Connect public, paid and private patent data with Google Patents Public Datasets

Integrated process for synthesizing alcohols, ethers, and olefins from alkanes

Download PDF

Info

Publication number
US20020198416A1
US20020198416A1 US10054004 US5400402A US2002198416A1 US 20020198416 A1 US20020198416 A1 US 20020198416A1 US 10054004 US10054004 US 10054004 US 5400402 A US5400402 A US 5400402A US 2002198416 A1 US2002198416 A1 US 2002198416A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
metal
reaction
bromine
ch
methane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10054004
Other versions
US6486368B1 (en )
Inventor
Xiao Zhou
Ivan Lorkovic
Jeffrey Sherman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
REACTION 35 LLC
University of California
Original Assignee
University of California
GRT Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/24Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
    • C07D301/26Y being hydrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10General improvement of production processes causing greenhouse gases [GHG] emissions
    • Y02P20/12Energy input
    • Y02P20/121Energy efficiency measures, e.g. energy management
    • Y02P20/125Process integration

Abstract

Alcohols, ethers, and olefins are manufactured from alkanes by mixing an alkane and bromine in a reactor to form alkyl bromide and hydrogen bromide. The alkyl bromide only or the alkyl bromide and the hydrogen bromide are directed into contact with metal oxide to form an alcohol and/or an ether, or an olefin and metal bromide. The metal bromide is oxidized to form original metal oxide and bromine, both of which are recycled.

Description

    CROSS REFERENCE TO RELATED APPLICATION
  • [0001]
    This is a continuation-in-part application under 37 C.F.R. §1.63 of application Ser. No. 09/951,739 filed Sep. 11, 2001, currently pending, which is a continuation-in-part application of application Ser. No. 09/886,078 filed Jun. 20, 2001, currently pending.
  • TECHNICAL FIELD
  • [0002]
    This invention relates generally to the synthesis of alcohols, ethers, and olefins from alkanes, and more particularly to a method of and apparatus for manufacturing methanol and dimethyl ether from methane; for manufacturing ethanol, diethyl ether, and ethyl acetate from ethane; and for converting alkanes, which have more than two carbon atoms in their molecular structure, to their corresponding olefins.
  • BACKGROUND OF THE INVENTION
  • [0003]
    Methane has previously been converted to methanol by the halogenation of methane followed by hydrolysis of the methyl halide to form methanol. For example, gaseous chlorine has been used to chlorinate methane to form chlorinated methane, principally methyl chloride, together with other chlorides, i.e., dichloromethane, trichloromethane and carbon tetrachloride. Alternatively, methane has been subjected to oxychlorination with oxygen and hydrochloric acid to form the foregoing compounds. The chlorinated methanes produced are hydrolyzed in the vapor phase to produce methanol, formaldehyde, formic acid and by-products, including carbon dioxide and hydrochloric acid, depending on the chlorination selectivity. Hydrochloric acid is produced or used in the halogenation of methane by either method and must be recovered, dehydrated by azeotropic distillation and recycled. Corrosion and other problems involved with the handling of chlorine and hydrochloric acid are substantial.
  • [0004]
    U.S. Pat. No. 3,172,915 granted to Borkowski, et al. is directed to a process for converting methane to methanol. Borkowski discloses the chlorination of methane using ferric chloride at high temperatures to produce chloromethanes and hydrogen chloride. The process requires temperatures in the range of 220-800° C., more preferably 250-450° C., and long residence times, e.g., more than one hour. Further, the process is hindered by the production of a mixture of chlorination products, e.g., chloromethane, dichloromethane, trichloromethane and carbon tetrachloride, which must be separated before hydrolysis to methanol. Other disadvantages result from the energy required to dry the ferric chloride and from the corrosion and handling problems inherent with hydrochloric acid.
  • [0005]
    U.S. Pat. No. 5,243,098 granted to Miller discloses another method for converting methane to methanol. In the Miller process, the reaction of methane with cupric chloride produces chloromethane and hydrochloric acid. These intermediates are then reacted with steam and a catalyst containing magnesium oxide to produce methanol and magnesium chloride. Magnesium oxide is regenerated by treatment of the magnesium chloride by-product with air or oxygen. Cupric chloride is regenerated by treatment of the cuprous chloride by-product with air and hydrochloric acid. While these reactions proceed at favorable rates, attrition of the solid reactants, i.e., cupric and magnesium oxide, is significant. Special filters and processes are required to recover and regenerate the reactants in the required particle size. Miller also suggests cupric bromide and magnesium zeolite as alternative reactants. Because of the attrition of the reactants, difficulties associated with the handling of solids, and the special filters and processes required to regenerate the reactants, the Miller process has proved unsatisfactory. U.S. Pat. No. 5,334,777, also granted to Miller, discloses a nearly identical process for converting ethene to ethylene glycol.
  • [0006]
    U.S. Pat. No. 5,998,679 granted to Jorge Miller, discloses a process for converting alkanes and alkenes to the corresponding lower alkanols and diols. In the method of the invention, a gaseous halogen (bromine) is produced by decomposing a metal halide in a liquid having a melting point below and a boiling point above the decomposition temperature of the metal halide. The preferred liquid is molten hydrated ferric chloride maintained at a temperature between about 37-2800° C. The lower alkane or alkene is halogenated in a gas phase reaction with the halogen. The resulting alkyl halide or alkyl dihalide is contacted with a metal hydroxide, preferably an aqueous solution of ferric hydroxide, to regenerate the metal halide and produce the corresponding lower alkanol or diol. Problems with this process include low monohalogenation selectivity, and corrosiveness of the hydrated ferric halides, which may present a containment problem if the process is run at 280° C., where high pressure steam is required to maintain ferric halide hydration. Finally, the process produces a great deal of water and HCl or HBr, all of which are difficult to separate on a large scale from the desired product methanol.
  • [0007]
    Published international patent application WO 00/07718, naming Giuseppe Bellussi, Carlo Perego, and Laura Zanibelli as inventors, discloses a method for directly converting methane and oxygen to methanol over a metal halide/metal oxide catalyst. This is not a catalyst in the true sense, however, because the reaction involves transfer of halide from a metal halide via reaction with methane to a different metal oxide producing the metal halide and methanol downstream. Eventually the halide is leached and the catalyst loses activity.
  • [0008]
    Olah et al. (George A. Olah, et al. J. Am. Chem. Soc. 1985, 107, 7097-7105) discloses a method for converting methane to methanol via methyl halides (CH3Br and CH3Cl), which are then hydrolyzed to prepare methanol. In the process, CH3Br and CH3Cl are hydrolyzed over catalysts with excess steam generating a methanol, water, and a HCl or HBr mixture. The separation of methanol (about 2% by mole) from HCl or HBr and water on an industry scale (2000 tons per day) requires an enormous amount of energy and generates a great deal of aqueous HCl or HBr waste. Aqueous HCl and HBr are very corrosive as well.
  • SUMMARY OF THE INVENTION
  • [0009]
    The present invention comprises a process wherein bromine or a bromine-containing compound is used as an intermediate to convert alkanes to alcohols, ethers, or olefins by reaction with oxygen (or air). While the process can be used to convert a variety of alkanes, including methane, ethane, propane, butane, isobutane, pentanes, hexanes, cyclohexane etc. to their respective alcohols, ethers, or olefins, the conversion of methane to methanol and dimethyl ether is illustrative.
  • [0010]
    Methane reacts with bromine over a catalyst to form CH3Br and HBr. CH3Br and HBr react with a metal oxide to form a variable mixture of dimethyl ether (DME), water and methanol, and the metal bromide. The metal oxide and molecular bromine are regenerated by reaction of the metal bromide with air and/or oxygen. The regenerated bromine is recycled to react with methane while the regenerated metal oxide is used to convert more methyl bromide and HBr to methanol and DME, completing the reaction cycle.
  • [0011]
    The process can be easily carried out in a riser reactor. Compared to the current industrial two step process, in which methane and steam are first converted to CO and H2 at 800° C. followed by conversion to methanol over a Zn—Cu—Al—O catalyst at approximately 70-150 atmospheres, the process of the present invention operates at roughly atmospheric pressure and relatively low temperatures, thereby providing a safe and efficient process for methanol production.
  • [0012]
    The present invention operates with solid/gas mixtures at atmospheric pressure. In the process, the hydrogen halide is gaseous, and therefore not as corrosive as when aqueous at high temperatures. The reaction of Br2 with an alkane can reach more than 90% selectivity and high conversion to alkane-monobromide. The main side products, alkane dibromides such as CH2Br2, can be converted back to the monobromides by reaction with an alkane over another catalyst. Very few by-products are produced.
  • [0013]
    During operation, most of the Br atoms are trapped in the solid state, making the system less corrosive. Another advantage is that in the process, DME and alcohol (CH3OH) are not produced as a mixture with excess water. By controlling reaction conditions, almost pure DME and/or methanol is obtained directly so that it is not necessary to separate CH3OH from water. Finally, in the present process, methane and oxygen do not come into direct contact, resulting in improved safety.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0014]
    A more complete understanding of the present invention may be had by reference to the following Detailed Description when taken in connection with the accompanying Drawings, wherein:
  • [0015]
    [0015]FIG. 1 is a schematic illustration of a method of and apparatus for synthesizing alcohols and/or ethers from alkanes comprising a first version of the first embodiment of the invention;
  • [0016]
    [0016]FIG. 2 is a schematic illustration of a method of and apparatus for synthesizing alcohols and/or ethers from alkanes comprising a second version of the first embodiment of the invention; and
  • [0017]
    [0017]FIG. 3 is a schematic illustration of a method of and apparatus for synthesizing olefins from alkanes comprising a second embodiment of the invention.
  • DETAILED DESCRIPTION
  • [0018]
    Alkanes (methane, ethane, propane, butane, isobutane, pentanes, hexanes, cyclohexane etc.) react with molecular bromine over a catalyst composed of all possible metal compounds and mixtures thereof to form alkylbromides. For CH4 (although the process may be applied to higher alkanes as well), the process of the present invention can convert more than 50% CH4 to CH3Br and HBr, with selectivity higher than 90%. Most of the by-product is CH2Br2 plus 2 HBr, trace amounts of CHBr3 and CBr4, which can be catalytically reconverted to CH3Br by reacting CH2Br2, CHBr3, and CBr4 with CH4.
  • [0019]
    Referring to the Drawings, and particularly to FIG. 1, a method and apparatus 10 for synthesizing alcohols and ethers from alkanes using bromine comprising a first version of the first embodiment of the invention is schematically illustrated. In the operation of the method and apparatus 10, bromine is received from a suitable source through a line 12 and is directed to a bromine storage container 14. For example, bromine is easily manufactured from bromide, which is readily available from sea water.
  • [0020]
    As is well known, bromine is a liquid at room temperature. Liquid bromine from the storage container 14 is directed through a line 16 to a bromine vaporizer 18 wherein the bromine is converted from the liquid phase to the gas phase. From the vaporizer 18 the gaseous bromine is directed through a line 20 to a reactor 22.
  • [0021]
    Methane from a suitable source is directed to the reactor 22 through a line 24. Within the reactor 22 the methane and the gaseous bromine are mixed together over an appropriate solid catalyst, and the temperature of the mixture is raised to between about 20° C. and about 600° C., thereby converting the methane and the bromine to methyl bromide (CH3Br) and hydrogen bromide (HBr).
  • [0022]
    From the reactor 22, the CH3Br, the HBr, any unreacted methane and by-products CH2Br2, CHBr3, and CBr4 are directed to a condenser 34 through a line 30. The by products CH2Br2, CHBr3, and CBr4 are in the liquid state and are sent through a line 32 to a converter 28 to react with methane. In the converter 28 methane reacts with the by products CH2Br2, CHBr3, and CBr4 to form CH3Br. The newly formed CH3Br and unreacted CH2Br2, CHBr3, CBr4 and methane are sent to the condenser 34 through a line 26 and the line 30.
  • [0023]
    From the condenser 34 gas phase methane, HBr, and CH3Br are sent to a converter 52 through a line 36. In the converter 52 HBr and CH3Br react with metal oxide to form CH3OCH3, CH3OH, and H2O, which are sent to a separator 44 along with unreacted methane and CH3Br through a line 46.
  • [0024]
    In the separator 44 dimethyl either and methanol/water are separated as products and recovered at outlets 40 and 48, respectively. The methanol is subsequently removed from the water by distillation. CH3Br is sent back to the converter 52 through the line 38 and the line 36. Methane from the separator 44 is sent back to the bromination reactor 22 through the line 42 and the line 24.
  • [0025]
    In the converter 52, the original metal oxide is converted to metal bromide and must be regenerated. The metal bromide from the converter 52 is sent to a converter 58 through a line 54 to react with oxygen received from a source 74 through a line 72 to regenerate bromine and metal oxide. The regenerated metal oxide is sent back to the converter 52 through a line 56, while the bromine and unreacted oxygen are sent to a condenser 62 through a line 60, after which they are separated in a separator 68. The liquid bromine is sent to the storage container 14, while the oxygen is sent to the converter 58 through a blower 66 and a line 70.
  • [0026]
    Referring to FIG. 2, there is shown a method of and apparatus 100 for synthesizing alcohols and ethers from alkanes comprising a second version of the first embodiment of the invention. Methane and bromine are directed to a heat zone and vaporizer 102 where the bromine is converted from a liquid to a gas and mixed with methane at a temperature above the atmospheric boiling point of bromine. The gas mixture is passed into a bromination reactor 104 containing an appropriate solid catalyst. After the reaction, the mixture is directed to condenser a 106. The liquid phase contains by products CH2Br, CHBr3, and CBr4, while the gas phase contains bromomethane, HBr, and unreacted methane.
  • [0027]
    The by products CH2Br2, CHBr3, and CBr4 are sent to a converter 108 where they react with methane to form bromomethane. After the reaction the mixture is sent to the condenser 106.
  • [0028]
    The conversion of the by products CH2Br2, CHBr3, and CBr4 to bromomethane in the converter 108 is facilitated by the use of an electrophilic catalyst such as AlBr3, SbF5, etc. which provides a low barrier pathway allowing direct four centered exchange of H and Br. The reaction may be represented as follows:
  • [0029]
    The overall reaction is isothermic and therefore may be driven by fractional recovery of higher bromides and removal of bromomethane from the reaction mixture, all in the presence of excess methane.
  • [0030]
    The gas phase mixture from the condenser 106 is passed through a converter 110, where HBr reacts with the metal oxide to form metal bromide and water. The metal bromide is sent to a regenerator 120 to regenerate metal oxide. From the converter 110, the water, bromomethane, and methane are separated in a separator 112. Methane is recycled to the converter 108 and the vaporizer 102. Bromomethane is sent to the reactor 114. Water is sent to the reactor 118.
  • [0031]
    In the reactor 114 bromomethane reacts with metal oxide to generate dimethyl ether (DME) and metal bromide. Metal bromide is sent to the regenerator 120. The mixture of bromomethane and DME from the reactor 114 is sent to a separator 116. Bromomethane is recycled to the reactor 114, while DME is obtained as a product or directed to reactor 118. In the reactor 118 DME reacts with water (from the separator 112) over a catalyst to form methanol.
  • [0032]
    In the regenerator 120 metal bromide from the converter 110 and the reactor 114 reacts with air or oxygen to regenerate metal oxide and bromine. After regeneration the metal oxide is sent to the converter 110 and the reactor 114, while bromine is sent to the vaporizer 102. If air is used to provide the oxygen for metal oxide regeneration nitrogen may be purged from the system through the separator 122.
  • [0033]
    Referring to FIG. 3, there is shown a method and apparatus 200 for synthesizing olefins from alkanes, which have more than two carbon atoms in their molecular structure, comprising a second embodiment of the invention. The alkane and bromine are directed to a heat zone and vaporizer 202, operating at a temperature above the atmospheric boiling point of bromine, where the now gaseous bromine and methane are allowed to mix. The gas mixture is passed into a bromination reactor 204, which contains an appropriate solid catalyst. After the reaction the mixture is directed to a condenser 206. The heavier alkane multibromides (below 1%) are separated other uses, such as solvent or intermediates for other organic synthesis at an outlet 208, while the alkane monobromide, HBr, and unreacted alkane are sent to a reactor 210.
  • [0034]
    In the reactor 210 HBr reacts with metal oxide to form metal bromide and water. The metal bromide is sent to a regenerator 220 to be regenerated back to metal oxide. From the converter 210 the water, alkane monobromide, and alkane are separated in a separator 212. Unreacted alkane is recycled to a vaporizer 202, while the alkane monobromide is sent to a reactor 214. Water is easily separated from the alkane monobromide in the separator 212 as a by product.
  • [0035]
    In the reactor 214 alkane monobromide reacts with metal oxide to generate olefin and metal bromide. Metal bromide is sent to the regenerator 220 for regeneration back to metal oxide. The mixture of olefin and unreacted alkane monobromide from the reactor 214 is sent to a separator 216 where they are easily separated due to their wide different boiling points. Unreacted alkane monobromide, if any, is recycled to the reactor 214, while olefin is obtained as a product.
  • [0036]
    In the regenerator 220 metal bromide from the converter 210 and the rector 214 reacts with air or oxygen to regenerate metal oxide and bromine. After regeneration metal oxide is sent to the reactor 210 and the reactor 214, while bromine is sent to the vaporizer 202. If air is used as the source of oxygen for regeneration of the metal oxide nitrogen may be purged from the system by a separator 222.
  • EXAMPLES
  • [0037]
    Reaction 1:
  • [0038]
    Catalyst Preparation
  • [0039]
    Nb2O5 (0.8000 g) was mixed with 0.500 ml 96(w)% H2SO4, then the mixture was heated at 110° C. for 4 hours. The temperature increased to 500° C. within 6 hours, and kept at 500° C. for 4 hours. Catalyst C1 was obtained.
  • [0040]
    ZrO2 (2.0000 g) was mixed with H2SO4 (3.000 ml, 96 (w)%) then the mixture was heated at 110° C. for 4 hours. The temperature increased to 500° C. within 6 hours, and kept at 500° C. for 4 hours. Catalyst C2 was obtained.
  • [0041]
    Testing
  • [0042]
    Reaction Conditions:
  • [0043]
    The catalyst was tested at a methane flow of 1.5 ml/minute and Br2 flow Of 0.07 ml/hour. The reaction temperature was 400° C. The reaction was carried out in a micro reactor system. After 6 hours on line reaction, the reaction effluent was analyzed by a GC/MS. A methane conversion of 24% (mol) with 95% CH3Br was obtained. Summarizing the overall process in Reaction 1:
  • CH4+Br2>HBr+CH3Br+CH2Br2+CHBr3+CBr4 cat  (1)
  • [0044]
    Reaction 2:
  • Example 1
  • [0045]
    Reaction on M1
  • [0046]
    For all of the examples provided above the second stage of the process occurs as follows. After separation of the CH2Br2,CHBr3 and CBr4 products from the gas stream, the CH3Br, together with the HBr are passed into the next reactor, which contains M1 (50% CuO on ZrO2) and is maintained at 225° C. Flowing the reactant gases at 10 h−1 gives a 96% conversion of CH3Br+HBr to CH3OCH3 and H2O, or to CH3OH, or a mixture of CH3OH, CH3OCH3, and H2O, with 94% selectivity, the remaining product being CuBr2/ZrO2 and 6% CO2. Dimethyl ether and water are converted into methanol if desired in a third reactor containing catalysts.
  • Example 2
  • [0047]
    Zr Solution Preparation
  • [0048]
    Zr(OCH2CH2CH3)4 (70(w)% in isopropanol, 112.6 ml) was dissolved into acetic acid (275 ml) under stirring. After stirring for 10 minutes, the solution was diluted by water to make a total volume of 500 ml. A solution with a Zr concentration of 0.5M was obtained.
  • [0049]
    Preparation of M2
  • [0050]
    Cu(NO3)2 (0.5M, 7.200 ml) solution was added into BaBr2 (0.5M, 0.800 ml). A clear solution was obtained. To this solution, Zr solution (0.5M) as prepared above was added under stirring. After stirring a few seconds, a gel was obtained. The gel was dried at 110° C. for 4 hours, then heated to 500° C. within 6 hours, and kept at 500° C. for 4 hours. M2 was obtained.
  • [0051]
    The metal oxide mixture was tested at a CH3Br flow rate of 1.0 ml/minute at 230° C. In the first half hour, the average CH3Br conversion was 65%, and the average dimethyl ether selectivity was 90.5%.
  • [0052]
    Preparation of M3
  • [0053]
    Cu(NO3)2 (0.5M, 40.000 ml) solution was added into Zr solution (0.5M, 30.000 ml as prepared above). After stirring a few seconds, a gel was obtained. The gel was dried at 110° C. for 4 hours, then heated to 500° C. within 6 hours, and calcined at 500° C. for 4 hours. M3 was obtained.
  • [0054]
    Testing
  • [0055]
    The catalyst C2 (2.0000 g) was loaded in the first reactor (R1). A trap was loaded with 2.000g of M3. A second reactor (R2) was loaded with M3 (0.8500 g).
  • [0056]
    Reactants methane and bromine were fed into the first reactor (methane flow of 1.5 ml/minute, Br2 flow of 0.07 ml/hour). The reaction temperature was 390° C. After reaction in R1 (stabilized by online reaction for more than 8 hours) the resulting mixture was passed through the trap and a mixture of methane and CH3Br (containing 20% mol of CH3Br) was obtained. This gas mixture was fed directly into reactor R2 at 220° C. In the first hour an average CH3Br conversion of 91% with an average dimethyl ether selectivity of 75% was obtained. Summarizing the overall process in Reaction 2:
  • CH3Br+HBr+CuO>CH3OH+CuBr2  (2)
  • [0057]
    Possible variations of Reaction 2:
  • 2HBr+CuO>H2O+CuBr2  (2a)
  • 2CH3Br+CuO>CH3OCH3+CuBr2  (2b)
  • [0058]
    Reaction 3:
  • [0059]
    The solid CuBr2/ZrO2 was transferred from Reactor 2 to Reactor 3 and treated with O2 at 300° C. to yield Br2 and CuO/ZrO2 at 100% yield and conversion. This reaction may be run at 1000 h−1.
  • [0060]
    Summarizing the overall process in Reaction 3:
  • CuBr2/ZrO2+½O2>Br2+CuO/ZrO2  (3)
  • [0061]
    Overall:
  • CH4+½O2>CH3OH  (A)
  • [0062]
    Possible variation:
  • CH4+½O2>½CH3OCH3+½H2O  (B)
  • [0063]
    A third embodiment of the invention comprises a process for converting ethane to diethyl ether, ethanol, and ethyl acetate which may be carried out as illustrated in FIGS. 1, 2, and 3. In the process, ethane reacts with bromine to form bromomethane and HBr. The bromoethane then reacts with metal oxide to form diethyl ether, ethanol, ethyl acetate, and metal bromide. The metal bromide reacts with oxygen or air to regenerate the original metal oxide. In the process, bromine and metal oxide are recycled.
  • [0064]
    It is well known that ethane can easily react with bromine at low temperatures (below 400° C.) to form bromoethane or ethane dibromides. If a suitable catalyst is used, the selectivity to ethane monobromide or dibromides is high. The reaction is slightly exothermal and is very easy to control. In the next reaction, bromoethane is converted to diethyl ether with 60 to 80% conversion and selectivity over 80% with about 4% selectivity to ethanol and about 3% selectivity to ethyl acetate. Hence, high diethyl ether yield with useful ethanol and ethyl acetate by products is obtained in a single pass. In the process, there is no direct contact between oxygen and ethane thereby providing a high level of safety. If desired, the diethyl ether can be easily hydrolyzed to ethanol with water over a suitable catalyst.
  • EXAMPLE
  • [0065]
    Part A. Ethane Bromination Reaction
  • [0066]
    A mixture of ethane (6.0 ml/minute) and bromine (Br2 0.30 ml/hour) was passed into a reactor (glass tube, ID 0.38″, heating zone length 4″), and was heated to 330° C. The effluent was analyzed by GC/MS. 100% bromine conversion with 80% bromoethane selectivity was obtained. The by product with 20% selectivity was 1,1-dibromoethane. The 1,1-dibromoethane can be converted to bromoethane by reaction with ethane over a catalyst, such as a metal compound or a mixture of metal compounds.
  • [0067]
    The ethane bromination reaction can also be a catalysis reaction. The catalysts are compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, S, Cl, Br, F, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, O, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs or mixtures thereof. The reaction is preferably carried out at a temperature range of between about 50° C. to about 600° C. The reaction pressure is preferably from about 1 to about 200 atm. The reaction mixture can have a ratio of ethane to bromine from 0.1 to 100.
  • [0068]
    Part B. The Reaction of Bromoethane with Metal Oxides. Zr Solution Metal Oxide Preparation
  • [0069]
    Zr(OCH2CH2CH3)4 (70(w)% in isopropanol, 112.6 ml) was dissolved into acetic acid (275 ml) under stirring. After stirring for 10 minutes, the solution was diluted with water to make a total volume of 500 ml. A solution with a Zr concentration of 0.5M was obtained.
  • [0070]
    Preparation of M4
  • [0071]
    A Cu(NO3)2 (0.5M, 64.0 ml) solution was added into a Zr solution (0.5M, 64.0 ml) (as prepared above). After stirring for a few seconds, a gel was obtained. The gel was dried at 110° C. for 4 hours, then heated to 500° C. within 6 hours, and calcined at 500° C. for 4 hours. CuO/ZrO2 metal oxide (M4) was obtained.
  • [0072]
    Testing
  • [0073]
    Bromoethane (0.20 ml/hour) and helium (4.0 ml/minute) were passed through a reactor that was packed with 3.0000 grams M4, which was heated to 200° C. Within the first hour, an average bromoethane conversion of 70%, with diethyl ether 84 to 90% selectivity was obtained. The ethanol selectivity was about 4% and ethyl acetate selectivity was about 3%.
  • [0074]
    In the above reaction, the metal oxides can be oxides of the following metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, S, Cl, Br, F, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs or mixtures thereof.
  • [0075]
    The reaction can be carried out at a temperature range from about 50° C. to about 600° C. The reaction pressure is preferably from about 1 to about 200 atm. The reaction can be carried out with or without helium. The metal bromide is converted to metal oxide M4 in oxygen or in air to obtain metal oxide and bromine at a temperature range of about 50 to about 700° C. and pressure range from about 1 to about 300 atm.
  • [0076]
    A fourth embodiment of the invention comprises a process for converting saturated hydrocarbons (alkanes) to their corresponding olefins. For instance, ethane to ethylene, propane to propylene, butane to butene or butadiene, isobutane to isobutene, etc. The process of the third embodiment may be carried out as illustrated in FIG. 3.
  • [0077]
    In the process, alkane reacts with CBr4, CHBr3, or CH2Br2, or reacts with bromine to form brominated alkanes and HBr. The brominated alkane then reacts with metal oxide to form olefin and metal bromide. The metal bromide reacts with oxygen or air to regenerate the metal oxide. In the process, bromine and metal oxide are recycled.
  • [0078]
    In the prior art, olefins are made by hydrocarbon thermal cracking. The thermal cracking process also produces saturated hydrocarbons, such as propane, butane, isobutane, pentanes, and hexanes, which are usually difficult to convert to useful materials. For example, ethane can be converted to ethylene by thermal cracking at temperatures over 800° C. in an endothermic reaction, which consumes large amounts of energy, and also generates about 30% by product acetylene (C2H2). The acetylene must be hydrogenated back to ethylene which usually leads to over hydrogenation to ethane.
  • [0079]
    Propane is currently used as fuel, since there presently exists no efficient process that can convert propane to propylene.
  • [0080]
    There has been research directed at oxidizing alkanes to their corresponding olefins by reacting the alkane with oxygen over catalysts. However, low selectivity and low conversion rates were obtained. The reaction generates large amounts of heat, which can melt the catalyst as well as the reactor. Further, most of these processes involve the direct contact of the alkane with oxygen at high temperature and pressure, which is potentially dangerous.
  • [0081]
    It is well known that alkanes can easily react with CBr4, CHBr3, or CH2Br2, or react with bromine at low temperatures (below 400° C.) to form alkane monobromides or alkane dibromides. If a suitable catalyst is used, the selectivity to alkane monobromide or dibromide can be very high (more than 95% CH3CH2BrCH3 selectivity can be reached). The reaction is slightly exothermal and is very easy to control. In the next reaction, alkane bromide is converted to olefin with 100% conversion (one pass) and selectivity over 95%. Hence, high olefin yield can be obtained in a single pass. In the process, the direct contact of oxygen with alkane is avoided, making the operation safe. A further advantage of the present invention is the virtual elimination of byproducts, rendering recovery of the desired olefin substantially easier then the conventional process. An even further advantage of the present invention is the production of the olefin without the production of the corresponding alkyne, thus eliminating the need for partial hydrogenation.
  • EXAMPLE
  • [0082]
    Part A. Alkane Bromination Reaction
  • [0083]
    Propane Bromination Reaction
  • [0084]
    A mixture of propane (6.0 ml/minute) and bromine (Br2 0.30 ml/hour) was passed into a reactor (glass tube ID 0.38″, heating zone length 4″), which was heated to 270° C. The effluent was analyzed by GC/MS. 100% bromine conversion with 88.9% 2-bromopropane selectivity and 11.1% 1-bromopropane selectivity were obtained. This reaction can also be a catalysis reaction. The catalysts are compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, S, Cl, Br, F, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, 0, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs or mixtures of such compounds. The reaction can be carried out at a temperature range from about −10° C. to about 600° C. The reaction pressure can be from about 1 to about 200 atm. The reaction mixture can have a ratio of propane to bromine from 0.1 to 100.
  • [0085]
    Bromination of Isobutane
  • [0086]
    A mixture of isobutane (6.0 ml/minute) and bromine (Br2 0.30 ml/hour) was passed into a reactor (glass tube ID 0.38″, heating zone length 4″), which was heated to 220° C. The effluent was analyzed by GC/MS. 100% bromine conversion with 99% 2-bromo-2-methyl-propane selectivity was obtained.
  • [0087]
    This reaction can also be a catalysis reaction. The catalysts are compounds of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, S, Cl, Br, F, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, 0, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs or mixtures of such compounds. The reaction can be carried out at a temperature range from about −10° C. to about 600° C. The reaction pressure can be from about 1 to about 200 atm. The reaction mixture can have a ratio of isobutane to bromine from 0.1 to 100.
  • [0088]
    Part B. The Reaction of Alkane Bromides with Metal Oxides
  • [0089]
    Preparation of Zr Solution Metal Oxide
  • [0090]
    Zr(OCH2CH2CH3)4 (70(w)% in isopropanol, 112.6 ml) was dissolved into acetic acid (275 ml) under stirring. After stirring for 10 minutes, the solution was diluted with water to make a total volume of 500 ml. A solution with a Zr a concentration of 0.5M was obtained.
  • [0091]
    Preparation of M5
  • [0092]
    Cu(NO3)2 (0.5M, 4.00 ml) solution was added into CaBr2 (0.5M, 4.00 ml). A clear solution was obtained. To this solution, Zr solution (0.5M, 8.0 ml) as prepared above was added under stirring. After stirring for a few seconds, a gel was obtained. The gel was dried at 110° C. for 4 hours, then heated to 500° C. within 6 hours, and calcined at 500° C. for 4 hours. M5 was obtained.
  • [0093]
    Preparation of M6
  • [0094]
    Cu(NO3)2 (0.5M, 7.20 ml) solution was added into BaBr2 (0.5M, 0.80 ml). A clear solution was obtained. To this solution, Zr solution (0.5M, 8.0 ml) as prepared above was added under stirring. After stirring for a few seconds, a gel was obtained. The gel was dried at 110° C. for 4 hours, then heated to 500° C. within 6 hours, and calcined at 500° C. for 4 hours. M6 was obtained.
  • [0095]
    Preparation of M7
  • [0096]
    A Cu(NO3)2 (0.5M, 8.00 ml) solution was added into Zr solution (0.5M, 8.0 ml) as prepared above was added under stirring. After stirring for a few seconds, a gel was obtained. The gel was dried at 110° C. for 4 hours, then heated to 500° C. within 6 hours, and calcined at 500° C. for 4 hours. M7 was obtained.
  • [0097]
    Testing on M5
  • [0098]
    2-bromopropane (0.25 ml/hour) and nitrogen (5.0 ml/minute) were passed through a reactor (glass tube ID 0.38″, heating zone length 4″) that was packed with 0.8701 gram M5 and heated to 200° C. 100% 2-bromopropane conversion with more than 95% propylene selectivity was obtained within the first 40 minutes. As the reaction proceeds, the CuO is converted to CuBr2, and the 2-bromopropane conversion rate decreases. When the reaction was carried out at 180° C., within the beginning 10 minutes, 99% propylene selectivity was reached with 2-bromopropane conversion more the 60%.
  • [0099]
    1-bromo-2-methyl-propane (0.29 ml/hour) and nitrogen (5.0 ml/minute) were passed through a reactor (glass tube ID 0.38″, heating zone length 4″) that was packed with 0.8701 gram M5 and heated to 220° C. 100% 1-bromo-2-methyl-propane conversion with more than 96% 2-methyl-propylene selectivity was obtained within the first hour. As the reaction progresses and the CuO is converted to CuBr2, the 2-bromopropane conversion decreases.
  • [0100]
    1-bromo-propane (0.24 ml/hour) and nitrogen (5.0 ml/minute) were passed through a reactor (glass tube ID 0.38″, heating zone length 4″) that was packed with 0.8701 gram M5 and heated to 220° C. 100% 1-bromo-propane conversion with more than 90% propylene selectivity was obtained within the first 20 minutes.
  • [0101]
    2-bromo-2-methyl-propane (0.31 ml/hour) and nitrogen (5.0 ml/minute) were passed through a reactor (glass tube ID 0.38″, heating zone length 4″) that was packed with 0.8701 gram M5 and heated to 180° C. 100% 2-bromo-2-methyl-propane conversion with more than 96% 2-methyl-propylene selectivity was obtained within the first hour.
  • [0102]
    Testing on M6
  • [0103]
    A mixture of 1-bromopropane and 2-bromopropane (volume 1:1) (0.25 ml/hour) and nitrogen (5.0 ml/minute) was passed through a reactor (glass tube ID 0.38″, heating zone length 4″) that was packed with 0.8980 gram M6 and heated to 200° C. 100% reactant conversion with more than 90% propylene selectivity was obtained within the first 10 minutes.
  • [0104]
    Testing on M7
  • [0105]
    A mixture of 1-bromo-2-methyl-propane and 2-bromo-2-methyl-propane (volume 1:1) (0.30 ml/hour) and nitrogen (5.0 ml/minute) were passed through a reactor (glass tube ID 0.38″, heating zone length 4″) that was packed with 0.8500 gram M7 and heated to 220° C. 100% reactant conversion with more than 95% propylene selectivity was obtained within the first 40 minutes.
  • [0106]
    The metal oxides used above can be oxides of the following metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, Sb, Bi, S, Cl, Br, F, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs and mixtures thereof. The reaction can be carried out at a temperature range from about 50° C. to about 600° C. The reaction pressure can be from about 1 to about 200 atm. The reaction can be carried out with or without nitrogen. The metal bromide was converted to metal oxide (M5, M6, and M7) in oxygen or in air to obtain metal oxide and bromine at a temperature range of about 50 to about 700° C. under pressure range from about 1 to about 300 atm.
  • [0107]
    It will therefore be understood that the method and apparatus of the present invention operates on a continuous or batch basis to convert alkanes to alcohols, ethers, and olefins. The method and apparatus of the present invention operates at relatively low temperatures and at low pressures and is therefore economical to manufacture and use. The bromine, which is utilized in the method and apparatus of the present invention, is continuously recycled. The metal oxide, which is utilized in the process is continuously refreshed.
  • [0108]
    Although preferred embodiments of the invention have been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it will be understood that the invention is not limited to the embodiments disclosed but is capable of numerous rearrangements, modifications, and substitutions of parts and elements without departing from the spirit of the invention.

Claims (12)

1. A method for converting methane to methanol comprising:
providing a quantity of methane;
providing a quantity of bromine;
reacting the methane with the bromine and thereby forming bromomethane, hydrogen bromide, and by products CH2Br2, CHBr3, and CBr4;
reacting the by products with methane in the presence of an electrophilic catalyst to form bromomethane;
directing the methyl bromide and the hydrogen bromide into engagement with a metal oxide catalyst and thereby forming methanol and a metal bromide;
oxidizing the metal bromide to form the original metal oxide and bromine;
recycling the metal oxide; and
recycling the bromine.
2. The method according to claim 1 wherein the step of reacting the by products with methane is carried out in the presence of excess methane.
3. The method according to claim 1 wherein the electrophilic catalyst is selected from the group including AlBr3 and SbF5.
4. The method according to claim 1 wherein the step of mixing the methane and the bromine is carried out at a methane to bromine ratio from about 1:10 to about 100:1 (by mole).
5. The method according to claim 1 wherein the step of mixing the methane and the bromine is carried out at a methane to bromine ratio from about 1:1 to about 10:1 (by mole).
6. The process according to claim 1 wherein the step of mixing the methane and the bromine is carried out at a methane to bromine ratio from about 1:1 to about 5:1 (by mole).
7. The method according to claim 1 wherein the step of mixing the methane and the bromine is carried out at a temperature of between about 20° C. and about 400° C.
8. The process according to claim 1 wherein the step of mixing the methane and the bromine to form the methyl bromide and hydrogen bromide and the step of contacting the methyl bromide and the hydrogen bromide with a metal oxide are carried out continuously.
9. The process according to claim 1 wherein the step of mixing the methane and the bromine to form the methyl bromide and hydrogen bromide and the step of contacting the methyl bromide and the hydrogen bromide with a metal oxide are carried out in a batch reaction.
10. The method according to claim 1 wherein the step of oxidizing the metal bromide to form the original metal oxide catalyst and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out continuously.
11. The method according to claim 1 wherein the step of oxidizing the metal bromide to form the original metal oxide catalyst and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out in a batch reaction.
12. An apparatus for converting methane to methanol and/or ether comprising:
a first reactor;
means for directing methane and bromine into the reactor to produce bromomethane, hydrogen bromide, and by products CH2Br2, CHBr3, and CBr4;
a second reactor;
means for directing at least the by products and methane into the second reactor for reaction in the presence of an electrophilic catalyst to form bromomethane;
a reaction bed comprising a solid metal oxide;
means for directing bromomethane and hydrogen bromide from the first and second reactors into contact with the metal oxide to form methanol and/or ether and metal bromide;
means for oxidizing the metal bromide to form the original metal oxide and bromine; and
means for recycling the original metal oxide and the bromine.
US10054004 2001-06-20 2002-01-24 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes Expired - Fee Related US6486368B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09886078 US6472572B1 (en) 2001-06-20 2001-06-20 Integrated process for synthesizing alcohols and ethers from alkanes
US09951739 US6465696B1 (en) 2001-06-20 2001-09-11 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US10054004 US6486368B1 (en) 2001-06-20 2002-01-24 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
US10054004 US6486368B1 (en) 2001-06-20 2002-01-24 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
EP20100176682 EP2277847A3 (en) 2002-01-24 2002-07-17 Integrated Process for Synthesizing Alcohols, Ethers, and Olefins from Alkanes
PCT/US2002/022817 WO2003062172B1 (en) 2002-01-24 2002-07-17 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
CA 2710351 CA2710351A1 (en) 2002-01-24 2002-07-17 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
CA 2471295 CA2471295C (en) 2002-01-24 2002-07-17 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
CN 02827498 CN1271020C (en) 2002-01-24 2002-07-17 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
JP2003562057A JP4309283B2 (en) 2002-01-24 2002-07-17 Integrated process for synthesizing alcohols from alkenes, ethers, and olefins
EP20020748199 EP1474371B1 (en) 2002-01-24 2002-07-17 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
RU2004125653A RU2004125653A (en) 2002-01-24 2002-07-17 An integrated process for the synthesis of alcohols, ethers and olefins from alkanes
US10298440 US20030069452A1 (en) 2001-06-20 2002-11-19 Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics
US10307789 US20030078456A1 (en) 2001-06-20 2002-12-02 Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US10365346 US20030120121A1 (en) 2001-06-20 2003-02-12 Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics
US10365087 US6713655B2 (en) 2001-06-20 2003-02-12 Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US10375464 US7148390B2 (en) 2001-06-20 2003-02-27 Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US10430240 US7161050B2 (en) 2001-06-20 2003-08-19 Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US11098997 US20050192468A1 (en) 2001-06-20 2005-04-05 Hydrocarbon conversion process improvements
US12692831 US7838708B2 (en) 2001-06-20 2010-01-25 Hydrocarbon conversion process improvements
US12904030 US8415512B2 (en) 2001-06-20 2010-10-13 Hydrocarbon conversion process improvements

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09951739 Continuation-In-Part US6465696B1 (en) 2001-06-20 2001-09-11 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US20806802 Continuation-In-Part 2002-07-29 2002-07-29

Publications (2)

Publication Number Publication Date
US6486368B1 US6486368B1 (en) 2002-11-26
US20020198416A1 true true US20020198416A1 (en) 2002-12-26

Family

ID=27128781

Family Applications (1)

Application Number Title Priority Date Filing Date
US10054004 Expired - Fee Related US6486368B1 (en) 2001-06-20 2002-01-24 Integrated process for synthesizing alcohols, ethers, and olefins from alkanes

Country Status (1)

Country Link
US (1) US6486368B1 (en)

Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040267074A1 (en) * 2001-04-18 2004-12-30 Philip Grosso Zone reactor
US20050038310A1 (en) * 2003-07-15 2005-02-17 Lorkovic Ivan M. Hydrocarbon synthesis
US20050192468A1 (en) * 2001-06-20 2005-09-01 Sherman Jeffrey H. Hydrocarbon conversion process improvements
US20050215837A1 (en) * 2004-03-23 2005-09-29 Shell Oil Company The utilization of zirconium and zirconium based alloys for the containment of halogen containing environments used in the production of olefins, alcohols, ethers, and olefin oxides from alkanes
US20050234277A1 (en) * 2004-04-16 2005-10-20 Waycuilis John J Process for converting gaseous alkanes to liquid hydrocarbons
US20050245772A1 (en) * 2004-04-30 2005-11-03 Fong Howard L Derivatives of alcohols and olefins
US20050245771A1 (en) * 2004-04-21 2005-11-03 Fong Howard L Process to convert alkanes into primary alcohols
WO2005105709A1 (en) * 2004-04-21 2005-11-10 Shell Internationale Research Maatschappij B.V. Process to convert linear alkanes into alpha olefins
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US20060100469A1 (en) * 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons
EP1660419A1 (en) * 2003-08-19 2006-05-31 GRT, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US20060229228A1 (en) * 2005-04-11 2006-10-12 Zachary John Anthony Komon Method of making alkoxylates
US7148390B2 (en) 2001-06-20 2006-12-12 Grt, Inc. Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US20090247796A1 (en) * 2004-04-16 2009-10-01 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US20130158324A1 (en) * 2011-12-16 2013-06-20 Marathon Gtf Technology, Ltd. Processes and Systems for Conversion of Alkyl Bromides to Higher Molecular Weight Hydrocarbons in Circulating Catalyst Reactor-Regenerator Systems
US8575403B2 (en) 2010-05-07 2013-11-05 Celanese International Corporation Hydrolysis of ethyl acetate in ethanol separation process
US8592635B2 (en) 2011-04-26 2013-11-26 Celanese International Corporation Integrated ethanol production by extracting halides from acetic acid
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US8664454B2 (en) 2010-07-09 2014-03-04 Celanese International Corporation Process for production of ethanol using a mixed feed using copper containing catalyst
US8704008B2 (en) 2010-07-09 2014-04-22 Celanese International Corporation Process for producing ethanol using a stacked bed reactor
US8710279B2 (en) 2010-07-09 2014-04-29 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US8748673B2 (en) 2011-11-18 2014-06-10 Celanese International Corporation Process of recovery of ethanol from hydrogenolysis process
US8754268B2 (en) 2011-04-26 2014-06-17 Celanese International Corporation Process for removing water from alcohol mixtures
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US8802901B2 (en) 2011-11-18 2014-08-12 Celanese International Corporation Continuous ethyl acetate production and hydrogenolysis thereof
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8829251B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Liquid esterification method to produce ester feed for hydrogenolysis
US8829249B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Integrated esterification and hydrogenolysis process for producing ethanol
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8853468B2 (en) 2011-11-18 2014-10-07 Celanese International Corporation Vapor esterification method to produce ester feed for hydrogenolysis
US8859827B2 (en) 2011-11-18 2014-10-14 Celanese International Corporation Esterifying acetic acid to produce ester feed for hydrogenolysis
US8895786B2 (en) 2011-08-03 2014-11-25 Celanese International Corporation Processes for increasing alcohol production
US8927790B2 (en) 2011-12-15 2015-01-06 Celanese International Corporation Multiple vapor feeds for hydrogenation process to produce alcohol
US8975451B2 (en) 2013-03-15 2015-03-10 Celanese International Corporation Single phase ester feed for hydrogenolysis
US9024089B2 (en) 2011-11-18 2015-05-05 Celanese International Corporation Esterification process using extractive separation to produce feed for hydrogenolysis
US9073816B2 (en) 2011-04-26 2015-07-07 Celanese International Corporation Reducing ethyl acetate concentration in recycle streams for ethanol production processes
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US9272970B2 (en) 2010-07-09 2016-03-01 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
CN105709751A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Catalyst for preparing dimethyl ether from bromomethane, and preparation method and application thereof

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030069452A1 (en) * 2001-06-20 2003-04-10 Sherman Jeffrey H. Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics
JP2005010545A (en) * 2003-06-20 2005-01-13 Hitachi Ltd Transmission type screen and back projection type video display device using same
US20090054274A1 (en) * 2005-03-28 2009-02-26 Howard Lam-Ho Fong Formation of Heteroatom Containing Derivatives of Paraffins
US20090270655A1 (en) * 2005-03-28 2009-10-29 Howard Lam-Ho Fong Conversion of Alkylhalides Into Alcohol Alkoxylates
WO2006104909A3 (en) * 2005-03-28 2007-03-22 Shell Int Research Catalytic distillation process for primary haloalkanes
US20060229475A1 (en) * 2005-04-11 2006-10-12 Weiss Michael J Synthesis of hydroxylated hydrocarbons
US20090163749A1 (en) * 2006-03-20 2009-06-25 Microvast Technologies, Ltd. Conversion of methane into c3˜c13 hydrocarbons
CN100582064C (en) * 2006-03-20 2010-01-20 微宏科技(湖州)有限公司 Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method
CN101284756A (en) * 2007-04-13 2008-10-15 微宏科技(湖州)有限公司 Purification method for HBr in hydrocarbons
US7696390B2 (en) * 2008-06-10 2010-04-13 Stauffer John E Methanol synthesis
WO2012149137A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Process for the production of ethanol from an acetic acid feed and a recycled ethyl acetate feed
US20120259145A1 (en) * 2011-04-06 2012-10-11 Stauffer John E Manufacture of methanol
US8440868B2 (en) * 2011-04-06 2013-05-14 John E. Stauffer Manufacture of methanol

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172915A (en) * 1965-03-09 Preparation of oxygenated methane derivatives
US3310380A (en) * 1964-02-13 1967-03-21 Universal Oil Prod Co Bromine recovery
US5243098A (en) * 1992-11-04 1993-09-07 Energia Andina Ltd. Conversion of methane to methanol
US5998679A (en) * 1998-05-20 1999-12-07 Jlm Technology, Ltd. Methods for converting lower alkanes and alkanes to alcohols and diols
WO2000007718A1 (en) * 1998-08-05 2000-02-17 Enitecnologie S.P.A. Catalyst and process for the oxidation of methane to methanol

Cited By (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US20040267074A1 (en) * 2001-04-18 2004-12-30 Philip Grosso Zone reactor
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US20050192468A1 (en) * 2001-06-20 2005-09-01 Sherman Jeffrey H. Hydrocarbon conversion process improvements
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US7148390B2 (en) 2001-06-20 2006-12-12 Grt, Inc. Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US20050038310A1 (en) * 2003-07-15 2005-02-17 Lorkovic Ivan M. Hydrocarbon synthesis
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
JP2007525477A (en) * 2003-07-15 2007-09-06 ザ・レジェンツ・オブ・ザ・ユニバーシティ・オブ・カリフォルニアThe Regents of The University of California Synthesis of hydrocarbons
JP2012092134A (en) * 2003-07-15 2012-05-17 Grt Inc Hydrocarbon synthesis
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
EP1660419A1 (en) * 2003-08-19 2006-05-31 GRT, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
WO2005095310A2 (en) * 2004-03-23 2005-10-13 Shell Internationale Research Maatschappij B.V. The utilization of zirconium and zirconium based alloys for the containment of halogen containing environments used in the production of olefins, alcohols, ethers, ethoxylates glycols, and olefin oxides from alkanes
WO2005095310A3 (en) * 2004-03-23 2005-12-08 Shell Oil Co The utilization of zirconium and zirconium based alloys for the containment of halogen containing environments used in the production of olefins, alcohols, ethers, ethoxylates glycols, and olefin oxides from alkanes
US20050215837A1 (en) * 2004-03-23 2005-09-29 Shell Oil Company The utilization of zirconium and zirconium based alloys for the containment of halogen containing environments used in the production of olefins, alcohols, ethers, and olefin oxides from alkanes
US20060100469A1 (en) * 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US20050234277A1 (en) * 2004-04-16 2005-10-20 Waycuilis John J Process for converting gaseous alkanes to liquid hydrocarbons
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8232441B2 (en) 2004-04-16 2012-07-31 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US20080183022A1 (en) * 2004-04-16 2008-07-31 Waycuilis John J Process for converting gaseous alkanes to liquid hydrocarbons
US20080200740A1 (en) * 2004-04-16 2008-08-21 Marathon Oil Company Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US20090247796A1 (en) * 2004-04-16 2009-10-01 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US20080171898A1 (en) * 2004-04-16 2008-07-17 Waycuilis John J Process for converting gaseous alkanes to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7462752B2 (en) 2004-04-21 2008-12-09 Shell Oil Company Process to convert linear alkanes into alpha olefins
WO2005105709A1 (en) * 2004-04-21 2005-11-10 Shell Internationale Research Maatschappij B.V. Process to convert linear alkanes into alpha olefins
US20050245771A1 (en) * 2004-04-21 2005-11-03 Fong Howard L Process to convert alkanes into primary alcohols
US7091387B2 (en) 2004-04-21 2006-08-15 Shell Oil Company Process to convert alkanes into primary alcohols
US20050245772A1 (en) * 2004-04-30 2005-11-03 Fong Howard L Derivatives of alcohols and olefins
WO2005110953A1 (en) * 2004-04-30 2005-11-24 Shell Internationale Research Maatschappij B.V. Derivatives of alcohols and olefins
US20060229228A1 (en) * 2005-04-11 2006-10-12 Zachary John Anthony Komon Method of making alkoxylates
US20090069606A1 (en) * 2005-04-11 2009-03-12 Grt, Inc. Method of making alkoxylates
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US7998438B2 (en) 2007-05-24 2011-08-16 Grt, Inc. Zone reactor incorporating reversible hydrogen halide capture and release
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
US7968755B2 (en) 2008-10-01 2011-06-28 Sajet Development Llc Process and catalyst for converting alkanes
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8575403B2 (en) 2010-05-07 2013-11-05 Celanese International Corporation Hydrolysis of ethyl acetate in ethanol separation process
US8710279B2 (en) 2010-07-09 2014-04-29 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US8664454B2 (en) 2010-07-09 2014-03-04 Celanese International Corporation Process for production of ethanol using a mixed feed using copper containing catalyst
US8704008B2 (en) 2010-07-09 2014-04-22 Celanese International Corporation Process for producing ethanol using a stacked bed reactor
US9272970B2 (en) 2010-07-09 2016-03-01 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US9670119B2 (en) 2010-07-09 2017-06-06 Celanese International Corporation Process for producing ethanol using multiple beds each having different catalysts
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8754268B2 (en) 2011-04-26 2014-06-17 Celanese International Corporation Process for removing water from alcohol mixtures
US9073816B2 (en) 2011-04-26 2015-07-07 Celanese International Corporation Reducing ethyl acetate concentration in recycle streams for ethanol production processes
US8592635B2 (en) 2011-04-26 2013-11-26 Celanese International Corporation Integrated ethanol production by extracting halides from acetic acid
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8895786B2 (en) 2011-08-03 2014-11-25 Celanese International Corporation Processes for increasing alcohol production
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US8853468B2 (en) 2011-11-18 2014-10-07 Celanese International Corporation Vapor esterification method to produce ester feed for hydrogenolysis
US8829251B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Liquid esterification method to produce ester feed for hydrogenolysis
US8802901B2 (en) 2011-11-18 2014-08-12 Celanese International Corporation Continuous ethyl acetate production and hydrogenolysis thereof
US8748673B2 (en) 2011-11-18 2014-06-10 Celanese International Corporation Process of recovery of ethanol from hydrogenolysis process
US9024089B2 (en) 2011-11-18 2015-05-05 Celanese International Corporation Esterification process using extractive separation to produce feed for hydrogenolysis
US8829249B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Integrated esterification and hydrogenolysis process for producing ethanol
US8859827B2 (en) 2011-11-18 2014-10-14 Celanese International Corporation Esterifying acetic acid to produce ester feed for hydrogenolysis
US8927790B2 (en) 2011-12-15 2015-01-06 Celanese International Corporation Multiple vapor feeds for hydrogenation process to produce alcohol
US20130158324A1 (en) * 2011-12-16 2013-06-20 Marathon Gtf Technology, Ltd. Processes and Systems for Conversion of Alkyl Bromides to Higher Molecular Weight Hydrocarbons in Circulating Catalyst Reactor-Regenerator Systems
US9193641B2 (en) * 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US8975451B2 (en) 2013-03-15 2015-03-10 Celanese International Corporation Single phase ester feed for hydrogenolysis
CN105709751A (en) * 2014-12-04 2016-06-29 中国石油化工股份有限公司 Catalyst for preparing dimethyl ether from bromomethane, and preparation method and application thereof

Also Published As

Publication number Publication date Type
US6486368B1 (en) 2002-11-26 grant

Similar Documents

Publication Publication Date Title
US3670037A (en) Catalyst system
US4300005A (en) Preparation of vinyl chloride
US6187976B1 (en) Process for the preparation of fluorine containing hydrohalocarbons
US3427359A (en) Oxychlorination of hydrocarbons and a catalyst therefor
US4962252A (en) Process for the production of alkenyl-substituted benzene derivatives
US6844475B1 (en) Low temperature production of 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd)
US6984763B2 (en) Oxidative halogenation and optional dehydrogenation of c3+hydrocarbons
US20050245772A1 (en) Derivatives of alcohols and olefins
US4973786A (en) Process for the pyrolytic oxidation of methane to higher molecular weight hydrocarbons and synthesis gas
US20070112229A1 (en) Method for producing fluorinated organic compounds
US8076521B2 (en) Process for the manufacture of hydrofluoroolefins
US5243098A (en) Conversion of methane to methanol
Olah et al. Selective monohalogenation of methane over supported acid or platinum metal catalysts and hydrolysis of methyl halides over γ-alumina-supported metal oxide/hydroxide catalysts: a feasible path for the oxidative conversion of methane into methyl alcohol/dimethyl ether
US4194990A (en) Catalyst and process for the production of chlorofluorinated hydrocarbons
US6403840B1 (en) Process for synthesizing olefin oxides
US6797845B1 (en) Process for vinyl chloride manufacture from ethane and ethylene with immediate HCl recovery from reactor effluent
US20040152929A1 (en) Process for vinyl chloride manufacture from ethane and ethylene with air feed and alternative hcl processing methods
WO2005042451A2 (en) Process for producing fluoropropenes
US6933417B1 (en) Process for vinyl chloride manufacture from ethane and ethylene with partial CHl recovery from reactor effluent
US5895825A (en) Preparation of 1,1,1,3,3-pentafluoropropane
US6143921A (en) Method for producing vinyl acetate monomer from ethane or ethylene oxidation
US5998679A (en) Methods for converting lower alkanes and alkanes to alcohols and diols
US20100121119A1 (en) Hydrocarbon Conversion Process Improvements
US6909024B1 (en) Process for the conversion of ethylene to vinyl chloride and novel catalyst compositions useful for such process
WO2001038275A1 (en) Dehydrohalogenation of halogenated alkanes using rare earth halide or oxyhalide catalyst

Legal Events

Date Code Title Description
AS Assignment

Owner name: GRT, INC., TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHERMAN, JEFFREY H.;REEL/FRAME:012528/0423

Effective date: 20020117

Owner name: REGENTS OF THE UNIVERSITY OF CALIFORNIA, THE, CALI

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHOU, XIAO PING;LORKOVIC, IVAN MARC;REEL/FRAME:012528/0441

Effective date: 20020117

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

SULP Surcharge for late payment
AS Assignment

Owner name: HOOK, THOMAS W., TEXAS

Free format text: SECURITY AGREEMENT;ASSIGNOR:GRT, INC.;REEL/FRAME:028498/0541

Effective date: 20120703

AS Assignment

Owner name: REACTION 35, LLC, TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GRT, INC.;REEL/FRAME:031778/0327

Effective date: 20131209

Owner name: REACTION 35, LLC, TEXAS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:HOOK, THOMAS W.;REEL/FRAME:031784/0696

Effective date: 20131209

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Expired due to failure to pay maintenance fee

Effective date: 20141126