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EP0991734B1 - Procede d'elimination de dechets halogenes et/ou renfermant des hydrocarbures - Google Patents

Procede d'elimination de dechets halogenes et/ou renfermant des hydrocarbures Download PDF

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Publication number
EP0991734B1
EP0991734B1 EP98933611A EP98933611A EP0991734B1 EP 0991734 B1 EP0991734 B1 EP 0991734B1 EP 98933611 A EP98933611 A EP 98933611A EP 98933611 A EP98933611 A EP 98933611A EP 0991734 B1 EP0991734 B1 EP 0991734B1
Authority
EP
European Patent Office
Prior art keywords
waste products
hydroxide
halogenated
gas
melt
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 - Lifetime
Application number
EP98933611A
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German (de)
English (en)
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EP0991734A1 (fr
Inventor
Guy Rollinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pac Holding SA
Original Assignee
Pac Holding SA
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Filing date
Publication date
Priority claimed from LU90079A external-priority patent/LU90079B1/de
Application filed by Pac Holding SA filed Critical Pac Holding SA
Publication of EP0991734A1 publication Critical patent/EP0991734A1/fr
Application granted granted Critical
Publication of EP0991734B1 publication Critical patent/EP0991734B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation

Definitions

  • the present invention relates to a method for disposal hydrocarbon and / or halogenated waste products.
  • EP-A-0 592 057 discloses a process for the pyrolysis of organic Waste materials, preferably from used vehicle tires, and a Device for performing the method.
  • the pyrolysis takes place under air and Exclusion of water and is carried out under reduced pressure, preferably in one Metal bath, at a working temperature of 450-550 ° C, preferably below 500 ° C, operated.
  • From US-A-3 252 773 is a process for the production of known hydrogen-containing gas from carbon-containing solid, the carbon-containing solid, a copper-containing catalyst and water vapor in Bring contact with an alkali metal melt under conditions under which hydrogen-rich gas is generated.
  • This gas formation is in one Temperature range from 427 to 982 ° C executed.
  • the object of the present invention is to develop a method that allows various hydrocarbon and / or halogenated Dispose of waste products in an environmentally friendly manner.
  • This object is achieved by a disposal method hydrocarbon-containing and / or halogenated waste products solved at which the waste products in the absence of oxygen and moisture in one Hydroxide melt can be implemented at temperatures from 580 to 900 ° C.
  • the hydroxide is from the Group of alkali metal hydroxides selected.
  • the hydroxide is preferably sodium hydroxide and / or Potassium hydroxide.
  • the process is the ratio between sodium hydroxide and potassium hydroxide between 1: 0 and 1:10 and preferably at 1: 0.5.
  • metal hydrides and possibly also can be used in the process other hydrocarbons occur.
  • the resulting alkali hydride requires careful handling because it is extremely reactive.
  • Alkali hydroxide melt or a hydrocarbon used In order to eliminate alkali hydrides from the gas, one is preferably used Alkali hydroxide melt or a hydrocarbon used.
  • the resulting alkali metal hydrides can either be used to obtain Metals or for the production of hydrogen.
  • the one there Resulting alkali metal hydroxides can be returned to the process.
  • hydrocarbon-containing waste products solvents, Tars, waste oils, lubricants, greases, varnishes, paints, waxes and not halogenated plastics
  • halogenated plastics such as Polyethylene, polypropylene, polystyrene, Polycarbonates or rubber and as halogenated waste materials solvents such as e.g .: chloroform, methylene chloride, tetra- and trichlorethylene, tetrachloroethane, Coolant or refrigerant (CFC), PCB, dioxins, furans, brake fluid, pesticides, Use fungicides and herbicides, halogenated plastics.
  • the melt may also contain a catalyst that is not metal oxide which is reducible by sodium hydride and which, if possible, is resistant to sulfur and / or sulfur compounds.
  • the reactor materials are preferably selected from materials that are Alkali hydrides do not contain any metalates and, if possible, none or only a small amount Form the circumference of metal carbonyls.
  • Fig. 1 a scheme of the plant for the disposal of hydrocarbon and / or halogenated waste products.
  • the hydrocarbonaceous and / or halogenated waste products are filled into a hopper 1 and then by means of a pump 2 a line, which is provided with a shut-off valve 3, into the reactor 4 introduced.
  • the reactor 4 has a heating element 5 and can by a Shut-off valve 6 can be connected to a nitrogen supply 7. after the hydrocarbon-containing and / or halogenated waste products with the im Reactor 4 contained melt have reacted, the products are one first gas scrubber 8 supplied, in which the solids are retained. The Solids can then be removed via a discharge device 9.
  • the Washing medium is circulated by a pump 10.
  • the gases freed from the solids are then removed by a Gas compressor 11 led to a second scrubbing column 12 in which different Gases can be washed out.
  • the solids formed can by a stopcock 13 are drained.
  • the gases purified in this way are through the upper part of the Washing column 12 discharged through a line 14.
  • the above Input materials in one Alkali hydroxide melt consisting of 2 parts of sodium hydroxide (NaOH) and a portion of potassium hydroxide (KOH) at temperatures from 750 ° C to about 820 ° C with exclusion of air or oxygen under atmospheric pressure, i.e. 1.013 bar. ⁇ 0.05 bar thermochemically converted.
  • reaction or reaction products formed thermodynamically preferred under these process parameters are primarily gaseous hydrogen (H 2 ) in addition to smaller percentages of methane (CH 4 ).
  • hydrogen and methane are different secondary compounds based on the respective melt components formed.
  • alkali metals here: metallic sodium, metallic potassium
  • alkali metal carbonates here: sodium carbonate, Na 2 CO 3 ; potassium carbonate, K 2 CO 3
  • alkali metal hydrides here: sodium hydride, NaH; Potassium hydride, KH.
  • the alkali metal hydrides can be chemically mixed with various types Metal oxides, metal chlorides and metal sulfides are reacted, so that pure or ultrapure metal can be obtained as reaction products.
  • the maximum amount of hydrogen that can be obtained in gaseous form is around 580 ° C up to about 900 ° C. At these higher temperatures it shifts Composition of the process gas on the hydrogen side, i.e. the percent less methane are contained in the process gas. At lower ones At temperatures, the amount of hydrogen is below the attainable maximum.
  • the composition of the gaseous components, in particular here Hydrogen and methane differ from the composition at approx. 800 ° C, in such a way that larger amounts of methane are formed. At Test temperatures beyond 900 ° C can not be a greater yield Achieve hydrogen as thermal decomposition processes increase.
  • the formation of environmentally hazardous emissions such as carbon monoxide and Carbon dioxide favors that are not formed under normal process conditions become; i.e. Carbon and oxygen components become thermodynamic favored stored as alkali metal carbonates.
  • the reactor (ST37 normal steel, 4 m high, 200 - 400 mm inside diameter) via a gas-tight connection with the Alkali metal hydroxides are filled. Then the content is displayed using a electric heating (pipe heater or heating half-shells) to a temperature heated from approx. 750 ° C.
  • a homogeneous melt forms, which is a melting point eutectic, owns.
  • the temperature is measured using a Ni-CrNi or Pt-PtRh Thermocouple, what about a gas-tight connector in the middle of the reactor protrudes so that the temperature of the melt can be tapped there.
  • Nitrogen nozzles are first introduced into the melt. The nitrogen mixes the melt and at the same time displaces the rest, possibly in the Air in the system.
  • the various hydrocarbon and / or halogenated waste products be started in the reactor.
  • the contribution is made via a Eccentric screw pump that either contains the substances to be introduced or distributed in several intake systems.
  • the use of several Inlet systems allow the capacity of the reactor to be increased.
  • Alkaline metals are formed as further, secondary products, Alkali metal carbonates, alkali metal hydrides and alkali metal chlorides. These substances form at slightly lower temperatures so that they cool down crystallize and in a washing column continuously rinsed with paraffin oil can be held back. The unconverted remain in the reactor itself Alkali metal hydroxides, as well as part of the alkali metal carbonates and Alkali metal chlorides
  • the reaction causes a slight excess pressure of about 0.05 bar Normal pressure, based on the corresponding partial pressures of the resulting ones Gases.
  • This second washing column contains a zinc sulfate solution (ZnSO 4 ). If the various feedstocks contain sulfur components, hydrogen sulfide (H 2 S) is formed in the reactor. This should be removed from the gases due to its toxicity and smell. This is done by a chemical precipitation reaction in the second gas scrubbing column. In gas washing, zinc sulfide (ZnS) is formed, which is obtained as a crystalline substance that sinks to the bottom of the washing column and can be separated off there by a discharge mechanism. Another by-product of gas scrubbing is sulfuric acid (H 2 SO 4 ). This fact makes it possible to make a statement about the content of hydrogen sulfide formed by continuously checking the pH of the washing liquid.
  • ZnSO 4 zinc sulfate solution
  • the resulting hydrogen and methane are removed by gas scrubbing not affected by the zinc sulfate solution and can be used as intended Energy generation can be used.
  • seals e.g. metal-coated ceramic seals, overpressure protection and in particular Leakage indicators can be installed.
  • the substances remaining in the reactor, as well as unreacted Metal hydroxides can either be discontinuous or continuous from the System are removed.
  • This pipe is over a sump with a special thread provided and screwed gastight. Now if the reactor contents from the If the reactor is to be released, the screw connection is loosened and the tube is heated by means of a heating coil to about 250 ° C. The melt previously in the Drain pipe has run and solidified there, becomes liquid again. So it will "Natural grafting" loosened and the reactor contents can be in the drip pan flow and cool there without risk.
  • engine oil was at a temperature of 743 ° C and a pressure of 1.05 bar implemented according to the method described above.
  • waste oil (A) was at a temperature of 758 ° C and a pressure of 1.05 bar and a mixture (B) of waste oil and paint at 762 ° C and a pressure of 1.06 bar according to the procedure described above implemented.
  • sample 3 (A) and sample 4 (B) was taken during the process and examined for N 2 , CO 2 , O 2 , CO, H 2 , CH 4 and C 2 H 8 .
  • the accuracy of the analysis is +/- 5 vol% relative.
  • Example 1 One gas sample each (samples C, D, E, F, G correspond to the different mixtures) was taken during the process and analyzed for CO 2 , O 2 , CO, H 2 , CH 4 , C 2 H 6 , C 2 H 4 , C 3 H 8 and C 2 H 2 examined.
  • the individual components were determined as in Example 1: The examination of the gas samples had the following results connection Sample C vol.% Sample D vol.% CO 2 0.00 0.01 O 2 0.72 1.07 CO 0.0001 0.0001 H 2 86.3 81.6 CH 4 11.5 14.7 C 2 H 6 0.26 0.53 C 2 H 4 0.01 traces C 3 H 8 0.02 0.03 C 2 H 2 0.01 0.05
  • 1,1,1-trichloroethane was used at a temperature of 786 ° C and a pressure of 1.013 bar +/- 0.06 bar after that described above Procedure implemented.
  • a gas sample (Sample 5) was taken during the process and on carbon, oxygen, nitrogen, carbon monoxide, hydrogen, methane, ethane, ethylene, propane, propylene, n-butane, i-butane, n-butylene, i-butylene, acethylene , Chloroalkanes, benzene, toluene and xylene were examined.
  • the examination of the gas samples had the following results.

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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)
  • Processing Of Solid Wastes (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Claims (8)

  1. Procédé d'élimination de déchets halogénés et/ou contenant des hydrocarbures, les déchets étant convertis dans un bain d'hydroxyde fondu en l'absence d'oxygène et d'humidité, caractérisé en ce que la température du bain d'hydroxyde fondu est comprise entre 580° C et 900° C.
  2. Procédé selon la revendication 1, caractérisé en ce que l'hydroxyde est sélectionné dans le groupe des hydroxydes d'alcalis.
  3. Procédé selon la revendication 2, caractérisé en ce que l'hydroxyde est l'hydroxyde de sodium et/ou l'hydroxyde de potassium.
  4. Procédé selon la revendication 3, caractérisé en ce que le rapport entre l'hydroxyde de sodium et l'hydroxyde de potassium est compris entre 1:0 et 1:10.
  5. Procédé selon la revendication 4, caractérisé en ce que le rapport entre l'hydroxyde de sodium et l'hydroxyde de potassium se situe à 1:0,5.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que dans le procédé, on forme principalement de l'hydrogène, du méthane, des carbonates, et en supplément des chlorures métalliques lorsque l'on utilise des déchets halogénés.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que de petites quantités d'hydrures sont encore produites dans le procédé.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que comme déchets contenant des hydrocarbures, on utilise des solvants, des goudrons, des huiles usées, des lubrifiants, des graisses, des vernis, des peintures, des cires et des matières synthétiques non halogénées telles que, par exemple, le polyéthylène, le polypropylène, des polystyrènes ou du caoutchouc, et comme déchets halogénés, des solvants tels que, par exemple, : le chloroforme, le chlorure de méthylène, le tétra et le trichloréthylène, le tétrachloroéthane, des fluides de refroidissement ou cryogéniques (CFC), des PCB, des dioxines, des furanes, des liquides de frein, des pesticides, des fongicides, des herbicides et des matières synthétiques halogénées.
EP98933611A 1997-06-12 1998-06-12 Procede d'elimination de dechets halogenes et/ou renfermant des hydrocarbures Expired - Lifetime EP0991734B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
LU90079A LU90079B1 (de) 1997-06-12 1997-06-12 Verfahren zur Entsorgung kohlenwasserstoffhaltiger Abfallprodukte
LU90079 1997-06-12
LU90135 1997-09-10
LU90135A LU90135A7 (de) 1997-06-12 1997-09-10 Verfahren zur Entsorgung kohlenfasserstoffhaltiger und/oder halogenierter Abfallprodukte
PCT/EP1998/003566 WO1998056871A1 (fr) 1997-06-12 1998-06-12 Procede d'elimination de dechets halogenes et/ou renfermant des hydrocarbures

Publications (2)

Publication Number Publication Date
EP0991734A1 EP0991734A1 (fr) 2000-04-12
EP0991734B1 true EP0991734B1 (fr) 2001-08-29

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Application Number Title Priority Date Filing Date
EP98933611A Expired - Lifetime EP0991734B1 (fr) 1997-06-12 1998-06-12 Procede d'elimination de dechets halogenes et/ou renfermant des hydrocarbures

Country Status (12)

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US (1) US6488728B1 (fr)
EP (1) EP0991734B1 (fr)
JP (1) JP4023832B2 (fr)
CN (1) CN1213778C (fr)
AT (1) ATE204898T1 (fr)
AU (1) AU744057C (fr)
CA (1) CA2293759C (fr)
DE (1) DE59801332D1 (fr)
DK (1) DK0991734T3 (fr)
ES (1) ES2163873T3 (fr)
PT (1) PT991734E (fr)
WO (1) WO1998056871A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006040662B3 (de) * 2006-08-30 2008-03-27 Pac Holding S.A. Verfahren und Vorrichtung zur Verwertung von sauerstoffhaltigen Polymeren

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DZ2947A1 (fr) 1998-11-25 2004-03-15 Chiesi Farma Spa Inhalateur à compteur de dose sous pression.
US7722690B2 (en) * 2006-09-29 2010-05-25 Kellogg Brown & Root Llc Methods for producing synthesis gas
US8888875B2 (en) * 2006-12-28 2014-11-18 Kellogg Brown & Root Llc Methods for feedstock pretreatment and transport to gasification
US9133405B2 (en) 2010-12-30 2015-09-15 Kellogg Brown & Root Llc Systems and methods for gasifying a feedstock
CN104845663A (zh) * 2015-03-27 2015-08-19 北京燕联化工技术有限公司 一种油品高效脱氯剂及油品脱氯方法
US9850433B2 (en) 2015-12-31 2017-12-26 Chz Technologies, Llc Multistage thermolysis method for safe and efficient conversion of E-waste materials
KR101884517B1 (ko) * 2016-05-23 2018-08-01 울산대학교 산학협력단 할로겐 함유 플라스틱의 분리방법
CN106216357B (zh) * 2016-07-29 2018-11-23 陈佳男 一种聚苯乙烯塑料垃圾处理方法
US10640711B2 (en) 2018-06-05 2020-05-05 Chz Technologies, Llc Multistage thermolysis method for safe and efficient conversion of treated wood waste sources

Citations (1)

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US3252773A (en) * 1962-06-11 1966-05-24 Pullman Inc Gasification of carbonaceous fuels

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DE4234385A1 (de) 1992-10-06 1994-04-07 Formex Trading Gmbh Verfahren zur Pyrolyse von organischen Stoffen
US5315055A (en) * 1992-12-30 1994-05-24 Ohio University Method of cracking polymeric materials catalyzed by copper
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006040662B3 (de) * 2006-08-30 2008-03-27 Pac Holding S.A. Verfahren und Vorrichtung zur Verwertung von sauerstoffhaltigen Polymeren

Also Published As

Publication number Publication date
ES2163873T3 (es) 2002-02-01
DE59801332D1 (de) 2001-10-04
CN1264414A (zh) 2000-08-23
AU744057C (en) 2003-04-10
CA2293759C (fr) 2008-01-22
PT991734E (pt) 2002-02-28
DK0991734T3 (da) 2001-12-17
EP0991734A1 (fr) 2000-04-12
AU744057B2 (en) 2002-02-14
JP4023832B2 (ja) 2007-12-19
CA2293759A1 (fr) 1998-12-17
JP2002503145A (ja) 2002-01-29
WO1998056871A1 (fr) 1998-12-17
AU8337098A (en) 1998-12-30
ATE204898T1 (de) 2001-09-15
CN1213778C (zh) 2005-08-10
US6488728B1 (en) 2002-12-03

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