WO2004052513A1 - Destruction des halocarbures - Google Patents

Destruction des halocarbures Download PDF

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Publication number
WO2004052513A1
WO2004052513A1 PCT/GB2003/005415 GB0305415W WO2004052513A1 WO 2004052513 A1 WO2004052513 A1 WO 2004052513A1 GB 0305415 W GB0305415 W GB 0305415W WO 2004052513 A1 WO2004052513 A1 WO 2004052513A1
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Prior art keywords
halo
catalyst
cfc
reaction
substituted
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PCT/GB2003/005415
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English (en)
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James Thomson
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Ceimig Limited
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Priority to AU2003290252A priority Critical patent/AU2003290252A1/en
Priority to EP03782616A priority patent/EP1608456A1/fr
Publication of WO2004052513A1 publication Critical patent/WO2004052513A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2066—Fluorine
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Definitions

  • This invention relates to the molecular fragmentation of halo-substituted hydrocarbons.
  • this invention relates to the catalytic destruction of chlorofluorocarbons (CFCs) .
  • CFCs are inert, non-toxic and non-flammable chemicals containing atoms of carbon, chlorine and fluorine.
  • Catalysis is regarded as having the greatest potential to safely dispose of CFCs. So far, two types of catalysts have been studied: supported Pd catalysts over which hydrogenolysis is performed [6, 7, 8, 9]; and hydrolysis catalysts such as metal oxides (Ti0 2 ; Zr0 2 ; 0 3 ) [10, 11, 12] , metal sulphates [13] and metal phosphates [14] .
  • supported Pd catalysts over which hydrogenolysis is performed [6, 7, 8, 9]
  • hydrolysis catalysts such as metal oxides (Ti0 2 ; Zr0 2 ; 0 3 ) [10, 11, 12] , metal sulphates [13] and metal phosphates [14] .
  • supported Pd catalysts quickly deactivate as they are easily attacked by hydrochloric acid generated in si tu resulting in a loss of both the metal and the support areas [6] .
  • the hydrolysis catalysts show both greater stability towards deactivation and activity at lower operating temperatures, usually less than 500°C.
  • 0 3 /Ti0 2 is reported to achieve complete conversion of CFC- 12 at 265°C [11] , and sulphate promoted Ti 2 -Zr0 2 at 280°C [20] .
  • water prevents the fluorination of the Ti and metals and hence their loss by evaporation.
  • Metal phosphates were previously used to obtain a greater 0 2 supply in the hydrolysis reaction.
  • this system has only been tested with pure CFCs on a small scale. It would also not be suitable for CFCs containing impurities as found in refrigeration equipment .
  • a method of catalytically destroying halo-substituted hydrocarbons comprising the steps of first mixing a gas comprising a halo-substituted hydrocarbon with steam or hydrogen and steam to form a gas mixture and thereafter passing the gas mixture over a catalyst capable of destroying halo-substituted hydrocarbons wherein the temperature of the catalyst is about 100-800°C.
  • destroying the halo-substituted hydrocarbon herein is meant converting the halo-substituted hydrocarbon into a more environmentally friendly form.
  • the chain length of the halo- substituted hydrocarbon may be reduced.
  • the shorter chain molecules may, for example, be methane and ethane.
  • the number of carbon-halo bonds such as carbon-chlorine, carbon-fluorine, carbon- bromine and carbon-iodine bonds are reduced.
  • the catalyst may be supported on an inert carrier.
  • the inert carrier may be a ceramic.
  • the ceramic may be alumina and in particular ⁇ -Al 2 0 3 .
  • the catalyst comprises any of the following: palladium, rhodium, ruthenium, silver, gold, gallium, zinc and/or zirconia.
  • the catalyst may, for example, be a palladium and zinc based catalyst and, in particular, may be a PdZn/ZrO x based catalyst.
  • the catalyst used may be PdZn/ZrO x - ⁇ -Al 2 0 3 .
  • the ratio of Pd:Zn may range from 2:1 to 1:4. In particular, the ratio of Pd:Zn may be 1:2.
  • x may range from 1 to 3.0 and preferably 1.5 to 2.0.
  • the catalyst used may also be in the form of an extrudate or in a monolith.
  • the halo-substituted hydrocarbon may be a hydrochlorofluorocarbon, a chlorofluorocarbon (CFC) , a chlorocarbon or a fluorocarbon.
  • the hydrocarbon may be in a saturated or unsaturated form.
  • the halo-substituted hydrocarbon may be selected, for example, from any of the following: bromocarbon; bromochlorocarbon; bromochloroiodocarbon; bromochlorofluorocarbon; bromochlorofluoroiodocarbon; bromofluorocarbon; bromofluroriodocarbon; bromoiodocarbon; chlorocarbon; chlorofluorocarbon; chlorofluoroiodocarbon; chloroiodocarbon; (per) fluorocarbon; fluoroiodocarbon; hydrobromocarbon; hydrobromochlorocarbon; hydrobromochlorofluorocarbon; hydrobromochlorofluoroiodocarbon; hydrobromochloroiodocarbon ; hydrobromochloroiodocarbon ; hydrobromofluorocarbon; hydrobromofluorocarbon; hydrobromofluorocarbon; hydrobromofluoroiodocarbon; hydrobromoi
  • the halo-substituted carbon is a chlorofluorocarbon (CFC) .
  • CFC chlorofluorocarbon
  • the halo-substituted carbon may be selected from any of the following: CFC- 11; CFC- 12; CFC- 13; CFC-111; CFC-113; CFC-114; CFC-115; CFC 211 - 217 or mixtures thereof .
  • the halo-substituted hydrocarbon for example CFC
  • CFC CFC
  • the reaction temperature may be held in the range of 110-800°C and is typically about 600°C.
  • the halo-substituted hydrocarbon for example
  • CFC may also be destroyed via a hydrolysis reaction wherein the halo-substituted hydrocarbon is reacted with steam.
  • carrier gas such as N 2 is used and bubbled both through the halo-substituted hydrocarbon and a water reservoir and then reacted over the catalyst.
  • the reaction may be carried out at high pressure such as
  • the reaction temperature may be about 500- 700°C or is typically 600°C.
  • the halo-substituted hydrocarbons such as CFCs may be converted into C0 2 , HCl, HF, HBr and HI.
  • the C0 2 , HCl and HF may be easily disposed of or reused in other processes.
  • a catalyst as used in the first aspect for use in the destruction of halo- substituted hydrocarbons.
  • apparatus for catalytically destroying halo-substituted hydrocarbons comprising a catalyst as used in the first aspect.
  • a method of catalytically destroying halo-substituted hydrocarbons comprising the steps of first mixing a gas comprising a halo-substituted hydrocarbon with hydrogen to form a gas mixture and thereafter passing the gas mixture over a PdZn/ZrO x - ⁇ - Al0 3 catalyst wherein the temperature of the catalyst is about 400-800°C.
  • the ratio of Pd:Zn may range from 2:1 to 1:4 and may, in particular, be 1:2.
  • the halo- substituted hydrocarbon may therefore be destroyed via a hydrogenolysis reaction wherein the halo- substituted hydrocarbon, for example CFC, is reacted with H 2 .
  • N 2 which is used as a carrier gas
  • H 2 may be passed, for example, bubbled, through the halo- substituted hydrocarbon and reacted over the catalyst .
  • the reaction temperature may typically be about 600°C.
  • the catalyst used may also be in the form of an extrudate or in a monolith.
  • the halo- substituted hydrocarbon may be a hydrochlorofluorocarbon, a chlorofluorocarbon (CFC) , a chlorocarbon or a fluorocarbon.
  • the hydrocarbon may be in a saturated or unsaturated form.
  • the halo-substituted hydrocarbon may be selected, for example, from any of the following: bromocarbon ; bromochlorocarbon ; bromochloroiodocarbon; bromochlorofluorocarbon ; bromochlorofluoroiodocarbon , • bromofluorocarbon ; bromofluroriodocarbon ; bromoiodocarbon; chlorocarbon ; chlorofluorocarbon ; chlorofluoroiodocarbon; chloroiodocarbon ; (per) fluorocarbon; fluoroiodocarbon ; hydrobromocarbon ; hydrobromochlorocarbon ; hydrobromochlorofluorocarbon; hydrobromochlorofluoroiodocarbon; hydrobromochloroiodocarbon; hydrobromochloroiodocarbon; hydrobromofluorocarbon; hydrobromoiodocarbon; hydrochlorocarbon; hydrochlorofluorocarbon;
  • the halo-substituted carbon may be selected from any of the following: CFC- 11; CFC- 12; CFC- 113; CFC- 114 and CFC- 115, or mixtures thereof.
  • the halo-substituted hydrocarbons such as CFCs may be converted into C0 2 , HCl and HF.
  • the C0 2/ HCl and HF may be easily disposed of or reused in other processes.
  • a PdZn/ZrO x - ⁇ -Al 2 0 3 catalyst for use in a hydrogenolysis reaction in the destruction of halo-substituted hydrocarbons.
  • apparatus for catalytically destroying halo-substituted hydrocarbons comprising a PdZn/ZrO x - ⁇ - Al 2 0 3 catalyst .
  • FIG. 1 is a representation of apparatus used to carry out the catalytic destruction of CFCs according to the present invention
  • Figure 2 is a representation of CFC- 113 peak areas on catalytic destruction at different temperatures and H 2 flow rates according to the present invention
  • Figure 3 is a deactivation study using catalytic extrudate at 600°C according to the present invention.
  • Figure 4 is a representation of a catalytic deactivation study using catalytic monolith at 600°C according to the present invention
  • Figure 5 is a chromatographic representation of gases formed from a catalytic extrudate at the start of the reductively induced steam reaction where the temperature of the water is 75°C;
  • Figure 6 is a chromatographic representation of gases formed from a catalytic extrudate at the halfway point of a reductively induced steam reaction wherein the temperature of the water is 75°C
  • Figure 7 is a chromatographic representation of gases formed from a catalytic extrudate at the halfway point of a reductively induced steam reaction wherein the temperature of the water is 95°C;
  • Figure 8 is chromatographic representation of gases formed from a catalytic extrudate at the end of a reductively induced steam reaction wherein the temperature of the water is 95°C
  • Figure 9 is a chromatographic representation of gases formed from a catalytic extrudate using a thermal conductivity detector of a reductively induced steam reaction wherein the temperature of the water is 95°C;
  • Figure 10 is chromatographic representation of gases formed from a catalytic extrudate at the start of a hydrogenolysis reaction
  • Figure 11 is a chromatographic representation of gases formed from a catalytic extrudate at the halfway point of a hydrogenolysis reaction
  • Figure 12 is a chromatographic representation of gases formed from a catalytic extrudate at the end of a hydrogenolysis reaction
  • Figure 13 is a chromatographic representation of gases formed from a catalytic monolith at the start of a reductively induced steam reaction wherein the temperature of the water is 95°C;
  • Figure 14 is a chromatographic representation of gases formed from a catalytic monolith at the halfway point of a reductively induced steam reaction wherein the temperature of the water is 95°C;
  • Figure 15 is a chromatographic representation of gases formed from a catalytic monolith at the end of a reductively induced steam reaction wherein the temperature of the water is 95°C;
  • Figure 16 is a chromatographic representation of gases formed from a catalytic monolith at the start of a hydrogenolysis reaction
  • Figure 17 is a chromatographic representation of gases formed from a catalytic monolith at the end of a hydrogenolysis reaction
  • Figure 18 is a chromatographic representation of gases formed from a catalytic monolith at the start of a steam reaction wherein the temperature of the water is 95°C;
  • Figure 19 is a chromatographic representation of gases formed from a catalytic monolith at the end of a steam reaction wherein the temperature of the water is 95°C;
  • Figure 20 is an overlay of chromatographic representations of gases formed from a reductively induced steam reaction and a hydrogenolysis reaction using a catalytic extrudate wherein the temperature of the water is 95°C;
  • Figure 21 is an overlay of chromatographic representations of gases formed from a reductively induced steam reaction, hydrogenolysis and a steam reaction using a catalytic monolith wherein the temperature of the water is 95°C;
  • Figure 22 is a representation of hydrogenolysis of carbon tetrachloride;
  • Figure 23 is a representation of the HCL eluent during hydrogenolysis of carbon tetrachloride
  • Figure 24 is a representation of the selectivity of CHC1 3 to hydrocarbons by hydrogenolysis
  • Figure 25 is a representation of selectivity of CH 2 C1 2 to hydrocarbons by hydrogenolysis
  • Figure 26 is a representation of selectivity of CC1 4 to hydrocarbons by hydrolysis
  • Figure 27 is a representation of temperature dependence of HCl eluent during reaction of CC1 4 in the presence of H 2 /steam
  • Figure 28 is a representation of the determination of light-off temperature for the conversion of CFC-113
  • Figure 29 is a representation of the effect of reaction environment on conversion of CFC-113 at 600°C.
  • FIG. 1 Shown in Figure 1, there is a schematic representation of apparatus, generally designated 10, for the catalytic destruction of CFCs.
  • CFC containing gas is first of all fed through a CFC bubbler 12 which has an ice bath 13 and an H 2 0 bubbler 14.
  • a series of flow meters 16, 18, 20 may feed in 0 2 , H 2 , N 2 , respectively.
  • a pressure gauge 22 monitors the flow.
  • the CFC containing gas is then fed to a reactor 24 containing a catalyst 26.
  • a furnace 28 is used to heat the reactor 24 and the catalyst 26 to about, for example,
  • Trap 30 is used to collect any excess aqueous acid formed in the reaction. Gases are passed out via vent 32.
  • a series of bubblers 34 (a to n) is then used prior to the gas being tested by gas chromatography and a thermal conductivity detector (i.e. GC/TCD) or gas chromatography and a flame ionisation detector (i.e. GC/FID) .
  • a thermal conductivity detector i.e. GC/TCD
  • a flame ionisation detector i.e. GC/FID
  • a 0.5 x 0.5 x 6 inch monolith section was coated twice with a 10wt% ⁇ Al 2 0 3 sol based on the uptake of the ⁇ -Al 2 0 3 (0.4069g) , 0.0438g of palladium (II) nitrate hydrate, Pd(N0 3 ) 2 .H 2 0, (0.2mmol; Aldrich Chemical Co.) and 0.1149g of zinc nitrate hexahydrate, Zn (N0 3 ) 2 .6H0, (0.4mmol; Aldrich Chemical Co.) were dissolved in 0.1wt% Pd.Zn(l:2) 100% ZrO x sol (0.136ml) .
  • Batch A was dried at 350°C under dinitrogen, N 2 (BICOFN; SScm nin “1 ) for 20 min followed by calcinations in dioxygen, 0 2 (B0C;35cm 3 min “1 ) for 2h.
  • the reactor temperature was then decreased to 50°C at a ramp rate of 10°C min “1 under N 2 (10cm 3 min "1 ) overnight (18h) .
  • Reduction of Batch B was performed with a 25% H 2 /N 2 feedstream (100cm 3 min "1 ) .
  • the reduction temperature was ramped to 350°C at 1°C min "1 and held constant at 50°C intervals for lh each. Once 350°C was reached, the reverse temperature programme was performed. Finally, the reactor was heated up to 600°C at 5°C min "1 under N 2 (10cm 3 min "1 ) .
  • Batch B was dried at 350°C under dinitrogen, N 2 (10cm 3 min “1 ) for 14h followed by calcination in 0 2 (40cm 3 min “1 ) for 5h.
  • the reactor was flushed with N 2 (45cm 3 min “1 ) for lh.
  • the reactor temperature was then decreased to 50°C at a ramp rate of 10°C min “1 under N 2 (10cm 3 min “1 ) overnight for 18h.
  • Reduction of Batch B was performed with a 25% H 2 /N 2 feedstream at 100cm 3 min "1 .
  • the reduction temperature was ramped to 350°C at 1°C min "1 and held constant at 50°C intervals for lh each. Once 350°C was reached, the reverse temperature program was performed. Finally, the reactor was heated up to 600°C at 5°C min "1 under N 2 (10cm 3 min "1 ) .
  • Batch C was dried at 350°C under dinitrogen, N 2 (35cm 3 min “1 ) for 20 min followed by calcinations in N 2 (80cm 3 min " x ) for lh.
  • the reactor was flushed with N 2 (10cm 3 min “1 ) overnight and the reactor temperature was decreased to 50°C at a ramp rate of 1°C min "1 .
  • Reduction of Batch C was performed with a 20% H 2 /N 2 feedstream (100cm 3 min "1 ) .
  • the reduction temperature was ramped to 350°C at 1°C min "1 and held constant at 50°C intervals for lh each. Once 350°C was reached, the reverse temperature programme was performed. Finally, the reactor was heated up to 600°C at 1°C min "1 under N 2 (10cm 3 min "1 ) .
  • the CFC was reacted with dihydrogen, H 2 .
  • H 2 dihydrogen
  • the CFC bubbler 12 was submerged in an ice bath 13 and held at 0°C to give a time-averaged feed rate of 72.7 ⁇ 6.6 ⁇ l min "1 .
  • the reaction was carried out at a pressure of 800 torr and a reaction temperature of 600°C.
  • the reductively induced steam reaction was performed by passing N 2 (15-55cm 3 min “1 ) , H 2 (10-50cm 3 min “1 ) , and CFC at 72.7 ⁇ 6.6 ⁇ l min "1 and steam over the catalyst 26.
  • the CFC was reacted with steam.
  • the carrier gas N 65cm 3 min "1
  • the carrier gas N was bubbled through both the CFC bubbler 12 (held at 0°C to give a time-averaged feed rate of 72.7 ⁇ 6.6 ⁇ l min "1 ) and the H 2 0 bubbler 14 was held at 95°C and reacted over the catalyst 26.
  • the reaction was carried out at a pressure of 800 torr and a reaction temperature of 600°C.
  • the gas hourly spaced velocity (GHSV) was set to
  • GC on-line gas chromatography
  • FID flame ionisation detector
  • TCD thermal conductivity detector
  • the GC settings were set as shown in the table below.
  • the GC oven temperature was held at 170°C overnight to facilitate desorption of any residue left in the column.
  • H hydrogenolysis
  • rs reductively induced steam reaction
  • -/* reaction carried out with and without trap
  • FID flame ionisation detector
  • TCD thermal conductivity detector
  • Figure 2 is a representation of different reaction conditions for the reductively induced steam reaction of CFC-113.
  • Figure 3 is a representation of a study of the deactivation of catalyst Batch B.
  • the percentage conversion of CFC-113 was measured as a function of time. It should be noted from Figure 3 that the scale of the percentage CFC-113 conversion ranges from 96-100%. From Figure 3 it can be seen that a conversion of greater than 99% was achieved for most of the time at 600°C and is independent of the reaction type. In the reductively induced steam reaction, the temperature rise of the water reservoir after 18h on stream improved that percentage conversion to greater than 99.9% once the system was stabilised. (The initial unsteady state at higher water temperature may be a result of the back pressure problems that occurred during the reactions) .
  • the CFC-113 conversion during the hydrogenolysis (27.7 - 46.4h on stream) was also consistently greater than 99.7% at 600°C.
  • Figure 4 shows a deactivation study of the catalytic monolith Batch C which shows that the percentage of conversion of CFC-113 ranges from 80-100%. From Figure 3 it can be seen that at 600°C, in the H 2 /steam reaction a conversion of greater than 99% was achieved.
  • the chromatographs shown in Figures 5 to 8 show samples taken at the start, halfway and at the end of the reductively induced steam reaction carried out over the extrudate. Since the temperature of the water reservoirs was increased halfway through the experiment, two chromatographs are given for this stage during the experiment. It can be seen that the most prominent peak occurs at 6.8 ⁇ 0.2min followed by a peak at 2.48 ⁇ 0.04min. The effect of the increased water temperature can be noticed by the fact that the peak area of the by-products is smaller.
  • the chromatograph shown in Figure 9 shows a distinct
  • the H 2 /steam reaction over the monolith is shown in the chromatographs shown in Figures 13 to 15. As in the case of the extrudate, the largest peak occurs at 6.4 ⁇ 0.2min and the second largest at 2.43 ⁇ 0.02min.
  • the chromatographs shown in Figures 16 and 17 show that the product distribution of hydrogenolysis over the monolith is initially similar to the one of the extrudate with peaks at 1.67min, 2.45min and 6.66min. (However, as the catalyst deactivated towards the end, the peak at 2.45min disappears) .
  • the reaction is thermally driven and effective at 600°C. This is more than twice as high a temperature than that of Ti0 2 based model catalyst where a complete CFC- 112 conversion is reported at 265°C for W0 3 /Ti0 2 [11] .
  • the Pd. Zn(l :2) /ZrO x - ⁇ -Al 2 0 3 catalyst used in the present invention is capable of burning off carbon as proven by the C0 2 detection from the TCD data shown in Figure 10. Both 0 3 and Ti0 2 are not active for burning hydrocarbons and there is no known chemistry for HFA or hydrocarbon conversion for these metal oxides.
  • the GHSVs shows that the extrudate system could have been run at 40 times higher flow rate and the turnover frequency data shows that the monolith catalyst has a good capacity to deal with a large amount of CFCs.
  • the ability of Pd. Zn (1 : 2) /ZrO x - ⁇ -Al 2 0 3 to catalytically destroy CFCs has therefore been shown. Firstly at 600°C, on average greater than 99% conversion was achieved using hydrogenolysis and a reductively induced steam reaction over a period 44h on stream. A monolith system has also shown a greater than 99% conversion for a H 2 /steam reaction and also for the hydrogenolysis before the activity rapidly declined after 36h on stream.
  • the stability of the catalyst is also supported by the constant value obtained for the formation of hydrogen chloride as shown in Figure 23 where the mass balance for chloride ion is ca 45%.
  • the formation of organics of C > ⁇ is consistent with radicalisation of the surface adsorbed moieties.
  • the susceptibility of the halocarbon to undergo radical mechanisms may also be observed by bromoform and halons .
  • the major product species is methane indicating that the rate of formation of methane (i.e. methyl and hydrogen radical combination) is greater than the rate of methyl radical combination.
  • the catalyst shows during the hydrogenolysis of carbon tetrachloride good stability over a reaction period of 19h with a hydrocarbon output of methane and ethane as the main products (see Figure 22) . With time on line the catalyst is being chlorinated during the process as evidenced by the chlorine mass balance (see Figure 23). After 10.5h the partial pressure of methane clearly decreases as the partial pressure of ethane increases. The formation of C > ⁇ species is consistent with a radical mechanism of the adsorbed surface species as shown below:
  • CCl 4 (g) ⁇ CCl4(a s) ⁇ CCl3( a ds) + Cl ( a ds) CCl 3 (ads) ⁇ CCl 2 (ads) + Cl ( a ds) CCl 2 (ads) ⁇ CCl(ads) + Cl ( a ds) CCl(ads) ⁇ C(a s) + Cl( a da)

Abstract

La présente invention concerne la fragmentation moléculaire d'hydrocarbures substitués par des halogènes. La présente invention concerne plus particulièrement la destruction catalytique de chlorofluorocarbures (CFC) à l'aide d'un catalyseur à base de PdZn/ZrOX-?-Al2O3.
PCT/GB2003/005415 2002-12-11 2003-12-11 Destruction des halocarbures WO2004052513A1 (fr)

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Application Number Priority Date Filing Date Title
AU2003290252A AU2003290252A1 (en) 2002-12-11 2003-12-11 Halocarbon destruction
EP03782616A EP1608456A1 (fr) 2002-12-11 2003-12-11 Destruction des halocarbures

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GBGB0228810.8 2002-12-11
GBGB0228810.8A GB0228810D0 (en) 2002-12-11 2002-12-11 Halocarbon destruction

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US8043574B1 (en) 2011-04-12 2011-10-25 Midwest Refrigerants, Llc Apparatus for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide
US8128902B2 (en) 2011-04-12 2012-03-06 Midwest Refrigerants, Llc Method for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide
DE102012223636A1 (de) * 2012-12-18 2014-06-18 Bhs-Sonthofen Gmbh Anlage zum Recyceln von Kühlgeräten
US8834830B2 (en) 2012-09-07 2014-09-16 Midwest Inorganics LLC Method for the preparation of anhydrous hydrogen halides, inorganic substances and/or inorganic hydrides by using as reactants inorganic halides and reducing agents
EP4321238A1 (fr) * 2022-08-08 2024-02-14 Grillo-Werke Aktiengesellschaft Déhalogénation des hydrocarbures halogénés

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US8043574B1 (en) 2011-04-12 2011-10-25 Midwest Refrigerants, Llc Apparatus for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide
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EP4321238A1 (fr) * 2022-08-08 2024-02-14 Grillo-Werke Aktiengesellschaft Déhalogénation des hydrocarbures halogénés

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