Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
  • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
  • C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
  • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
  • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
  • C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons

Definitions

• This invention is directed to an apparatus and process for producing vinyl chloride monomer from ethane and ethylene. Especially, this invention is directed to processes for producing vinyl chloride monomer (VCM) where (1) ethane concentration is significant in input streams to the affiliated reactor, and (2) consideration is given to alternative hydrogen chloride processing methods.
• VCM vinyl chloride monomer
• Vinyl chloride is a key material in modern commerce, and most processes deployed today derive vinyl chloride from 1 ,2-dichloroethane (EDC) where the EDC is first-derived from ethylene; so, at least a three-operation overall system is used (ethylene from primary hydrocarbons, preponderantly via thermal cracking; ethylene to EDC; and then EDC to vinyl chloride).
• VINYL CHLORIDE which issued on August 17, 1966 describes use of multivalent metals, including those in the lanthanum series, in the production of vinyl chloride from ethane.
• the patent describes use of certain catalysts provided that "steam, available chlorine and oxygen are used in specific controlled ratios.”
• the described system operates at a temperature of between 500 and 750°C.
• Available chlorine in the described technology optionally includes 1 ,2-dichloroethane.
• GB Patent 1,492,945 entitled “PROCESS FOR PRODUCING VINYL CHLORIDE” which issued on November 23, 1977 to John Lynn Barclay discloses a process for the production of vinyl chloride using lanthanum in a copper-based ethane-to- vinyl catalyst. The authors describe that the lanthanum is present to favorably alter the volatility of copper at the elevated temperature required for operation. Examples show the advantage of excess hydrogen chloride in the affiliated reaction.
• GB Patent 2,095,242 entitled “PREPARATION OF MONOCHLORO-OLEFINS BY OXYCHLORINATION OF ALKANES” which issued on September 29, 1982 to David Roger Pyke and Robert Reid describes a "process for the production of monochlorinated olefins which comprises bringing into reaction at elevated temperature a gaseous mixture comprising an alkane, a source of chlorine and molecular oxygen in the presence of a ... catalyst comprising metallic silver and/or a compound thereof and one or more compounds of manganese, cobalt or nickel".
• the authors indicate that mixtures of ethane and ethylene can be fed to the catalyst. No examples are given and the specific advantages of ethane/ethylene mixtures are not disclosed.
• GB Patent 2,101,596 entitled “OXYCHLORINATION OF ALKANES TO MONOCHLORINATED OLEFINS" which issued on January 19, 1983 to Robert Reid and David Pyke describes a "process for the production of monochlorinated olefins which comprises bringing into reaction at elevated temperature a gaseous mixture comprising an alkane, a source of chlorine and molecular oxygen in the presence of a ... catalyst comprising compounds of copper, manganese and titanium and is useful in the production of vinyl chloride from ethane.”
• the authors further describe that "the products of reaction are, in one embodiment, isolated and used as such or are, in one embodiment, recycled ... to the reactor ... to increase the yield of monochlorinated olefin.”
• the authors indicate that mixtures of ethane and ethylene can be fed to the catalyst. No examples are given and the specific advantages of ethane/ethylene mixtures are not disclosed.
• US Patent 3,644,561 entitled “OXYDEHYDROGENATION OF ETHANE” which issued on February 22, 1972 to William Q. Beard, Jr. and US Patent 3,769,362 entitled “OXYDEHYDROGENATION OF ETHANE” which issued on October 30, 1973 to William Q. Beard, Jr. relate closely to those above and describe processes for the oxydehydrogenation of ethane to ethylene in the presence of excess quantities of hydrogen halide.
• the patent describes a catalyst of either copper or iron halide further stabilized with rare earth halide where the ratio of rare earth to copper or iron halide is greater than 1:1.
• ETHANE which issued on March 17, 1992 to John E. Stauf er describes chlorocarbons as a chlorine source in an ethane-to-VCM process. This patent describes methods where chlorohydrocarbons may be used to capture HCl for subsequent use in the production of vinyl. EVC Corporation has been active in ethane-to- vinyl technology, and the following four patents have resulted from their efforts in development.
• EP 667,845 entitled “OXYCHLORINATION CATALYST” which issued on January 14, 1998 to Ray Hardman and Ian Michael Clegg describes a copper-based catalyst with a stabilization package for ethane-to-vinyl catalysis. This catalyst appears to be relevant to the further technology described in the following three US patents.
• the 1 ,2-dichloroethane is subsequently cracked at elevated temperature to yield VCM and hydrogen chloride (HCl).
• the HCl produced is in turn fed to an oxychlorination reactor where it is reacted with ethylene and oxygen to yield more 1 ,2-dichl ⁇ roethane.
• This 1,2-dichloroethane is also fed to thermal cracking to produce VCM.
• Such a process is described in US Patent 5,210,358 entitled "CATALYST COMPOSITION AND PROCESS FOR THE PREPARATION OF ETHYLENE FROM ETHANE" which issued on May 11, 1993 to Angelo J. Magistro.
• Ethylene cost represents a significant fraction of the total cost of production of VCM and requires expensive assets to produce. Ethane is less expensive than ethylene, and production of VCM from ethane should, therefore, reasonably lower the production cost of VCM in comparison to the production cost of VCM when manufactured primarily from purified and separated ethylene.
• Catalysts for the production of 1 ,2-dichloroethane by oxychlorination of ethylene share many common characteristics. Catalysts capable of performing this chemistry have been classified as modified Deacon catalysts [Olah, G. A., Molnar, A., Hydrocarbon Chemistry, John Wiley & Sons (New York, 1995), pg 226].
• Deacon chemistry refers to the Deacon reaction, the oxidation of HCl to yield elemental chlorine and water.
• oxychlorination is the utilization of HCl for chlorination and that the HCl is converted oxidatively into Cl 2 by means of the Deacon process [Selective Oxychlorination of Hydrocarbons: A Critical Analysis, Catalytica Associates, Inc., Study 4164A, October 1982, page 1].
• the ability of oxychlorination catalysts to produce free chlorine (Cl 2 ) thus defines them.
• oxychlorination of alkanes has been linked to the production of free chlorine in the system [Selective Oxychlorination of Hydrocarbons: A Critical Analysis, Catalytica Associates, Inc., Study 4164A, October 1982, page 21 and references therein].
• These catalysts employ supported metals capable of accessing more than one stable oxidation state, such as copper and iron.
• oxychlorination is the oxidative addition of two chlorine atoms to ethylene from HCl or another reduced chlorine source.
• catalysts which are capable of production of free chlorine. Such catalysts will convert ethylene to 1,2-dichloroethane at low temperatures. At higher temperatures, 1,2- dichloroethane will be disposed to thermally crack to yield HCl and vinyl chloride. Oxychlorination catalysts chlorinate olefinic materials to still higher chlorocarbons. Thus, just as ethylene is converted to 1,2-dichloroethane, vinyl chloride is converted to 1,1,2- trichloroethane. Processes using oxychlorination catalysts inherently produce higher chlorinated side-products.
• Catalysts used for ethane-to-VCM manufacture are frequently stabilized against the migration of the first-row transition metals, as described and reviewed in GB Patent 1,492,945; GB Patent 2,101,596; US Patent 3,644,561; US Patent 4,300,005; and US Patent 5,728,905.
• Use of chlorocarbons as chlorine sources in ethane-to-VCM processes has been disclosed in GB Patent 1,039,369; GB Patent 2,101,596; US Patent 5,097,083; US Patent 5,663,465; and US Patent 5,763,710.
• GB Patent 1,039,369 requires that water be fed to the reactor system.
• GB Patent 2,101,596 is specific to copper catalysts.
• US Patent 5,663,465 describes a process which uses a direct chlorination step to convert ethylene to EDC prior to feeding it back to the VCM reactor.
• the catalyst of this application demonstrates utility in reacting significant quantities of both ethane and ethylene into vinyl chloride monomer and thereby opens a door to new approaches in processes for vinyl chloride manufacture.
• the catalyst action yields hydrogen chloride in the reaction product.
• management of hydrogen chloride (and affiliated hydrochloric acid) within the process is a key issue to be resolved when a catalyst system capable of conversion of both ethane and ethylene into vinyl chloride monomer is used.
• the present invention provides embodiments for fulfilling these needs, by providing an apparatus and process for handling hydrogen chloride generated from the ethane/ethylene-to-vinyl reactor by essentially fully recovering it from the reactor effluent in the first unit operation after the ethane/ethylene-to-vinyl reaction step or stage.
• this invention provides a method of manufacturing vinyl chloride, comprising: (a) combining reactants including ethane, ethylene, or mixtures thereof with an oxygen source and a chlorine source in a reactor containing a suitable catalyst under conditions sufficient to convert substantially all of the C2 hydrocarbon fed and to produce a product stream comprising vinyl chloride and hydrogen chloride; and (b) recycling unreacted hydrogen chloride back for use in the combining step.
• This process can be run using air as an oxygen source.
• this invention provides a method of manufacturing vinyl chloride, comprising: (a) combining reactants including ethane and optionally ethylene with an oxygen source and a chlorine source in a reactor containing a suitable catalyst under conditions sufficient to produce vinyl chloride and hydrogen chloride; (b) catalytically reacting essentially all of said hydrogen chloride in a second reactor to provide a second reactor effluent essentially devoid of hydrogen chloride; and (c) recycling said second reactor effluent to catalytically react together with said ethane, said optional ethylene, said oxygen source, and said chlorine source in said combining step.
• Figure 1 shows characterization, as best understood from earlier publications, of a contemplated ethane-to- vinyl chloride process employing a catalyst capable of converting ethane to VCM.
• Figure 2 shows an ethane/ethylene-to-vinyl chloride process, as reproduced from Figure 2 of International Patent Publication No. WO 01/38272 (May 31, 2001).
• the process employs a catalyst capable of converting ethane and ethylene to VCM via oxydehydro-chlorination with a second oxychlorination reactor for ethylene conversion to ethylene dichloride.
• Figure 3 shows an ethane/ethylene-to-vinyl chloride process, as reproduced from Figure 3 of International Patent Publication No. WO 01/38272 (May 31, 2001).
• the process employs a catalyst capable of converting ethane and ethylene to VCM via oxydehydro-chlorination in a first reactor with a second stage reactor system.
• Figure 4 reproduced from Figure 4 of International Patent Publication No. WO 01/38272 (May 31, 2001), shows the ethane/ethylene-to-vinyl chloride process of Figure 3 with an incorporated vinyl furnace and vinyl finishing operation.
• Figure 5 illustrates an embodiment of this invention wherein air is employed as the source of oxygen for the ethane/ethylene-to-vinyl chloride process with hydrogen chloride recovery and recycle.
• C2 hydrocarbon starting materials are reacted essentially to extinction, thereby eliminating a C2 hydrocarbon recycle.
• Figure 5a illustrates another embodiment of this invention employing air as an oxygen source, similar to the embodiment of Figure 5, with the exception that a hydrogenation unit operation is added to convert cw/tr ⁇ ns-dichloroethylenes to 1 ,2- dichloroethane (ethylene dichloride, EDC).
• EDC ethylene dichloride
• Figure 5b illustrates another embodiment of this invention employing air as an oxygen source, similar to the embodiment of Figure 5, with the exception that Figure 5b has a different configuration of unit operations from Figures 5 and 5a.
• Figure 6 illustrates an embodiment of this invention wherein HCl from the ethane/ethylene-to-vinyl chloride process is employed as a "wet" feed to a conventional oxychlorination reactor in which oxygen and ethylene are fed to form ethylene dichloride, which is recycled back to the primary reactor.
• Figure 6a illustrates an alternative scheme to the embodiment of Figure 6, wherein a hydrogenation step is included for hydrogenating cwJra «5-l,2-dichloroethlenes to 1,2- dichloroethane.
• Figure 6b illustrates another alternative scheme to the embodiment of Figure 6, wherein a C2 absorption and stripper block and recycle is omitted since the C2 hydrocarbon starting materials are reacted essentially to extinction.
• Figure 6c illustrates another alternative scheme to the embodiment of Figure 6 wherein the C2 absorption and stripper block and recycle is omitted and a hydrogenation unit is included.
• Figure 7 illustrates another alternative scheme to the embodiment of Figure 6, wherein aqueous HCl (the HCl is formed in the primary reactor) is used to form ethylene chloride and ethylene dichloride, which are fed to the primary reactor.
• aqueous HCl the HCl is formed in the primary reactor
• Figure 7a illustrates an alternative scheme to the embodiment of Figure 7 wherein a hydrogenation step is included.
• Figure 7b illustrates an alternative scheme to the embodiment of Figure 7 wherein a hydrogenation unit is included, and wherein air is employed as the source of oxygen for the primary reactor such that the C2 starting hydrocarbons are reacted essentially to extinction, and thus, a C2 recycle subsystem is eliminated.
• oxychlorination is conventionally referenced as the oxidative addition of two chlorine atoms to ethylene from HCl or other reduced chlorine source. Catalysts capable of performing this chemistry have been classified as modified Deacon catalysts [Olah, G. A., Molnar, A., Hydrocarbon Chemistry, John Wiley & Sons (New York, 1995), pg 226].
• Deacon chemistry refers to the Deacon reaction, the oxidation of HCl to yield elemental chlorine and water.
• the preferred process described herein preferably utilizes oxydehydro-chlorination in converting ethane-containing and ethylene-containing streams to VCM at high selectivity.
• Oxydehydro-chlorination is the conversion of a hydrocarbon, using oxygen and a chlorine source, to a chlorinated hydrocarbon wherein the carbons either maintain their initial valence or have their valency reduced (that is, sp carbons remain sp 3 or are converted to sp 2 , and sp 2 carbons remain sp 2 or are converted to sp).
• the oxydehydro- chlorination catalyst is also an active catalyst for the elimination of HCl from saturated chlorohydrocarbons. Recycle of ethyl chloride and 1,2-dichloroethane is, in some cases, advantageously employed in the production of vinyl chloride. The remaining significant chlorinated organic side-products are the dichloroethylenes. These materials are, in one embodiment, hydrogenated to yield 1 ,2-dichloroethane. 1 ,2-dichloroethane is a large volume chemical and is either sold or recycled. In an alternative embodiment, EDC is hydrogenated completely to yield ethane and HCl.
• this invention provides a method of manufacturing vinyl chloride, comprising: (a) combining reactants including ethane, ethylene, or mixtures thereof with an oxygen source and a chlorine source in a reactor containing a suitable catalyst under conditions sufficient to convert substantially all of the C2 hydrocarbon fed and to produce a product stream comprising vinyl chloride and hydrogen chloride; and (b) recycling unreacted hydrogen chloride back for use in the combining step.
• the phrase "under conditions sufficient to convert substantially all of the C2 hydrocarbon fed” shall mean that greater than about 95 mole percent, preferably, greater than about 97 mole percent, of the C2 hydrocarbon fed (ethane, ethylene, or mixtures thereof) is converted to products.
• the unconverted C2 hydrocarbon shall comprise no greater than about 5 mole percent, preferably, no greater than about 3 mole percent, of a non-condensable lights stream obtained from the effluent of the reactor in step (a).
• a C2 recycle subsystem back to the reactor of step (a) is preferably eliminated from the process.
• the process of this invention can be run using air as an oxygen source, as explained in detail hereinafter. Further details of this invention are set forth in the description to follow and the Figures associated therewith, particularly Figures 5, 5a, and 5b.
• the product stream contains cw/tran.s-l,2-dechloroethylenes, which are hydrogenated with hydrogen in a hydrogenation reactor to form 1,2-dichloroethane (EDC), which itself is recycled, at least in part, to the oxydehydro-chlorination reactor of step (a).
• EDC 1,2-dichloroethane
• this invention provides a method of manufacturing vinyl chloride, comprising: (a) combining reactants including ethane, optionally ethylene, an oxygen source, and a chlorine source in a reactor containing a suitable catalyst under conditions sufficient to produce vinyl chloride and hydrogen chloride; (b) catalytically reacting essentially all of said hydrogen chloride in a second reactor to provide a second reactor effluent essentially devoid of hydrogen chloride; and (c) recycling said second reactor effluent to catalytically react together with said ethane, said optional ethylene, said oxygen source, and said chlorine source in said combining step.
• the phrase "essentially devoid of hydrogen chloride” shall mean that essentially all of the hydrogen chloride is consumed in step (b), such that unconverted hydrogen chloride, if any at all, falls below a recoverable concentration. Additional features and advantages of the second aspect of the invention are set forth hereinafter and illustrated in the figures, particularly, Figures 6, 6a-6c, 7, and 7a-7c.
• the hydrogen chloride recovered from the oxydehydro-chlorination effluent stream of step (a) is employed in a conventional oxychlorination reactor, for example those typical of the prior art, to convert ethylene in the presence of oxygen and the hydrogen chloride to ethylene dichloride, which itself is recycled to the primary oxydehydro-chlorination reactor of step (a).
• the hydrogen chloride recovered from the oxydehydro-chlorination effluent stream of step (a) is employed in a liquid phase aqueous oxychlorination process wherein ethylene in the presence of oxygen and the hydrogen chloride is converted to ethylene dichloride, which itself is recycled to the primary oxydehydro-chlorination reactor (a).
• the oxygen source is air
• the C2 hydrocarbon fed in step (a) that is, ethane and optionally ethylene
• the C2 hydrocarbon fed in step (a) that is, ethane and optionally ethylene
• the C2 hydrocarbon fed in step (a) that is, ethane and optionally ethylene
• the C2 hydrocarbon fed in step (a) is reacted essentially to extinction, that is, greater than 95 mole percent, and preferably, greater than about 97 mole percent, of the C2 hydrocarbon fed is converted to products.
• the product stream contains cis/trans- 1 ,2-dechloroethylenes, which are hydrogenated with hydrogen in a hydrogenation reactor to 1 ,2-dichloroethane (EDC), which itself is recycled, at least in part, to the oxydehydro-chlorination reactor.
• EDC ,2-dichloroethane
• Ethane to VCM Process 100 shows characterization of a contemplated ethane-to-vinyl chloride process employing a catalyst capable of converting ethane to VCM; in this regard, the process does not provide for input of significant quantities of ethylene from either recycle streams or feed-streams to the ethane- VCM reactor (Ethane Reactor 102). It should also be noted that, since an ethane-to-vinyl manufacturing system of appropriate normal manufacturing scale has not, to the best knowledge of the inventors, been yet constructed, proposed process approaches are the only sources for embodiments which have been previously conceptualized.
• Process 100 is a unified and simplified approximation to processes collectively reviewed in several publications respective to investigations and developments at EVC Corporation: Vinyl Chloride/Ethyl ene Dichloride 94/95-5 (March, 1996; Chemical Systems, Inc.; Tarrytown, New York); EP 667,845; US Patent 5,663,465; US Patent 5,728,905; and US Patent 5,763,710.
• Ethane Reactor 102 outputs a fluid stream to Quench Column 106 where HCl is quenched from the reactor output effluent.
• Quench Column 106 forwards a raw strong HCl aqueous stream to Phase Separation Subsystem 108.
• Phase Separation Subsystem 108 outputs a fluid stream to Anhydrous HCl Recovery Subsystem 110 where aqueous hydrogen chloride (hydrochloric acid), anhydrous HCl, and water are separated from the raw strong HCl aqueous stream.
• Anhydrous HCl Recovery Subsystem 110 outputs Stream 130 to recycle anhydrous hydrogen chloride to Ethane Reactor 102, and Anhydrous HCl Recovery Subsystem 110 also outputs water (for subsequent use or to waste recovery).
• Anhydrous HCl Recovery Subsystem 110 returns a relatively dilute aqueous stream of HCl (hydrochloric acid) via Stream 128 to Quench Column 106.
• Quench Column 106 also outputs a fluid stream to Lights Column 114 where a lights stream containing ethylene is further removed from the reactor effluent product stream.
• Lights Column 114 outputs the lights stream to Direct Chlorination Reactor 112 where chlorine (Stream 126) is added to directly chlorinate ethylene in the lights stream into EDC (1,2-dichloroethane).
• EDC is recovered in EDC Recovery Column 116 for recycle to Ethane Reactor 102, and a certain amount of the remaining lights gas is recycled to Ethane Reactor 102 as Stream 134 with CO (carbon monoxide) composition instrumentation providing a measurement (not shown) for use in a control system's (not shown) determination of an appropriate portion of the remaining lights gas for processing via Vent Oxidation Unit 118 to generate a vent stream for removal of CO, CO 2 , and other impurities from the system.
• CO carbon monoxide
• Effluent from Lights Column 114 which does not proceed to Direct Chlorination Reactor 112 forwards (a) first, to Drying Subsystem 120 for removal of water; (b) further, to VCM Purification Column 122 for separation of VCM (vinyl chloride monomer) product; and then (c) further, to Heavies Column 124 for removal of heavies and generation of Stream 132.
• Stream 132 is a blended fluid of cw-l,2-dichloroethylene and trans-1,2- dichloroethylene, 1,2-dichloroethane, ethyl chloride, and other chlorinated organics.
• Drying Subsystem 120 removes water prior to Lights Column 114, with the VCM-carrying effluent from Lights Column 114 being forwarded (a) first, to VCM Purification Column 122 for separation of VCM (vinyl chloride monomer) product and then (b) further, to Heavies Column 124 for removal of heavies and generation of Stream 132.
• VCM vinyl chloride monomer
• Stream 132 forwards to RC1 (chlorinated organics) Hydrogenation Reactor 104 where addition of hydrogen effects a recycle stream for forwarding to Ethane Reactor 102.
• RC1 chlorinated organics
• Figures 2, 3, and 4 there are provided various embodiments of converting ethane, ethylene, or mixtures thereof with an oxygen source and a chlorine source to vinyl chloride monomer (VCM) in a one-step reactor.
• VCM vinyl chloride monomer
• Figures 2, 3, and 4 illustrate a one-step process that eliminates the need for an ethane to ethylene cracker by typically using a preferred rare earth catalyst, as described hereinafter.
• Figures 2, 3, and 4 typically operate in a "fuel-rich" regime where unconverted hydrocarbon feed (ethane and/or ethylene) is recovered and recycled.
• HCl present in the product stream is recovered and recycled in the process of Figure 2, or alternatively, reacted to extinction or near-extinction in the process of Figures 3 and 4.
• the present invention described herein provides modifications to the generalized one-step process illustrated in Figures 2, 3, and 4. Accordingly, the process embodiments of Figures 2, 3, and 4 are described in detail hereinafter.
• Ethane to VCM Oxydehydro-chlorination Process 200 shows an ethane/ethylene-to- vinyl chloride process employing a catalyst capable of converting ethane and ethylene to VCM via oxydehydro-chlorination; in this regard, the process provides for input of significant quantities of both ethane and ethylene from either recycle streams or feed- streams to the reactor ( Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202).
• Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 receives input from (a) feed streams Ethane Feed Stream 222, HCl Feed Stream 224, Oxygen Feed Stream 226, and Chlorine Feed Stream 228 and (b) recycle streams Ethyl Chloride Stream 230, Hydrogen chloride (HCl) Stream 266, and Lights Recycle Stream 248 as well a portion of EDC Stream 262 when EDC is advantageously used for recycle according to the market and operational conditions at a particular moment of manufacture.
• Patent Case No. 44649 to Mark E. Jones, Michael M. Olken, and Daniel A. Hickman, entitled "A PROCESS FOR THE
• the catalyst used in Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 comprises at least one rare earth material.
• the rare earths are a group of 17 elements consisting of scandium (atomic number 21), yttrium (atomic number 39) and the lanthanides (atomic numbers 57-71) [James B. Hedrick, U.S. Geological Survey - Minerals Information - 1997, "Rare-Earth Metals"].
• the catalyst can be provided as either a porous, bulk material or it can be supported on a suitable support.
• Preferred rare earth materials are those based on lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, and lutetium.
• Most preferred rare earth materials for use in the aforementioned VCM process are based on those rare earth elements that are typically considered as being single valency materials. Catalytic performance of multi- valency materials appears to be less desirable than those that are single valency.
• cerium is known to be an oxidation- reduction catalyst having the ability to access both the 3 + and 4 + stable oxidation states. This is one reason why, if the rare earth material is based on cerium, the catalyst further comprises at least one more rare earth element other than cerium.
• the cerium is provided in a molar ratio that is less than the total amount of other rare earths present in the catalyst. More preferably, however, substantially no cerium is present in the catalyst.
• substantially no cerium it is meant that any cerium is in an amount less than 33 atom percent of the rare earth components, preferably less than 20 atom percent, and most preferably less than 10 atom percent.
• the rare earth material for the catalyst is more preferably based upon lanthanum, neodymium, praseodymium or mixtures of these. Most preferably, at least one of the rare earths used in the catalyst is lanthanum. Furthermore, the catalyst is substantially free of iron and copper, especially as regards the ethylene feed. In general, the presence of materials that are capable of oxidation-reduction (redox) is undesirable for the catalyst. It is preferable for the catalyst to also be substantially free of other transition metals that have more than one stable oxidation state. For example, manganese is another transition metal that is preferably excluded from the catalyst. By “substantially free” it is meant that the atom ratio of rare earth element to redox metal in the catalyst is greater than 1, preferably greater than 10, more preferably greater than 15, and most preferably greater than 50.
• the catalyst may also be deposited on an inert support.
• Preferred inert supports include alumina, silica gel, silica-alumina, silica-magnesia, bauxite, magnesia, silicon carbide, titanium oxide, zirconium oxide, zirconium silicate, and combinations thereof.
• the support is not a zeolite.
• the rare earth material component of the catalyst typically comprises from 3 weight percent (wt percent) to 85 wt percent of the total weight of the catalyst and support.
• the catalyst may be supported on the support using methods already known in the art. It may also be advantageous to include other elements within the catalyst in both of the porous, bulk material and supported forms.
• preferable elemental additives include alkaline earths, boron, phosphorous, sulfur, silicon, germanium, titanium, zirconium, hafnium, aluminum, and combinations thereof. These elements can be present to alter the catalytic performance of the composition or to improve the mechanical properties (for example attrition-resistance) of the material.
• the catalyst composition Prior to combining the ethane-containing, ethylene-containing, or ethane/ethylene- containing feed, oxygen source, and chlorine source in the reactor for the VCM process embodiment of this invention, it is preferable for the catalyst composition to comprise a salt of at least one rare earth element, with the proviso that the catalyst is substantially free of iron and copper and with the further proviso that when cerium is employed the catalyst further comprises at least one more rare earth element other than cerium.
• the salt of at least one rare earth element is preferably selected from rare earth oxychlorides, rare earth chlorides, rare earth oxides, and combinations thereof, with the proviso that the catalyst is substantially free of iron and copper and with the further proviso that when cerium is used the catalyst further comprises at least one more rare earth element other than cerium.
• the salt comprises a rare earth oxychloride of the formula MOC1, wherein M is at least one rare earth element chosen from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium, or mixtures thereof, with the proviso that, when cerium is present, at least one more rare earth element other than cerium is also present.
• the salt is a porous, bulk lanthanum oxychloride (LaOCl) material.
• This material beneficially does not undergo gross changes (for example, fracturing) when chlorinated in situ in this process, and provides the further beneficial property of water solubility in the context of this process after a period of use (LaOCl is initially water-insoluble), so that should spent catalyst need to be removed from a fluidized bed, fixed bed reactor or other process equipment or vessels, this can be done without hydroblasting or conventional labor- intensive mechanical techniques, by simply flushing the spent catalyst from the reactor in question with water.
• the salt when it is a rare earth oxychloride (MOC1), it has a BET surface area of at least 12 m 2 /g, preferably at least 15 m 2 /g, more preferably at least 20 m 2 /g, and most preferably at least 30 m 2 /g. Generally, the BET surface area is less than 200 m 2 /g.
• the nitrogen adsorption isotherm was measured at 77K and the surface area was calculated from the isotherm data utilizing the BET method (Brunauer, S., Emmett, P.H., and Teller, E., Journal of the American Chemical Society, 60, 309 (1938)).
• the MOCl phases possess characteristic powder X-Ray Diffraction (XRD) patterns that are distinct from the MC1 3 phases.
• M can be a mixture of at least two rare earths selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium.
• a catalyst is formed in situ from the salt of at least one rare earth element.
• the in situ formed catalyst comprises a chloride of the rare earth component.
• M is a rare earth component selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium and mixtures thereof, with the proviso that when cerium is present the catalyst further comprises at least one more rare earth element other than cerium.
• M is a rare earth component selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium and mixtures thereof, with the proviso that when cerium is present the catalyst further comprises at least one more rare earth element other than cerium.
• the salt when it is a rare earth chloride (MC1 3 ), it has a BET surface area of at least 5 m 2 /g, preferably at least 10 m 2 /g, more preferably at least 15 m 2 /g, more preferably at least 20 m 2 /g, and most preferably at least 30 m 2 /g.
• One method for forming the composition comprising the rare earth oxychloride (MOCl) comprises the following steps: (a) preparing a solution of a chloride salt of the rare earth element or elements in a solvent comprising either water, an alcohol, or mixtures thereof; (b) adding a nitrogen-containing base to cause the formation of a precipitate; and (c) collecting, drying and calcining the precipitate in order to form the MOCl material.
• the nitrogen-containing base is selected from ammonium hydroxide, alkyl amine, aryl amine, arylalkyl amine, alkyl ammonium hydroxide, aryl ammonium hydroxide, arylalkyl ammonium hydroxide, and mixtures thereof.
• the nitrogen-containing base may also be provided as a mixture of a nitrogen-containing base with other bases that do not contain nitrogen.
• the nitrogen-containing base is tetra-alkyl ammonium hydroxide.
• the solvent in Step (a) may be water. Drying of the catalytically-useful composition can be done in any manner, including by spray drying, drying in a purged oven and other known methods. For a fluidized bed mode of operation, a spray-dried catalyst can be employed.
• Another method for forming the catalyst composition comprising the rare earth chloride (MC1 ) comprises the following steps: (a) preparing a solution of a chloride salt of the rare earth element or elements in a solvent comprising either water, an alcohol, or mixtures thereof; (b) adding a nitrogen-containing base to cause the formation of a precipitate; (c) collecting, drying and calcining the precipitate; and (d) contacting the calcined precipitate with a chlorine source.
• one application of this method would be to precipitate LaCl 3 solution with a nitrogen containing base, dry it, add it to the reactor, heat it to 400°C in the reactor to perform the calcination, and then contact the calcined precipitate with a chlorine source to form the catalyst composition in situ in the reactor.
• Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 catalytically reacts together ethane, ethylene, hydrogen chloride, oxygen, and chlorine along with at least one recycle stream to yield Reactor Effluent Stream 232; and it is of special note that the molar ratio of ethane to ethylene derived from all feeds to Ethane/Ethylene To VCM Oxydehydro- chlorination Reactor 202 is between 0.02 and 50 (note that the particular operational ratio at any moment is determined by issues in operational process status) without long- term detriment to catalyst functionality. Depending on market and operational conditions at a particular moment of manufacture, ethylene is added to Reactor 202 via Ethylene Stream 289.
• a more preferred molar ratio of ethane to ethylene derived from all feeds to Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 is between 0.1 and 10.
• one mode is for Ethylene Stream 289 to have a flow of zero and for the molar ratio of ethane to ethylene derived from all feeds to Ethane/Ethylene To VCM Oxydehydro- chlorination Reactor 202 to be between 1 and 6, with variance therein dependent upon local process conditions and catalyst life-cycle considerations.
• Chlorine sources selected from hydrogen chloride, chlorine, and a saturated chlorohydrocarbon
• HCl Feed Stream 224 Chlorine Feed Stream 228, any portion of EDC Stream 262 chosen for recycle, and any other recycled or raw material feed streams containing, without limitation, at least one of a chlorinated methane or a chlorinated ethane (for example, without limitation, carbon tetrachloride, 1,2-dichloroethane, ethyl chloride, 1,1-dichloroethane, and 1,1,2-trichloroethane) collectively provide chlorine to the oxydehydro-chlorination reaction; these streams are individually variable from moment to moment in real-time operation for providing the stoichiometric chlorine needed for VCM conversion.
• a chlorinated methane or a chlorinated ethane for example, without limitation, carbon tetrachloride, 1,2-dichloroethane, ethyl chloride, 1,1-d
• EDC from EDC Stream 262 market conditions affecting the opportunity for direct sale determine the appropriate amount for either recycle to Reactor 202 or direct sale.
• operation of Process 200 is alternatively conducted so that (a) 1,2-dichloroethane generated in Reactor 202 is purified for sale, (b) 1,2-dichloroethane generated in Reactor 202 is purified for recycle to Reactor 202, and/or (c) 1,2-dichloroethane generated Reactor 202 is purified for cracking in a vinyl furnace.
• the EDC is also, at occasional times, advantageously purchased for use as a chlorine source.
• Cooling Condenser 204 treats Reactor Effluent Stream 232 to provide (a) a raw product (vapor) stream having a first portion of hydrogen chloride and (b) a raw cooled (aqueous) hydrogen chloride stream having the remainder of the hydrogen chloride which exited Reactor 202; the raw product (vapor) stream is Stream 240.
• Phase Separation Subsystem 206 for removal of residual organic compounds from the raw cooled HCl.
• Phase Separation Subsystem 206 is, in alternative embodiments, a decanter, a stripper, or a combination of a decanter and stripper. From Phase Separation Subsystem 206 the removed organic materials (essentially in liquid phase) are conveyed to Lights Column 210 via Stream 242, and the separated raw cooled (essentially aqueous liquid) HCl is conveyed as Stream 236 to Anhydrous HCl Recovery Subsystem 208.
• Anhydrous HCl Recovery Subsystem 208 receives (aqueous) Stream 274 from Vent Oxidation Unit 214 (a thermal oxidation or other oxidation unit useful for vent stream purification to acceptable environmental compositions), and (aqueous) Stream 236 and generates output stream 266 as anhydrous HCl recycle to Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202.
• Stream 268 outputs water from Anhydrous HCl Recovery Subsystem 208 for subsequent use or to waste recovery.
• Anhydrous HCl Recovery Subsystem 208 provides functionality to recover an anhydrous hydrogen chloride stream from the raw cooled hydrogen chloride stream and other aqueous HCl streams of Process 200.
• Anhydrous HCl Recovery Subsystem 208 also recycles the anhydrous hydrogen chloride (vapor) stream via HCl Stream 266 to the reactor 202.
• anhydrous hydrogen chloride (vapor) stream via HCl Stream 266 to the reactor 202.
• Cooling Condenser 204 also outputs Stream 240 (vapor) to Lights Column 210 where a lights stream (vapor Stream 244) containing ethylene is further removed from the reactor effluent product stream. After separation of HCl and lights stream (Stream 244) from the reactor effluent,
• Lights Column 210 forwards Stream 252 for separation of a water product stream (Stream 256), a vinyl chloride monomer product stream (Stream 254), an ethyl chloride stream (Stream 230), a cw-l,2-dichloroethylene and trans- 1,2-dichloroethylene blended stream (Stream 260), a 1,2-dichloroethane stream (Stream 262), and a heavies stream (Stream 264).
• Stream 256 water product stream
• Stream 254 a vinyl chloride monomer product stream
• Stream 230 an ethyl chloride stream
• Stream 230 a cw-l,2-dichloroethylene and trans- 1,2-dichloroethylene blended stream
• Stream 260 1,2-dichloroethane stream
• Stream 264 heavies stream
• Drying Subsystem 216, VCM Purification Column 218, and Heavies Column 220 conveniently depict, therefore, the general separation systems (and, as such, should have the term "column” interpreted as a "virtual column” representing at least one physical column, although, in one contemplated embodiment, each column could be only a single physical column) for separation of Water Stream 256, VCM Product Stream 254, Ethyl Chloride Stream 230, Cisltrans-1,2- dichloroethylene Stream 260, and EDC Stream 262, with Heavies Stream 264 as organic material for destruction in a waste organic burner or use in an appropriate product where the general properties of Heavies Stream 264 are acceptable.
• Drying Subsystem 216 removes water prior to Lights Column 210, with the effluent from Lights Column 210 being forwarded to VCM Purification Column 218.
• VCM Purification Column 218, and Heavies Column 220 are alternatively conducted so that (a) 1,2-dichloroethane is purified for sale, (b) 1,2-dichloroethane is purified for recycle to Reactor 202, and/or (c) 1,2- dichloroethane is purified for cracking in a vinyl furnace.
• Stream 244 is forwarded to Ethylene Oxychlorination Reactor 282 where oxygen is added and an oxychlorination reaction effected with a traditional oxychlorination catalyst to consume the bulk of HCl and generate EDC.
• the output from Ethylene Oxychlorination Reactor 282 is forwarded as Stream 284 to Residual HCl Treatment Unit 286 which scrubs any residual HCl from Stream 284 and outputs essentially an essentially aqueous stream with some HCl as Stream 288 to waste treatment.
• Residual HCl Treatment Unit 286 also outputs stream 290 to EDC Column 292 where Crude EDC Stream 294 is separated and forwarded to Drying Subsystem 216.
• Output from EDC Column 292 (Stream 273) is divided into a first stream portion forwarded directly in Stream 248 to Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 and into a second stream which forwards to C2 Absorption and Stripping Columns 212.
• C2 Absorption and Stripping Columns 212 absorb and strip C2 materials (ethane and ethylene) from the forwarded second stream portion of Stream 244 and insure the recycle of the C2 materials to Reactor 202 via C2 Recycle Stream 246 which, in combination the first stream portion from Stream 244, forms Stream 248.
• C2 Absorption and Stripping Columns 212 also outputs a purge stream to Vent Oxidation Unit 214 which outputs Vent Stream 250 to the atmosphere and also (aqueous) Stream 274 to Anhydrous HCl Recovery Subsystem 208.
• CO (carbon monoxide) composition instrumentation provides a measurement (not shown) for use in a control system's (not shown) determination of an appropriate portion of the remaining lights gas for processing via C2 Absorption and Stripping Columns 212 and Vent Oxidation Unit 214 to generate Vent Stream 250 so that CO does not accumulate to unacceptable levels in the process. Simulated relative stream flows and stream compositions for Ethane to VCM
• Oxydehydro-chlorination Process 200 are appreciated from a consideration of Table 1.
• Table 1 mass unit/time unit data uses laboratory-derived catalyst performance measurements for lanthanum oxychloride at 400 degrees Celsius and essentially ambient pressure; further details on the preferred catalyst are appreciated from a study of "A PROCESS FOR THE CONVERSION OF ETHYLENE TO VINYL CHLORIDE, AND NOVEL CATALYST COMPOSITIONS USEFUL FOR SUCH PROCESS,” referenced hereinabove.
• Table 1 shows some flows as a zero in the context of the simulation generating the data, but such a numeric value is not intended to mean a total absence of flow or absence of need for a stream.
• Table 1 does not show Ethylene Feed Stream 289; in this regard, and divulging an earlier point, when market and operational conditions at a particular moment of manufacture permit, the most preferred mode is for Ethylene Stream 289 to have a flow of zero. However, under certain conditions, Ethylene Stream 289 does contribute an economically beneficial flow.
• Ethane/Ethylene to VCM Oxydehydro-chlorination Dual Reactor System 300 modifies Ethane to VCM Oxydehydro-chlorination Process 200 to interpose Stage 2 Reactor 296 between Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 and Cooling Condenser 204.
• Second stage reactor 296 functions to react hydrogen chloride output to extinction by any means, such as, conventional oxychlorination or reaction of HCl with ethylene to make ethyl chloride.
• Output Lights Stream 244, from Product Split 210, is also divided into a first stream that is forwarded directly in Stream 248 to Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 and into a second stream that forwards to C2 Absorption and Stripping Columns 212.
• C2 Absorption and Stripping Columns 212 absorb and strip C2 materials from the forwarded portion of Stream 244 and ensure the recycle of the C2 materials to Reactor 202 via C2 Recycle Stream 246 and Stream 248.
• C2 Absorption and Stripping Columns 212 also outputs a purge stream to Vent Oxidation Unit 214, which outputs Vent Stream 250 to the atmosphere. Note that there is no need for Anhydrous HCl Recovery Subsystem 208 since essentially no HCl is present in Stage 2 Reactor 296 effluent.
• FIG. 4 shows VCM-Furnace-Augmented Ethane/Ethylene to VCM Oxydehydro- chlorination Dual Reactor System 400 comprising Oxydehydro-chlorination Reactor 202 and Second Stage Reactor 296, with some HCl present in Stage 2 Reactor 296 effluent.
• Quench Column 204 treats Reactor Effluent Stream 232 to essentially completely remove residual HCl by quenching the reactor effluent stream to provide a raw product stream essentially devoid of hydrogen chloride.
• a raw cooled hydrogen chloride stream (Stream 234) is also output from Quench Column 204; Stream 234 is conveyed to Phase Separation Subsystem 206 for removal of organic compounds from the raw cooled HCl.
• a C2 steam (ethane, ethylene, or both ethane and ethylene), HCl, air, and chlorine are introduced into Oxydehydro-chlorination Reactor 502 via lines 503, 504, 505, and 506, respectively.
• the HCl is optionally added via line 504, as needed or if available.
• HCl is also introduced as recycle from HCl Recovery unit 538 via line 508.
• ethylene chloride (EtCl) can be recycled from the VCM purification unit 522 and introduced to the Reactor 502 via line 558.
• Ethylene dichloride (EDC) can also be recycled from the EDC purification unit 524 and introduced to Reactor 502 via line 560.
• the Reactor Effluent Stream 523 is cooled and condensed in unit 510 where the Effluent Sfream 523 is treated to provide (a) a Raw Product (vapor) Stream having a first portion of hydrogen chloride that exits via line 511 and (b) a raw cooled (aqueous) hydrogen chloride stream having the remainder of the hydrogen chloride which exited Reactor 502 and which exits the Cooling Condenser 510 via line 512.
• the raw cooled hydrogen chloride stream is treated in Phase Separation Subsystem 516 to remove residual organic compounds.
• the Phase Separation Subsystem may be an alternative embodiment discussed for Figure 2.
• the residual organic compounds are conveyed to a Product Split 518 via line 517, with the separated raw cooled (essentially aqueous liquid) HCl being sent to the Anhydrous HCl Recovery Subsystem 538.
• Aqueous HCl is introduced to the HCl Recovery Subsystem 538 via line 539.
• Recovered HCl (anhydrous) is recycled to the Reactor 502 via line 508.
• Anhydrous HCl Recovery Subsystem 538 provides functionality to recover an anhydrous hydrogen chloride stream from the raw cooled hydrogen chloride stream and other aqueous HCl streams from the Reactor 502.
• Anhydrous HCl Recovery Subsystem 538 also recycles the anhydrous hydrogen chloride (vapor) stream to Reactor 502.
• the HCl Recovery Subsystem employs a distillation process to recover the anhydrous HCl from the aqueous HCl streams.
• the anhydrous HCl may be recycled.
• Product Split 518 a lights stream is separated which exits via line 515.
• the lights stream contains ethylene and may include other components.
• the balance of the effluent, which contains VCM and may contain other components, is forwarded via line 516 to separation in series to the Drying Subsystem 520, VCM Purification 522, and EDC Purification 524.
• VCM Purification 522 contains VCM and may contain other components
• EDC Purification 524 contains EDC Purification 524.
• Drying Subsystem 520, VCM Purification 522, and EDC Purification 524 conveniently depict, therefore, the general separation systems for separation of Water Stream 556, VCM Product Stream 557, Ethyl Chloride Stream 558, C/s7tr ⁇ ns- 1,2-dichloroethylene Stream 559, and EDC Stream 560, with Heavies Stream 561 as organic material for destruction or use in an appropriate product where the general properties of Heavies Stream 561 are acceptable.
• Drying Subsystem 520 removes water prior to Product Split 518, with the effluent from Product Split 518 being forwarded to VCM Purification 522. The lights stream from Product Split 518, which exited via line 515, is sent to HCl
• HCl Absorption Subsystem 570 an absorber may be used to removed trace amounts of HCl from the gaseous compounds and return the HCl to HCl Recovery Subsystem 538 such as through line 539.
• the HCl-stripped stream exits the HCl Absorption Subsystem via line 571 to Vent Oxidation Unit 580 where any remaining combustible compounds are converted to carbon dioxide (CO 2 ) which may be vented to the atmosphere.
• CO 2 carbon dioxide
• the lights stream contains recoverable quantities of C2 hydrocarbons, such as ethylene or ethane
• appropriate means to recover those hydrocarbons can be interposed between the HCl adsorption unit and the Vent treatment. Collected hydrocarbons would then be returned to unit reactor 502.
• the process produces essentially produces no recoverable quantity of C2 hydrocarbons.
• a relatively small amount of C2 hydrocarbon ethane, ethylene, or mixture thereof
• This may be referred to as a "fuel lean" process.
• the large amount of air produces a very high conversion of C2 hydrocarbon and with the chlorinated organic products being condensable. This results in a one-pass operation with a large amount of venting, with recycle of HCl.
• the rate of addition of the reactant C2 hydrocarbon, air, and chlorine source vary depending on conditions, and are readily determined by one of skill in the art.
• Figure 5a illustrates another embodiment of this invention where air is employed as the source of oxygen for the ethane, ethylene, or ethane/ethylene-to-vinyl chloride process.
• the process scheme depicted in Figure 5a is basically the same as that of Figure 5, except that a RC1 (chlorinated organic compounds) Hydrogenation Reactor 590 is included, where addition of hydrogen effects hydrogenation of the cisl trans- 1 ,2-dichloroethylene from the EDC Purification to form ethylene dichloride, which can be recycled back to the Reactor 502 as a source of chlorine via line 591.
• RC1 chlorinated organic compounds
• EDC stream 560 may optionally be present to assist in balancing the concentration of cis- and trans- 1 ,2-dichloroethylene fed to the Hydrogenation Reactor 590. It may be removed for sale, or may be recycled to Reactor 502. This process scheme has the advantage of producing a stream composed of a single compound, ethylene dichloride, rather than a mixed stream including the cisltrans-1,2- dichloroethylene, the former of which may be recycled back to the Reactor 502.
• Figure 5b illustrates another embodiment of this invention wherein the effluent from the Reactor 502 is fed directly to HCl Absorption Subsystem 570, which serves to separate a gaseous stream 571 that contains vinyl chloride and other components which is sent to the Cooling Condenser 510, and a second stream (the liquid phase) 572 that is sent to the Phase Separation Subsystem 516.
• Phase Separation Subsystem 516 serves to remove residual organic compounds.
• the Phase Separation Subsystem may be an alternative embodiment, as discussed for the previous figures.
• the residual organic compounds are conveyed to the Drying Subsystem 520, which proceeds as discussed above in the discussion of Figure 5.
• the HCl-rich sfream from Phase Separation Subsystem 516 is sent to HCl Recovery Subsystem 538 where HCl is isolated then recycled to Reactor 502 as stream 508.
• Figure 6 illustrates an alternative embodiment of this invention where HCl from the ethane-to-vinyl chloride or ethane/ethylene-to-vinyl chloride process is employed as a "wet" feed to a conventional oxychlorination reactor where a secondary source of oxygen and ethylene are fed to form ethylene dichloride, which is recycled back to the Oxydehydro- chlorination Reactor 602 in EDC line 643 with feed 660 of EDC being added, if desired.
• (i) ethane, (ii) HCl, (iii) oxygen, and (iv) chlorine are introduced into the Oxydehydro-chlorination Reactor 602 via lines 603, 605, and 606, respectively.
• ethylene can be added to the feed to Reactor 602 via recycle Sfream 672.
• HCl is optionally added via line 604.
• ethylene chloride (EtCl) can be recycled from the VCM purification unit 622 and introduced to the Reactor 602 via line 658.
• the Reactor Effluent Stream 623 is cooled and condensed in unit 610 where the Effluent Stream 623 is treated to provide (a) a Raw Product (vapor) Sfream having a first portion of hydrogen chloride that exits via line 611 and (b) a raw cooled (aqueous) hydrogen chloride stream having the remainder of the hydrogen chloride, which exited Reactor 602 and which exits the Cooling Condenser 610 via line 612.
• the raw cooled hydrogen chloride stream is treated in Phase Separation Subsystem
• the Phase Separation Subsystem may be an alternative embodiment as discussed in the previous figures.
• the residual organic compounds are conveyed via line 617 to a Product Split 618, with the separated raw cooled (essentially aqueous liquid) HCl being sent to the Aqueous HCl Recovery Subsystem 638 via line 636.
• Aqueous HCl is introduced to the Aqueous HCl Recovery Subsystem 638 via line 639.
• water and HCl are vaporized as a constant boiling azeotropic mixture.
• the gaseous effluent is referred to as "wet" HCl, with the water basically functioning as a diluent for the HCl.
• the recovered wet HCl (a gaseous mixture of water and HCl) is conveyed to Conventional Oxychlorination Reactor 642 via line 640, with oxygen and ethylene being fed to the Conventional Oxychlorination Reactor 642 via lines 646 and 647, respectively.
• a conventional oxychlorination reactor is one that operates a gas phase reaction using a catalyst such as a copper/alumina catalyst to effect conversion of the oxygen, ethylene, and source of chlorine to ethylene dichloride (EDC), as discussed in the Background of this invention.
• This process thus advantageously recycles HCl produced by the oxydehydro-chlorination reaction that occurs in Reactor 602, using it to make ethylene dichloride (EDC) which, along with EDC 660, can be recycled to the Reactor 602 via line 643, or can be sold.
• EDC ethylene dichloride
• water is removed from the stream, which is denoted by line 644.
• Other waste products may be sent for Vent Treatment, as denoted by line 645.
• a lights stream is separated which exits via line 615.
• the lights stream from Product Split 618 which contains ethylene and may include other components and which exited via line 615, is split and recycled to the Reactor 602 via Stream 672 and to HCl Absorption Subsystem 670.
• the balance of the effluent which contains VCM and may contain other components such as ethyl chloride (EtCl), cfs/trans-l ⁇ -dichloroethylene, and ethylene dichloride, is forwarded via line 619 for separation in series to the Drying Subsystem 620, VCM Purification Column 622, and EDC Purification 624.
• Drying Subsystem 620, VCM Purification 622, and EDC Purification 624 conveniently depict, therefore, the general separation systems for separation of Water Stream 656, VCM Product Stream 657, Ethyl Chloride Stream 658, cisltrans-1,2- dichloroethylene Stream 659, and EDC Stream 660, with Heavies Stream 661 as organic material for destruction in a waste organic burner or use in an appropriate product where the general properties of Heavies Stream 661 are acceptable.
• Drying Subsystem 620 removes water prior to Product Split 618, with the effluent from Product Split 618 being forwarded to VCM Purification Column 622.
• the lights stream from Product Split 618, which contains ethylene and may include other components, that exited via line 615 is split and recycled to the Reactor 602 and to HCl Absorption Subsystem 670.
• an absorber may be used to remove trace amounts of HCl from the gaseous compounds and return the HCl to Aqueous HCl Vaporization Subsystem 638 such as through line 639.
• the HCl-stripped stream exits the HCl Absorption Subsystem 670 via line 671 to C2 Absorption and Stripper Subsystem.
• C2 Absorption and Stripping Columns 675 absorb and strip C2 materials (ethane and ethylene), then recycles the C2 materials to Reactor 602 via C2 Recycle Stream 676, which in combination with the first stream portion from line 615, forms Stream 672.
• C2 Abso ⁇ tion and Stripping Columns 675 also conveys a purge stream to Vent Treatment Unit 680 via line 681 where the vent is treated prior to release to the environment. This unit may provide means to convert any remaining combustible compounds to carbon dioxide (CO 2 ), which may be vented to the atmosphere.
• CO 2 carbon dioxide
• CO (carbon monoxide) composition instrumentation may provide a measurement (not shown) for use in a control system's (not shown) determination of an appropriate portion of the remaining lights gas for processing via C2 Abso ⁇ tion and Stripping Columns 675 and Vent Oxidation Unit 680 to generate Vent Stream 682, so that CO does not accumulate to unacceptable levels in the process.
• the scheme of Figure 6 has the advantage of separating and catalytically reacting HCl for conversion to EDC.
• the EDC can be recycled to the oxydehydro-chlorination reactor or may be used or otherwise sold.
• a hydrogen chloride recovery unit is eliminated from the scheme, which beneficially eliminates long-term corrosion problems.
• FIG. 6a illustrates an alternative scheme to the embodiment of Figure 6, wherein a hydrogenation step is included.
• the scheme is the same as in Figure 6 except that all or a portion of the cis/trans-l,2-dichloroethylene recovered from EDC Column 624 is fed via line 625 to Hydrogenation 626 (a conventional hydrogenation unit) where hydrogen is fed via line 627 and wherein the cts/trans-l,2-dichloroethylene is converted to EDC.
• the EDC effluent exits via line 628.
• This EDC can be recycled to the reactor via, for instance, via line 628 to line 643 into Reactor 602.
• This configuration provides the advantage of alternatively forming EDC from the /trans-l,2-dichloroethylene, which may not be a desirable co-product of the reaction scheme.
• Figure 6b illustrates another alternative scheme to the embodiment of Figure 6c, wherein a C2 abso ⁇ tion and stripper block and recycle is omitted.
• air is fed to Reactor via line 605.
• the process is operated in a fashion similar to the embodiment of the invention depicted in Figure 5 such that "fuel lean" conditions are implemented with the ethane, ethylene, or both ethane and ethylene being reacted to extinction in a single-pass operation.
• the process thus is designed to treat a large volume of gas to the vent 680. Since ethane is essentially fully converted, there is no recycle of lights unlike the scheme in Figure 6, but similar to the scheme of Figure 5. It should be appreciated that effluent from HCl Abso ⁇ tion Subsystem is conveyed directly via line 671 to the Vent Treatment Unit 680, with vent stream exiting via line 682.
• Figure 6c illustrates an alternative scheme to the embodiment of Figure 6b, wherein the C2 abso ⁇ tion and stripper block and recycle is again omitted but a hydrogenation unit 626 is included and the process is run using air instead of oxygen.
• This configuration has the advantage that HCl is recovered, and the cw/trans-l,2-dichloroethylene may be converted to EDC and recycled to the Reactor 602 or sold.
• This scheme employs conventional oxychlorination to assist in recycling the HCl by reacting it with ethylene and oxygen in the presence of an oxychlorination catalyst to form EDC.
• Figure 7 illustrates another alternative scheme to the embodiment of Figure 6, wherein aqueous HCl (the HCl is formed in the primary reactor) serves as a reaction medium and reactant used to form ethyl chloride, ethylene dichloride, or mixtures of the two. Ethyl chloride and ethylene dichloride sold or can be fed to the primary Reactor 602 to provide a source of chlorine.
• aqueous HCl the HCl is formed in the primary reactor
• Ethyl chloride and ethylene dichloride sold or can be fed to the primary Reactor 602 to provide a source of chlorine.
• Figure 7 is the same scheme as Figure 6, except that the raw cooled hydrogen chloride stream is treated in Phase Separation Subsystem 616 to remove residual organic compounds, with the residual organic compounds being conveyed via line 617 to a Product Split 618, and with the separated raw cooled (essentially aqueous liquid) HCl being sent with make up HCl to Reactor 690 (Kellogg process).
• the Reactor 690 may be operated in accordance with U.S. Patent 3,214,482 and GB 1,063,284. Ethylene and oxygen are fed to the Reactor 690 via feed streams 647 and 646, respectively, which reactor may employ a catalyst composition comprising an aqueous solution of active metal halide and either a solubilizing agent or promoter.
• Active metals include, but are not limited to copper, as described in GB 1,063,284, and iron, as described in US 3,214,482.
• the reaction of ethylene, oxygen, and HCl is typically run at a temperature of from about 100°C to about 350°C, more typically from about 120°C to about 180°C, under pressure sufficient to maintain the aqueous phase, using standard equipment and methodologies.
• the ethylene, oxygen, and HCl react to form ethyl chloride (EtCl), EDC, and water.
• EtCl ethyl chloride
• the EDC and EtCl are separated from the water via phase separation.
• the EDC and EtCl are then fed to the Steam Stripper 694, with residual EDC and EtCl in the aqueous phase that is stripped from the aqueous phase exiting via line 695 to Vaporization Unit 692.
• the Vaporization Unit 692 is typically a heat exchange process that vaporizes the EDC and EtCl streams, with the resulting effluent being recycled to Reactor 602 via line 696.
• the remainder of the process flow depicted in Figure 7 is described above in the description of Figure 6.
• the process design of Figure 7 has the advantage of including an alternative reactor for use in recovering HCl from the process in the form of EDC and/ or EtCl, which can be recycled to the primary Reactor 602, or used, or sold directly.
• Figure 7a illustrates an alternative scheme to the embodiment of Figure 7 wherein a hydrogenation step is included.
• Figure 7a is identical to Figure 7, except that a Hydrogenation Unit 626 is included.
• a discussion of Hydrogenation Unit 626 is described in the section above concerning Figure 6a.
• An advantage to this process flow scheme is that the cw/trans-l,2-dichloroethylene is converted to EDC, which maybe used or sold or which may be recycled to the Reactor 602 to thereby improve the overall yield of vinyl chloride monomer.
• Figure 7b illustrates an alternative scheme to the embodiment of Figure 7 wherein air is employed as the source of oxygen for the primary reactor.
• This process flow scheme is the same as that of Figure 7, with the exception that the C2 hydrocarbon abso ⁇ tion and stripper 675 and C2 hydrocarbon recycle streams 672/676 are absent.
• the scheme is operated with the ethane, ethylene, or both ethane and ethylene being reacted to extinction whereby there is no recycle of lights to Reactor 602 via line 672 as in Figure 7a.
• air serves as the preferred oxidant.
• Figure 7c illustrates another alternative scheme for the embodiment of Figure 7b.
• Figure 7c is the same as Figure 7b, except that a Hydrogenation Unit 626 is included, which converts a flow of /trans-l,2-dichloroethylene to EDC.
• the EDC can be sold or recycled as a chlorine source to Reactor 602.
• Table 2 presents further detail in components identified in the Figures. Certain unit features may be recognizably similar from Figure to Figure, although the numbers for the specific unit feature may be different on different figures.
• a porous, refractory composition comprising lanthanum was prepared.
• a solution of LaCl in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (obtained from J.T. Baker Chemical Company) in 8 parts of deionized water.
• Dropwise addition with stirring of ammonium hydroxide (obtained from Fisher Scientific, certified ACS specification) to monral pH (by universal test paper) caused the formation of a gel.
• the mixture was centrifuged, and the solution decanted away from the solid. Approximately 150 ml of deionized water was added and the gel was stirred vigorously to disperse the solid.
• the resulting solution was centrifuged and the solution decanted away. This washing step was repeated two additional times. The collected, washed gel was dried for two hours at 120 degrees Celsius and subsequently calcined at 550 deg. C. for four hours in air. The resulting solid was crushed and sieved to yield particles suitable for additional testing. This procedure produced a solid matching the X-ray powder diffraction pattern of LaOCl.
• the particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, O 2 and inert gas (He and Ar mixture) could be fed to the reactor.
• the function of the argon was as an internal standard for the analysis of the reactor feed and effluent by gas chromatography. Space time is calculated as the volume of catalyst divided by the flow rate at standard conditions. Feed rates are molar ratios.
• the reactor system was immediately fed an ethane-containing stream with the stoichiometry of one ethane, one HCl and one oxygen. This provides balanced stoichiometry for the production of VCM from ethylene.
• Table 3 below sets forth the results of reactor testing using this composition.
• Column 1 of Table 3 shows the high selectivity to vinyl chloride when the catalyst system is fed ethylene under oxidizing conditions in the presence of HCl.
• the composition contains helium in order to mimic a reactor operated with air as the oxidant gas.
• Column 2 of Table 3 shows the high selectivity to vinyl chloride when the catalyst system is fed ethylene under oxidizing conditions in the presence of HCl.
• the composition is now fuel rich to avoid limitations imposed by flammability and contains no helium.
• ethylene is oxidatively converted to vinyl chloride using a variety of chlorine sources.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Avocado Research Chemicals Ltd.) in 6.6 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination at 550 deg C for four hours in air. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, HCl, oxygen, 1 ,2-dichloroethane, carbon tetrachloride and helium could be fed to the reactor.
• Space time is calculated as the volume of catalyst divided by the flow rate at standard temperature and pressure. Feed rates are molar ratios.
• the composition was heated to 400 deg C and treated with a 1:1 :3 HCl:O 2 :He mixture for 2 hours prior to the start of operation.
• the composition formed was operated to produce vinyl chloride by feeding ethylene, a chlorine source and oxygen at 400 deg C.
• the following table shows data obtained between 82 and 163 hours on sfream using different chlorine sources.
• Chlorine is supplied as HCl, carbon tefrachloride and 1,2-dichloroethane.
• VCM signifies vinyl chloride.
• Space time is calculated as the volume of catalyst divided by the flow rate at standard temperature and pressure.
• the reactors are operated with the reactor exit at ambient pressure. Both ethylene and 1 ,2-dichloroethane are termed to be C 2 species.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Avocado Research Chemicals Ltd.) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel and yielded a final pH of 8.85. The mixture was filtered to collect the solid. The collected material was calcined in air at 550 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• Table 5 shows data wherein the reactor feeds were adjusted such that the flux of ethylene (moles/minute) entering the reactor and the flux of ethylene exiting the reactor were substantially equal.
• Reactor feeds were similarly adjusted such that the fluxes of HCl entering and exiting the reactor were substantially equal.
• Oxygen conversion was set at slightly less than complete conversion to enable the monitoring of catalyst activity. Operated in this manner, the consumed feeds are ethane, oxygen, and chlorine. Both ethylene and HCl give the appearance of neither being created nor consumed. Space time is calculated as the volume of catalyst divided by the flow rate at standard temperature and pressure.
• the example further illustrates the use of chlorine gas as a chlorine source in the production of vinyl chloride.
• VCM signifies vinyl chloride.
• C 2 H4CI 2 is solely 1,2- dichloroethane.
• CO x is the combination of CO and CO 2 .
• Example 4 through Example 11 illustrate the preparation of numerous rare earth compositions, each containing only one rare earth material. Data illustrating the performance of these compositions are set forth in Table 6. Example 4
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Aldrich Chemical Company) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The gel was re-suspended in 6.66 parts of deionized water. Centrifiiging allowed collection of the gel. The collected gel was dried at 120 deg C prior to calcination at 550 deg C for four hours in air. The resulting solid was crushed and sieved.
• the sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• Powder x-ray diffraction shows the material to be LaOCl.
• the BET surface area is measured to be 42.06 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of NdCl 3 in water was prepared by dissolving one part of commercially available hydrated neodymium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• Powder x-ray diffraction shows the material to be NdOCl.
• the BET surface area is measured to be 22.71 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of PrCl 3 in water was prepared by dissolving one part of commercially available hydrated praseodymium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• Powder x-ray diffraction shows the material to be PrOCl.
• the BET surface area is measured to be 21.37 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of SmCl 3 in water was prepared by dissolving one part of commercially available hydrated samarium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination at 500 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• Powder x-ray diffraction shows the material to be SmOCl.
• the BET surface area is measured to be 30.09 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of HoCl 3 in water was prepared by dissolving one part of commercially available hydrated holmium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination at 500 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 20.92 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of ErCl 3 in water was prepared by dissolving one part of commercially available hydrated erbium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination at 500 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 19.80 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of YbCl 3 in water was prepared by dissolving one part of commercially available hydrated ytterbium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination at 500 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 2.23 m 2 /g.
• the specific performance data for this example are set forth below in Table 6.
• a solution of YC1 3 in water was prepared by dissolving one part of commercially available hydrated yttrium chloride (Alfa Aesar) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was filtered to collect the solid. The collected gel was dried at 120 deg C prior to calcination at 500 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 29.72 m 2 /g.
• the specific performance data for this example are set forth below in Table 6. Table 6: Rare Earth Oxychloride Compositions Operated to Produce Vinyl Chloride
• Example 12 shows the utility of bulk rare earth containing compositions for the conversion of ethylene containing streams to vinyl chloride.
• Example 12 through Example 16 show the utility of bulk rare earth containing compositions for the conversion of ethylene containing streams to vinyl chloride.
• Example 12 through Example 16 illustrate the preparation of numerous rare earth compositions, each containing a mixture of rare earth materials. Data illustrating the performance of these data are set forth in Table 7.
• Example 12 A solution of LaCl 3 and NdCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.67 parts of commercially available hydrated neodymium chloride (Alfa Aesar) in 13.33 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The final pH was measured as 8.96. The mixture was centrifuged to collect the solid.
• Example 13 The specific performance data for this example are set forth below in Table 7.
• Example 13 The specific performance data for this example are set forth below in Table 7.
• a solution of LaCl 3 and SmCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.67 parts of commercially available hydrated samarium chloride (Alfa Aesar) in 13.33 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The final pH was measured as 8.96. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The collected gel was dried at 80 deg C prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved.
• the sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 21.01 m 2 /g.
• the specific performance data for this example are set forth below in Table 7.
• a solution of LaCl 3 and YC1 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.52 parts of commercially available hydrated yttrium chloride (Alfa Aesar) in 13.33 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The final pH was measured as 8.96. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The collected gel was dried at 80 deg C prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor. The reactor was configured such that ethylene, ethane, HCl, oxygen, and inert
• Example 15 (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 20.98 m 2 /g.
• the specific performance data for this example are set forth below in Table 7.
• a solution of LaCl 3 and H0CI 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and one part of commercially available hydrated holmium chloride (Alfa Aesar) in 13.33 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The final pH was measured as 8.64. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The collected gel was dried at 80 deg C prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved.
• the sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the BET surface area is measured to be 19.68 m /g.
• the specific performance data for this example are set forth below in Table 7.
• a solution of LaCl 3 and HoCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) and 0.75 parts of commercially available hydrated ytterbium chloride (Alfa Aesar) in 13.33 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The final pH was measured as 9.10. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The collected gel was dried at 80 deg C prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor. The reactor was configured such that ethylene, ethane, HCl, oxygen, and inert
• Example 17 through Example 24 are compositions containing rare earth materials with other additives present.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Aldrich Chemical
• a lanthanum containing composition prepared using the method of Example 5 was ground with a mortar and pestle to form a fine powder.
• One part of the ground powder was combined with 0.43 parts BaCl 2 powder and further ground using a mortar and pestle to form an intimate mixture.
• the lanthanum and barium containing mixture was pressed to form chunks.
• the chunks were calcined at 800 deg C in air for 4 hours.
• the resulting material was placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the specific performance data for this example are set forth below in Table 8.
• Dried Grace Davison Grade 57 silica was dried at 120 deg C for 2 hours.
• a saturated solution of LaCl 3 in water was formed using commercially available hydrated lanthanum chloride.
• the dried silica was impregnated to the point of incipient wetness with the LaCl 3 solution.
• the impregnated silica was allowed to air dry for 2 days at ambient temperature. It was further dried at 120 deg C for 1 hour.
• the resulting material was placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the specific performance data for this example are set forth below in Table 8.
• Example 20 A solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 6.67 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The gel was re-suspended in 12.5 parts of acetone (Fisher Scientific), centrifuged, and the liquid decanted away and discarded. The acetone washing step was repeated 4 additional times using 8.3 parts acetone.
• the gel was re-suspended in 12.5 parts acetone and 1.15 parts of hexamethyldisilizane (purchased from Aldrich Chemical Company) was added and the solution was stirred for one hour. The mixture was centrifuged to collect the gel. The collected gel was allowed to air dry at ambient temperature prior to calcination in air at 550 deg C for four hours. The resulting solid was crushed and sieved. The sieved particles were placed in a pure nickel (alloy 200) reactor. The reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor. The BET surface area is measured to be 58.82 m 2 /g.
• Example 21 A solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0.043 parts of commercially available HfCl 4 (purchased from Acros Organics) in 10 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The collected gel was dried at 80 deg C overnight prior to calcination at 550 deg C for 4 hours.
• the specific performance data for this example are set forth below in Table 8.
• Example 22 A solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0.086 parts of commercially available HfCl 4 (purchased from Acros Organics) in 10 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded The collected gel was dried at 80 deg C overnight prior to calcination at 550 deg C for 4 hours. The specific performance data for this example are set forth below in Table 8.
• Example 23 A solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0.086 parts of commercially available HfCl 4 (purchased from Acros Organics) in 10 parts of deionized water. Rapid addition
• a solution of LaCl in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (Alfa Aesar) and 0.043 parts of commercially available ZrOCl (purchased from Acros Organics) in 10 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The gel was re-suspended in 6.67 parts deionized water and subsequently centrifuged. The solution was decanted away and discarded. The collected gel was calcined at 550 deg C for 4 hours. The specific performance data for this example are set forth below in Table 8.
• a solution of LaCl 3 in water was prepared by dissolving commercially available hydrated lanthanum chloride in deionized water to yield a 2.16 M solution.
• Commercially produced zirconium oxide obtained from Engelhard
• One part of the zirconium oxide was impregnated with 0.4 parts of the LaCl 3 solution.
• the sample was dried in air at room temperature and then calcined in air at 550 deg C for 4 hours.
• the resulting solid was crushed and sieved.
• the sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethylene, ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the specific performance data for this example are set forth below in Table 8.
• Example 25 shows the production of vinyl chloride from ethylene containing streams using lanthanum-based catalysts that contain other elements or are supported.
• Example 25 through Example 30 show some of the modifications possible to alter the preparation of useful rare earth compositions.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 10 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. A saturated solution of 0.61 parts benzyltriethylammonium chloride (purchased from Aldrich Chemical Company) in deionized water was prepared. The solution was added to the gel and stirred. The collected gel was calcined at 550 deg C for 4 hours.
• Table 9 This example illustrates the use of added ammonium salts to alter the preparation of rare earth compositions.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 10 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. One part glacial acetic acid was added to the gel and the gel re-dissolved. Addition of the solution to 26 parts of acetone caused the formation of a precipitate. The solution was decanted away and the solid was calcined at 550 deg C for 4 hours.
• Table 9 This example shows the preparation of useful lanthanum compositions by the decomposition of carboxylic acid adducts of chlorine containing rare earth compounds.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Spectrum Quality Products) in 10 parts of deionized water. Rapid addition with stirring of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. The collected gel was re-suspended in 3.33 parts of deionized water. Subsequent addition of 0.0311 parts of phosphoric acid reagent (purchased from Fisher Scientific) produced no visible change in the suspended gel. The mixture was again centrifuged and the solution decanted away from the phosphorus containing gel.
• the collected gel was calcined for at 550 deg C for 4 hours.
• the calcined solid had a BET surface area of 33.05 m 2 /g.
• the specific performance data for this example are set forth below in Table 9. This example shows the preparation of a rare earth composition also containing phosphorus, as phosphate.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Acros Organics) in 6.66 parts of deionized water.
• a solution was formed by mixing 0.95 parts of commercially available DABCO, or l,4-diazabicyclo[2.2.2]octane, (purchased from ICN Pharmaceuticals) dissolved in 2.6 parts of deionized water. Rapid mixing with stirring of the two solutions caused the formation of a gel. The mixture was centrifuged to collect the solid. The collected gel was re-suspended in 6.67 parts of deionized water. The mixture was again centrifuged and the solution decanted away from the gel.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Acros Organics) in 10 parts of deionized water. To this solution, 2.9 parts of commercially available teframethyl ammonium hydroxide (purchased from Aldrich Chemical Company) was added rapidly and with stirring, causing the formation of a gel. The mixture was centrifuged and the solution decanted away. The collected gel was resuspended in 6.67 parts of deionized water. The mixture was again centrifuged and the solution decanted away from the gel. The collected gel was calcined for 4 hours at 550 deg C.
• the calcined solid had a BET surface area of 80.35 m 2 /g.
• the specific performance data for this example are set forth below in Table 9. This example shows the utility of an alkyl ammonium hydroxide for formation of a useful rare earth composition.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (purchased from Avocado Research Chemicals Ltd.) in 6.67 parts of deionized water. To this solution, 1.63 parts of commercially available 5 N NaOH solution (Fisher Scientific) was added rapidly and with stirring, causing the formation of a gel. The mixture was centrifuged and the solution decanted away. The collected gel was calcined for 4 hours at 550 deg C. The calcined solid had a BET surface area of 16.23 m 2 /g.
• Table 9 This example shows the utility of non-nitrogen containing bases for the formation of catalytically interesting materials. Although potentially functional the tested materials appear to be inferior to those produced using nitrogen containing bases.
• a solution of LaCl 3 in water was prepared by dissolving one part of commercially available hydrated lanthanum chloride (96% minimum purity; supplied by AMR) in 6.67 parts of deionized water. Rapid addition with stirring of 1.33 parts of 6 M ammonium hydroxide in water (diluted certified ACS reagent, obtained from Fisher Scientific) caused the formation of a gel. The mixture was centrifuged to collect the solid. Solution was decanted away from the gel and discarded. The gel was re-suspended in 6.67 parts of deionized water. Centrifuging allowed collection of the gel. The collected gel was dried at 80 deg C prior to calcination at 550 deg C for four hours in air. The resulting solid was crushed and sieved.
• Powder x-ray diffraction shows the material to be LaOCl.
• the BET surface area is measured to be 36.0006 m /g.
• the sieved particles were placed in a pure nickel (alloy 200) reactor.
• the reactor was configured such that ethane, HCl, oxygen, and inert (helium and argon mixture) could be fed to the reactor.
• the reactor was operated at 400 deg C at near ambient pressure.
• the feeds were adjusted to give an ethane: HCl : oxygen: inert ratio of 1 : 2: 6.7: 24.5. Feed rates were adjusted to give >99.6% ethane conversion.

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