, 45% by weight of particles having a particle size of 1.18 to 1.7 mm, and a specific surface area of 75 m 2 / g. The wear rate was 0.20%.
この酸化チタンとシリカとの混合物の顆粒体を熱分解触媒として用いて、実施例１と同様にして、上記ポリエチレン樹脂がすべて熱分解されて、ガス化するまでの時間を測定したところ、１４分であった。 Using this granule of a mixture of titanium oxide and silica as a thermal decomposition catalyst, the time until the polyethylene resin was all thermally decomposed and gasified was measured in the same manner as in Example 1. Met.
比較例１
実施例１において得た酸化チタンの焼成物の粗砕物をエッジ処理することなく、分級して、粒径０．５〜１．１８ｍｍの粒子が８０重量％であり、粒径１．１８〜１．７ｍｍの粒子が２０重量％である粒度分布を有し、比表面積が４６ｍ2／ｇであり、摩耗率が３．５％の顆粒体を得た。この酸化チタンの顆粒体を熱分解触媒として用いて、実施例１と同様にして、上記ポリエチレン樹脂がすべて熱分解されて、ガス化するまでの時間を測定したところ、１８分であった。
Comparative Example 1
The coarsely baked titanium oxide obtained in Example 1 was classified without edge treatment, and particles having a particle size of 0.5 to 1.18 mm were 80% by weight, and a particle size of 1.18 to 1 A granule having a particle size distribution of 20% by weight of 0.7 mm particles, a specific surface area of 46 m 2 / g, and a wear rate of 3.5% was obtained. Using this titanium oxide granule as a thermal decomposition catalyst, the time until the polyethylene resin was all thermally decomposed and gasified was measured in the same manner as in Example 1, and it was 18 minutes.
１…反応容器
２…廃プラスチック片投入口
３…担体ガス
４…担体ガス管
５…熱分解触媒
６…廃プラスチック片
７…攪拌機
８…加熱装置
DESCRIPTION OF SYMBOLS 1 ... Reaction container 2 ... Waste plastic piece inlet 3 ... Carrier gas 4 ... Carrier gas pipe 5 ... Pyrolysis catalyst 6 ... Waste plastic piece 7 ... Stirrer 8 ... Heating device
Claims (3)
The proportion of particles having a particle size of 0.5 to 1.18 mm in the range of 60 to 90% by weight and the proportion of particles having a particle size of 1.18 to 1.7 mm is 10 to 40% by weight The method according to claim 1, wherein the method has a particle size distribution in the range of 1.0% and a wear rate of 1.0% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004126000A JP4602690B2 (en) | 2004-04-21 | 2004-04-21 | Disassembly method of waste plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004126000A JP4602690B2 (en) | 2004-04-21 | 2004-04-21 | Disassembly method of waste plastic |
Publications (3)
| Publication Number | Publication Date |
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| JP2005307007A true JP2005307007A (en) | 2005-11-04 |
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