WO2000002977A1 - Procede pour transformer en petrole des dechets plastiques contenant du chlore - Google Patents

Procede pour transformer en petrole des dechets plastiques contenant du chlore Download PDF

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Publication number
WO2000002977A1
WO2000002977A1 PCT/JP1999/003612 JP9903612W WO0002977A1 WO 2000002977 A1 WO2000002977 A1 WO 2000002977A1 JP 9903612 W JP9903612 W JP 9903612W WO 0002977 A1 WO0002977 A1 WO 0002977A1
Authority
WO
WIPO (PCT)
Prior art keywords
waste plastic
chlorine
aqueous solution
carbonate
waste
Prior art date
Application number
PCT/JP1999/003612
Other languages
English (en)
Japanese (ja)
Inventor
Yoshihisa Saito
Takehiko Moriya
Masanori Tabata
Naohiko Ukawa
Masato Kaneko
Kazuto Kobayashi
Shigeo Hasegawa
Wataru Matsubara
Kenji Iwasaki
Michio Ohshima
Original Assignee
Tohoku Electric Power Co., Inc.
Mitsubishi Heavy Industries, Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tohoku Electric Power Co., Inc., Mitsubishi Heavy Industries, Ltd. filed Critical Tohoku Electric Power Co., Inc.
Priority to EP99926929A priority Critical patent/EP1101812B1/fr
Priority to JP2000559200A priority patent/JP3586648B2/ja
Priority to DE69927596T priority patent/DE69927596D1/de
Publication of WO2000002977A1 publication Critical patent/WO2000002977A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste

Definitions

  • the present invention relates to a method for converting chlorine-based waste plastic to oil using supercritical water.
  • the waste plastic is chlorine-based plastic
  • chlorine ions are desorbed from the waste plastic when it is liquefied by supercritical water.
  • This chlorine causes severe corrosion of the stainless metal used in the oiling equipment.
  • oilification with supercritical water is performed at high temperatures and high pressures, so pitting corrosion, crevice corrosion, stress corrosion cracking, etc., occur in stainless steel metals due to chlorine ions.
  • the degree of corrosion depends on the composition of stainless steel and the concentration of desorbed chlorine.
  • nickel-resistant alloys with a special chemical composition that is resistant to corrosion is being studied as a material for the oiling equipment.
  • nickel-based alloys are expensive and equipment construction costs are very high.
  • waste plastic is thermally decomposed in a dechlorinator at 300 to 350 to remove chlorine, and then the waste plastic is converted to stainless steel oil, which is cheaper than nickel-based alloys.
  • a method has been developed in which it is introduced into equipment and turned into oil using supercritical water. However, in this case, the process becomes complicated and the number of devices constituting the device is increased as compared with the case of direct oiling. For this reason, the construction cost capability of the entire oil conversion facility will be extremely high. Disclosure of the invention
  • the present invention can be applied to an apparatus using inexpensive stainless steel metal, and can reduce chlorine-based waste plastic which requires a small number of equipment. It is intended to provide an oiling method.
  • the method for liquefying chlorine-based waste plastic comprises: a waste plastic containing chlorine-based plastic, the dissolved oxygen concentration of which is adjusted to 0.5 mg Z liter or less; An aqueous solution containing a hydroxide or carbonate of a class of metals or a mixture with an aqueous solution containing a plurality of these is heated to remove chlorine in the waste plastic under the transition process to supercritical conditions and / or under supercritical conditions. The waste plastic is decomposed.
  • the method for liquefying chlorinated waste plastic includes an aqueous solution containing a carbonate of an alkaline metal or a hydroxide or a carbonate of an alkaline earth metal, or a plurality of aqueous solutions thereof.
  • Heat the aqueous solution mix the molten waste plastic containing chlorine-based plastic into the aqueous solution under the supercritical condition transition process and / or the supercritical condition, and determine the dissolved oxygen concentration of the aqueous solution by mixing the waste plastic. It is adjusted to 0.5 mg / liter or less before or at the time of mixing, desorbs chlorine in the waste plastic mixed into the aqueous solution, and decomposes the waste plastic.
  • the chlorine desorbed from the waste plastic is converted into a carbonate of an alkaline metal or a hydroxide or carbonate of an alkaline earth metal. Can be neutralized.
  • nitrogen gas may be blown or an oxygen scavenger may be added as a means for adjusting the dissolved oxygen concentration.
  • sodium sulfite, sodium nitrite or hydrazine can be employed as the oxygen scavenger.
  • FIG. 1 is a flow chart showing a method for treating chlorine-based waste plastic according to a first example of the present invention.
  • FIG. 2 is a flow chart showing a method for treating chlorine-based waste plastic according to a second example of the present invention.
  • the chlorine-based waste plastic to be treated in the oiling method of the present invention is not limited as long as it contains chlorine, and examples thereof include vinyl chloride resin, polyvinylidene chloride, and polychloromouth trifluoroethylene. it can. Further, a mixture with waste plastics other than chlorine-based plastics, such as polyethylene, polypropylene, and polystyrene, may be used.
  • chlorinated waste plastics are ground to powder.
  • the size of the powder is preferably about 2 mm or less in diameter when the spheres have the same volume. If the powder is too large, it may not be possible to supply it smoothly when mixed with the aqueous solution and supplied to the oiling device, and the efficiency of the oiling treatment may be reduced.
  • the pulverized waste plastic has a dissolved oxygen concentration of 0.5 mgZ liter or less, and is mixed with an aqueous solution containing an alkali metal carbonate or an alkaline earth metal hydroxide or carbonate. Mixed.
  • the dissolved oxygen concentration may be adjusted after the generation of the mixed solution. That is, the pulverized waste plastic is mixed with an aqueous solution containing an alkali metal carbonate or an alkali earth metal hydroxide or carbonate to form a mixed solution, and then the mixed solution is mixed with the mixed solution.
  • the mixed solution may be treated so that the dissolved oxygen concentration becomes 0.5 mgZ liter or less.
  • Means for reducing the dissolved oxygen concentration in the aqueous solution or the mixed solution to 0.5 mgZ liter or less include, for example, blowing of nitrogen gas and addition of a deoxidizer.
  • the oxygen scavenger include sodium sulfite, sodium nitrite, hydrazine and the like. These oxygen absorbers may be used alone or in combination of two or more.
  • the aqueous solution mixed with the chlorinated waste plastic contains at least one selected from alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Specific examples thereof include sodium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide and the like.
  • the amount of these carbonates or hydroxides to be added is at least the equivalent of the total amount of dechlorination in the subcritical part and supercritical part described below, and preferably 1.1 to 1.2 equivalents.
  • the subcritical condition refers to a condition of a temperature of 250 to 350 and a pressure of 25 to 3 OMPa.
  • the part under subcritical conditions in the oil converter is called subcritical part.
  • the supercritical condition refers to a condition of a temperature of 350 to 550 ° C. and a pressure of 25 to 30 MPa.
  • the part under supercritical conditions in the oil conversion unit is called the supercritical part.
  • the chlorine-based waste plastic in the prepared mixture is dechlorinated under subcritical conditions, and the desorbed chlorine (hydrochloric acid) is immediately neutralized by the salt or hydroxide in the mixture. Therefore, during the subsequent treatment under supercritical conditions, no hydrochloric acid is present in the mixed solution, and the inner wall of the apparatus is not corroded by hydrochloric acid. In addition, even if salts and the like that were not used for neutralization under subcritical conditions remained in the mixed solution and entered the supercritical part, no alkali metal hydroxide was used. The mixture under supercritical conditions does not become strongly alkaline and does not cause corrosion.
  • the mixed solution from which chlorine has been desorbed under subcritical conditions is then decomposed into waste oil and gas under supercritical conditions.
  • the obtained oil and gas can be used as fuel.
  • waste plastics may be mixed into the aqueous solution after the aqueous solution is brought into subcritical or supercritical conditions.
  • thermoplastic plastics those obtained by applying heat and melting may be mixed into the aqueous solution.
  • the mixing may be a process in which the aqueous solution shifts to supercritical conditions, or may be mixed in an aqueous solution under supercritical conditions.
  • waste plastic is supplied to a mixer 1 and mixed with an aqueous solution supplied from a tank 2 to form a slurry.
  • the aqueous solution supplied from the tank 2 contains an alkali metal carbonate or an alkaline earth metal hydroxide or carbonate, and contains dissolved oxygen by nitrogen gas (N 2 ) or a deoxidizer.
  • N 2 nitrogen gas
  • the concentration has been adjusted to less than 0.5 mgZ liter.
  • the adjustment of the dissolved oxygen concentration using nitrogen gas, a deoxidizer, or the like may be performed on the mixer 1 or on the downstream side thereof.
  • the slurry in the mixer 1 is guided to an oiling device 4 by a slurry feeder 3.
  • the oiling device 4 first, the slurry is preheated in the preheating section 4a, and then chlorine contained in the waste plastic in the slurry is desorbed in the subcritical section 4b. The desorbed chlorine is neutralized by the carbonate or hydroxide in the slurry. Thereafter, the slurry moves to the supercritical section 4c, where the waste plastic in the slurry is decomposed.
  • the slurry is discharged from the oiling device and separated into oil and water by the oil / water separator 5. Part of the separated water is drained out of the system, and the remainder is supplied to the tank 2.
  • the tank 2 in addition to the water from the oiling device 4, supply water from outside the system and sodium carbonate in this example are supplied. As a result, the amount of the aqueous solution sent to the mixer 1 and the concentration of sodium carbonate are kept constant.
  • FIG. 2 shows another example of an embodiment of the method for liquefying chlorine-based waste plastic according to the present invention.
  • the same elements as those in FIG. 1 are denoted by the same reference numerals, and overlapping description will be omitted.
  • Thermoplastics can be used as a means of driving It is further melted and mixed into an aqueous solution whose dissolved oxygen concentration is adjusted to 0.5 mg / liter or less under the transition process to the supercritical condition of the oiler or under the supercritical condition.
  • Waste plastic in powder form having the composition shown in Table 1 was converted to oil using the equipment shown in Fig. 1.
  • the aqueous solution in the tank 2 was adjusted so as to have a dissolved oxygen concentration of 0.1 to 0.5 mgZ liter by blowing nitrogen gas and adding sodium sulfite.
  • tank 2 1.1 to 1.2 equivalents of sodium carbonate and the like contained in the waste plastic were continuously supplied.
  • an electric furnace having a reaction tube divided into three was used as an oiling device 4.
  • the reaction tube was made of SUS316 having an inner diameter of 5 mm, an outer diameter of 10 mm, and a length of 60 m, and was heated to the oily condition of the waste plastic in advance, and was 1% sodium carbonate.
  • An aqueous solution circulated for 50 hours and subjected to anticorrosion treatment was used.
  • the temperature inside the oil converter is set to 20 to 250 in the preheating section, to 250 to 350 in the subcritical section, and to 350 to 550 in the supercritical section, and the pressure is set to 250 It was adjusted so as to be ⁇ 300 kgf no cm2 (25-30 MPa).
  • the mixed liquid is formed into a slurry that is easy to flow and is continuously processed, but the present invention is not limited to this.
  • the treatment method and the apparatus can be greatly simplified as compared with the prior art. Does not occur.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de transformation de déchets plastiques contenant du chlore. Le procédé consiste à chauffer le mélange de déchets plastiques contenant du chlore avec une solution aqueuse d'un carbonate de métal alcalin, ou d'un hydroxyde, ou d'un carbonate de métal alcalino-terreux, ou avec une solution aqueuse contenant plusieurs de ces composés et ajustée de manière à présenter une faible concentration d'oxygène dissout d'au plus 0,5 mg/l, afin de libérer le chlore contenu dans les déchets plastiques et de décomposer lesdits déchets plastiques au cours du processus de transfert vers un état supercritique ou dans des conditions supercritiques. Le procédé consiste autrement à chauffer la solution aqueuse d'un carbonate de métal alcalin, ou d'un hydroxyde, ou d'un carbonate de métal alcalino-terreux, ou une solution aqueuse contenant plusieurs de ces composés, et à mélanger des déchets plastiques fondus qui comportent du plastique contenant du chlore dans une solution aqueuse au cours du processus de transfert vers un état supercritique ou dans des conditions supercritiques, la concentration d'oxygène dissout dans la solution aqueuse étant ajustée à au plus 0,5 mg/l, afin de libérer le chlore contenu dans les déchets plastiques et de décomposer lesdits déchets plastiques.
PCT/JP1999/003612 1998-07-08 1999-07-05 Procede pour transformer en petrole des dechets plastiques contenant du chlore WO2000002977A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99926929A EP1101812B1 (fr) 1998-07-08 1999-07-05 Procede pour transformer en petrole des dechets plastiques contenant du chlore
JP2000559200A JP3586648B2 (ja) 1998-07-08 1999-07-05 塩素系廃プラスチックの油化方法
DE69927596T DE69927596D1 (de) 1998-07-08 1999-07-05 Verfahren zur umwandlung von chlorhaltigen plastikabfällen zu öl

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP19285998 1998-07-08
JP10/192859 1998-07-08

Publications (1)

Publication Number Publication Date
WO2000002977A1 true WO2000002977A1 (fr) 2000-01-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/003612 WO2000002977A1 (fr) 1998-07-08 1999-07-05 Procede pour transformer en petrole des dechets plastiques contenant du chlore

Country Status (5)

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EP (1) EP1101812B1 (fr)
JP (1) JP3586648B2 (fr)
DE (1) DE69927596D1 (fr)
TW (1) TW585905B (fr)
WO (1) WO2000002977A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002074881A1 (fr) * 2001-03-19 2002-09-26 Deinking/Solvent Extraction Technologies Ltd. Reduction catalytique d'huiles lourdes, kerogenes, matieres plastiques, biomasses, boues et dechets organiques en hydrocarbures liquides legers, dioxyde de carbone et amines
JP2012228661A (ja) * 2011-04-26 2012-11-22 Muroran Institute Of Technology 水熱分解用吸着体、及びこれを用いた感染性有機廃棄物及び／又は含塩素有機廃棄物の処理方法
JP2023507079A (ja) * 2019-12-17 2023-02-21 サウジ アラビアン オイル カンパニー 超臨界水によるポリオレフィンからの液体炭化水素の生成

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2426253A1 (fr) 2003-04-22 2004-10-22 Hurdon A. Hooper Reduction du caoutchouc
WO2008054190A1 (fr) * 2006-10-30 2008-05-08 Claus Platen Procédé et système de conversion de déchets en combustibles et autres sous-produits
CN115232633B (zh) * 2022-08-18 2024-04-12 华北电力大学 一种废弃工程塑料热解联产酚类化学品和超级电容炭材料的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH108065A (ja) * 1996-06-19 1998-01-13 Nishikawa Rubber Co Ltd 難破砕性廃棄物の水熱連続油化装置
JPH1088146A (ja) * 1996-09-20 1998-04-07 Kanegafuchi Chem Ind Co Ltd ハロゲン含有樹脂の油化処理方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5142640B2 (fr) * 1971-12-09 1976-11-17
DE4243063C2 (de) * 1991-12-20 1996-01-11 Toshiba Kawasaki Kk Verfahren und Vorrichtung zur pyrolytischen Zersetzung von Kunststoff, insbesondere von Kunststoffabfällen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH108065A (ja) * 1996-06-19 1998-01-13 Nishikawa Rubber Co Ltd 難破砕性廃棄物の水熱連続油化装置
JPH1088146A (ja) * 1996-09-20 1998-04-07 Kanegafuchi Chem Ind Co Ltd ハロゲン含有樹脂の油化処理方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1101812A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002074881A1 (fr) * 2001-03-19 2002-09-26 Deinking/Solvent Extraction Technologies Ltd. Reduction catalytique d'huiles lourdes, kerogenes, matieres plastiques, biomasses, boues et dechets organiques en hydrocarbures liquides legers, dioxyde de carbone et amines
JP2012228661A (ja) * 2011-04-26 2012-11-22 Muroran Institute Of Technology 水熱分解用吸着体、及びこれを用いた感染性有機廃棄物及び／又は含塩素有機廃棄物の処理方法
JP2023507079A (ja) * 2019-12-17 2023-02-21 サウジ アラビアン オイル カンパニー 超臨界水によるポリオレフィンからの液体炭化水素の生成

Also Published As

Publication number Publication date
DE69927596D1 (de) 2006-02-16
EP1101812B1 (fr) 2005-10-05
EP1101812A4 (fr) 2004-07-21
EP1101812A1 (fr) 2001-05-23
JP3586648B2 (ja) 2004-11-10
TW585905B (en) 2004-05-01

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