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WO2001064578A1 - Transformation de chlorure d'hydrogene gazeux avec recuperation de chlore - Google Patents

Transformation de chlorure d'hydrogene gazeux avec recuperation de chlore Download PDF

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Publication number
WO2001064578A1
WO2001064578A1 PCT/US2001/006305 US0106305W WO0164578A1 WO 2001064578 A1 WO2001064578 A1 WO 2001064578A1 US 0106305 W US0106305 W US 0106305W WO 0164578 A1 WO0164578 A1 WO 0164578A1
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WO
WIPO (PCT)
Prior art keywords
gas
chlorine
hci
reaction
chloride
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Ceased
Application number
PCT/US2001/006305
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English (en)
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WO2001064578A8 (fr
Inventor
Robert A. Rapp
Philip Vais
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.)
Ohio State University
Original Assignee
Ohio State University
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 Ohio State University filed Critical Ohio State University
Priority to AU2001250784A priority Critical patent/AU2001250784A1/en
Publication of WO2001064578A1 publication Critical patent/WO2001064578A1/fr
Publication of WO2001064578A8 publication Critical patent/WO2001064578A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride

Definitions

  • the invention includes a method and apparatus directed toward the reactive removal of hydrogen chloride gas from a process stream with the possibility for recovery of molecular chlorine.
  • the invention is directed to the removal of HCI gas from a gas stream and the subsequent conversion of the intermediate product to generate molecular chlorine gas.
  • Background of the Invention Chlorine is extensively used by the chemical and petrochemical industries in the production and processing of organic feed stocks and products. Hydrogen chloride (HCI) and other volatile chlorides are environmentally hazardous waste products often formed during processing. Examples of such processes are the chlorination of benzene or toluene, the production of chlorine-bearing insecticides, the production of refrigerants and aerosols, and the production of silicones and polyurethanes.
  • the first process developed for the recovery of chlorine from HCI gas was called the Gossage invention (1836) which involved water washing of the gas in a coke- packed tower. The aqueous acid was then reacted with manganese dioxide to produce chlorine gas. This process was rather wasteful because large quantities of manganese dioxide were required and only 50% of the potential chlorine was recovered.
  • the Deacon process was vastly improved in the early 1900s by the development of more effective catalysts and the use of fluidized bed techniques. As a result of fluidization, a uniform temperature could be maintained without difficulties arising from the exothermic oxidation reaction.
  • the inability of the catalysts to achieve high activities even at the high temperatures of 400-650°C was overcome in the development of the Shell Process.
  • This process used a new copper-containing catalyst, which made conversion rates of 77-80% achievable.
  • This catalyst contained chlorides of the rare earth metals or scandium, yttrium, zirconium, thorium, and uranium and one or more alkali metal chlorides, with the best results occurring in conjunction with a silica gel substrate. Although the catalyst was in a semi-molten state, the reaction surface area was drastically increased, and lower reaction temperatures could be efficiently maintained to prevent the copper chloride vaporization.
  • the Deacon process was modified to overcome the conversion limitations in the Kel-Chlor process by operating at lower temperatures with sulfuric acid to absorb water as it was formed. With the water removed, the Deacon reaction could proceed to complete conversion.
  • the invention includes a method and apparatus directed toward the conversion of HCI gas with the possibility for recovery of chlorine from the intermediate reaction product.
  • the method comprises the steps of contacting a metal oxide with a gaseous stream containing HCI and H 2 so as to produce a metal chloride and water vapor which may be referred to as "chlorine fixing", and then reoxidizing the metal chloride to release chlorine, and optionally and preferably collecting or reusing the chlorine.
  • the metal oxide can preferably be selected from iron oxide or manganese oxide.
  • H 2 is present in excess of the stoichiometric amount so as to assist in reduction of the oxide and to drive the reaction to completion, the excess H 2 being present preferably in an amount of 1 part in 50 of the stoichiometric amount, more preferably in an amount of 1 part in 10 of the stoichiometric amount and most preferably in an amount of 1 part in 5 of the stoichiometric amount, or greater.
  • the apparatus for recovering the chlorine from hydrogen chloride gas may comprise a plurality of chambers containing a particulate metal oxide, with each of the chambers connected via a valve to a respective fluid conduit adapted to conduct a flow of gaseous fluid containing HCI and H 2 to each of the respective fluid conduits.
  • the apparatus additionally comprises a sensor in each of the chambers to sense when a reaction approaches completion and to signal a valve, such as a relay-activated valve, to release the gaseous fluid to the next chamber.
  • the invention preferably includes an improved direct oxidation method which utilizes iron oxide catalyst material to capture the chlorine from HCI gas and hydrogen gas.
  • the benefits of this invention are apparent in the thermodynamic calculations for this system in comparison to the previously established oxidation techniques.
  • Table 1 contains thermodynamic calculations for the manganese oxide catalyst system using the HSC Chemistry program (version 3.0) for PC Windows. Equilibrium partial pressure calculations were performed assuming a closed system at equilibrium at 1 atmosphere starting pressure. These calculations for manganese oxide are presented to illustrate the problems which arise for a system which behaves in a less than optimum manner.
  • thermodynamics for the similar reactions involving iron oxides shown in Table 2, are even more favorable for the capture of HCI to form a solid metal chloride. Furthermore, in contrast to the manganese oxide catalyst system, the reoxidation of the FeCI 2 solid product with oxygen results in the efficient release of Cl 2 gas containing negligible oxygen.
  • the comparable reactions in Table 2 are numbered the same as the similar reactions in Table 1.
  • reactions 1 and 4 in Table 2 show the reactions of iron oxides with HCI in the absence of excess hydrogen.
  • molecular chlorine is evolved as a reaction product.
  • the presence or addition of hydrogen in reactions 2 and 5 essentially prevents the formation of chlorine gas and also allows an even more favorable and essentially complete reaction with HCI gas (as can be seen from the respective equilibrium constants). Therefore, H 2 : HCI ratios in excess of 1 :4 for Fe 2 O 3 and 1 :6 for Fe 3 O 4 need to be maintained in order to prevent the formation of chlorine during the HCI capture process.
  • the iron oxide material system is slightly more complicated than manganese oxide because of the possible formation of a second chloride (FeCI 3 ).
  • This chloride is highly volatile at the expected chloridation reaction temperatures.
  • Such FeCI 3 vapor would be a major disadvantage for the iron oxide reactant because of the continuous evaporative loss of the material, as well as the contamination of the purge gas with the gaseous chloride species. Fortunately, this disadvantage is circumvented with the presence of excess hydrogen. As can be seen in reaction 7 in Table 2, in the presence of excess hydrogen, FeCI 3 is not thermodynamically stable and the FeCI 3 vapor pressure over FeCI 2 would be low.
  • the second aspect of the catalyst reaction system which must be optimized is the reoxidation of the chloridated catalyst (the chloride salt) to release molecular chlorine.
  • the chloridated catalyst the chloride salt
  • manganese oxide is effective in converting HCI to form MnCI 2 and the regeneration of the MnCI 2 by oxidation to form Mn 2 O 3 does take place manganese oxide does not appear to be the optimum catalyst material.
  • the equilibrium oxygen partial pressures in reactions 3 and 6 in Table 1 reveal that a high percentage of oxygen should be present after these reactions. Consequently, the exit gas from the reaction column during reoxidation by pure O 2 is a mixture of O 2 and Cl 2 gases. This mixture would then once again require additional processing for the separation of these gases.
  • FIG. 1 is a drawing of the multi-chambered apparatus used for recovery of chlorine from hydrogen chloride gas, in accordance with one embodiment of the invention. Detailed Description of the Preferred Embodiments
  • a mixture of argon plus chlorine gas is bubbled into an aluminum melt in order to reduce the dissolved contents of hydrogen, alkali metals and alkaline earth metals.
  • the melt holding tank is covered by a refractory lid to collect the evolving gas.
  • the preferred embodiment of the present invention is the use of a number of enclosed reaction columns containing pellets of fine powder of the iron oxide catalyst material, perhaps incorporated onto an inert ceramic support. Initially, the reaction columns would be heated externally to a reaction temperature of about 200-450°C, and
  • reaction temperature of about 200-450°C to release chlorine gas which could then be used directly as a reactant, as shown in Figure 1 , or otherwise compressed and bottled.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Treating Waste Gases (AREA)

Abstract

Procédé et appareil destinés à la récupération par voie de réaction du chlorure d'hydrogène gazeux à partir d'un flux de traitement, avec possibilité de récupération du chlore moléculaire. Dans un procédé préféré, le chlore est mis en contact avec de l'oxyde de fer particulaire à rapport élevé de la superficie au volume, en présence de l'hydrogène gazeux. On transforme le chlorure de fer ainsi obtenu pour obtenir un oxyde de fer et du chlore. Dans un deuxième mode de réalisation préféré, on fait circuler un premier flux de HCl et de H2 gazeux dans un premier lit d'oxyde réactif. Un capteur détermine le moment lorsque pratiquement toutes les matières de réaction du premier lit sont épuisées. Une vanne actionnée par le capteur dirige le flux gazeux vers un deuxième lit, la matière de réaction dans le premier lit étant régénérée et le chlore gazeux étant récupéré. Dans un mode de réalisation préféré, l'appareil de récupération du chlore à partir du chlorure d'hydrogène gazeux comprend plusieurs chambres de réaction dont chacune contient un oxyde de métal.
PCT/US2001/006305 2000-02-29 2001-02-28 Transformation de chlorure d'hydrogene gazeux avec recuperation de chlore Ceased WO2001064578A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001250784A AU2001250784A1 (en) 2000-02-29 2001-02-28 Conversion of hydrogen chloride gas with recovery of chlorine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US51513100A 2000-02-29 2000-02-29
US09/515,131 2000-02-29

Publications (2)

Publication Number Publication Date
WO2001064578A1 true WO2001064578A1 (fr) 2001-09-07
WO2001064578A8 WO2001064578A8 (fr) 2001-12-06

Family

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PCT/US2001/006305 Ceased WO2001064578A1 (fr) 2000-02-29 2001-02-28 Transformation de chlorure d'hydrogene gazeux avec recuperation de chlore

Country Status (2)

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AU (1) AU2001250784A1 (fr)
WO (1) WO2001064578A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2448038C1 (ru) * 2010-11-10 2012-04-20 Учреждение Российской академии наук Институт химии и химической технологии Сибирского отделения РАН (ИХХТ СО РАН) Способ конверсии хлороводорода для получения хлора
RU2448040C1 (ru) * 2010-11-30 2012-04-20 Учреждение Российской академии наук Институт химии и химической технологии Сибирского отделения РАН (ИХХТ СО РАН) Способ получения серы из сероводорода

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448255A (en) * 1943-12-07 1948-08-31 Shell Dev Catalysts for use in the production of chlorine
US4774070A (en) * 1986-02-19 1988-09-27 Mitsui Toatsu Chemicals, Incorporated Production process of chlorine
US5154911A (en) * 1989-11-02 1992-10-13 University Of Southern California Efficient method for the chemical production of chlorine and the separation of hydrogen chloride from complex mixtures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448255A (en) * 1943-12-07 1948-08-31 Shell Dev Catalysts for use in the production of chlorine
US4774070A (en) * 1986-02-19 1988-09-27 Mitsui Toatsu Chemicals, Incorporated Production process of chlorine
US5154911A (en) * 1989-11-02 1992-10-13 University Of Southern California Efficient method for the chemical production of chlorine and the separation of hydrogen chloride from complex mixtures

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2448038C1 (ru) * 2010-11-10 2012-04-20 Учреждение Российской академии наук Институт химии и химической технологии Сибирского отделения РАН (ИХХТ СО РАН) Способ конверсии хлороводорода для получения хлора
RU2448040C1 (ru) * 2010-11-30 2012-04-20 Учреждение Российской академии наук Институт химии и химической технологии Сибирского отделения РАН (ИХХТ СО РАН) Способ получения серы из сероводорода

Also Published As

Publication number Publication date
AU2001250784A1 (en) 2001-09-12
WO2001064578A8 (fr) 2001-12-06

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