US20020198416A1 - Integrated process for synthesizing alcohols, ethers, and olefins from alkanes - Google Patents
Integrated process for synthesizing alcohols, ethers, and olefins from alkanes Download PDFInfo
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- US20020198416A1 US20020198416A1 US10/054,004 US5400402A US2002198416A1 US 20020198416 A1 US20020198416 A1 US 20020198416A1 US 5400402 A US5400402 A US 5400402A US 2002198416 A1 US2002198416 A1 US 2002198416A1
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- KQILDNCMULFYNK-RKKUYXDDSA-H BrC(Br)(Br)Br.BrC(Br)Br.BrC(Br)Br.Br[Al](Br)Br.Br[Al](Br)Br.C.C.[2HH] Chemical compound BrC(Br)(Br)Br.BrC(Br)Br.BrC(Br)Br.Br[Al](Br)Br.Br[Al](Br)Br.C.C.[2HH] KQILDNCMULFYNK-RKKUYXDDSA-H 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- 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
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation 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
- C07C29/124—Preparation 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
Description
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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:
- 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;
- 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
- FIG. 3 is a schematic illustration of a method of and apparatus for synthesizing olefins from alkanes comprising a second embodiment of the invention.
- 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.
- 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 andapparatus 10, bromine is received from a suitable source through aline 12 and is directed to abromine storage container 14. For example, bromine is easily manufactured from bromide, which is readily available from sea water. - As is well known, bromine is a liquid at room temperature. Liquid bromine from the
storage container 14 is directed through aline 16 to abromine vaporizer 18 wherein the bromine is converted from the liquid phase to the gas phase. From thevaporizer 18 the gaseous bromine is directed through aline 20 to areactor 22. - Methane from a suitable source is directed to the
reactor 22 through aline 24. Within thereactor 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). - From the
reactor 22, the CH3Br, the HBr, any unreacted methane and by-products CH2Br2, CHBr3, and CBr4 are directed to acondenser 34 through aline 30. The by products CH2Br2, CHBr3, and CBr4 are in the liquid state and are sent through aline 32 to aconverter 28 to react with methane. In theconverter 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 thecondenser 34 through aline 26 and theline 30. - From the
condenser 34 gas phase methane, HBr, and CH3Br are sent to aconverter 52 through aline 36. In theconverter 52 HBr and CH3Br react with metal oxide to form CH3OCH3, CH3OH, and H2O, which are sent to aseparator 44 along with unreacted methane and CH3Br through aline 46. - In the
separator 44 dimethyl either and methanol/water are separated as products and recovered atoutlets converter 52 through theline 38 and theline 36. Methane from theseparator 44 is sent back to thebromination reactor 22 through theline 42 and theline 24. - In the
converter 52, the original metal oxide is converted to metal bromide and must be regenerated. The metal bromide from theconverter 52 is sent to aconverter 58 through aline 54 to react with oxygen received from asource 74 through aline 72 to regenerate bromine and metal oxide. The regenerated metal oxide is sent back to theconverter 52 through aline 56, while the bromine and unreacted oxygen are sent to acondenser 62 through aline 60, after which they are separated in aseparator 68. The liquid bromine is sent to thestorage container 14, while the oxygen is sent to theconverter 58 through ablower 66 and aline 70. - Referring to FIG. 2, there is shown a method of and apparatus100 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 abromination 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. - 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 thecondenser 106. -
- 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.
- The gas phase mixture from the
condenser 106 is passed through aconverter 110, where HBr reacts with the metal oxide to form metal bromide and water. The metal bromide is sent to aregenerator 120 to regenerate metal oxide. From theconverter 110, the water, bromomethane, and methane are separated in aseparator 112. Methane is recycled to theconverter 108 and thevaporizer 102. Bromomethane is sent to thereactor 114. Water is sent to thereactor 118. - In the
reactor 114 bromomethane reacts with metal oxide to generate dimethyl ether (DME) and metal bromide. Metal bromide is sent to theregenerator 120. The mixture of bromomethane and DME from thereactor 114 is sent to aseparator 116. Bromomethane is recycled to thereactor 114, while DME is obtained as a product or directed toreactor 118. In thereactor 118 DME reacts with water (from the separator 112) over a catalyst to form methanol. - In the
regenerator 120 metal bromide from theconverter 110 and thereactor 114 reacts with air or oxygen to regenerate metal oxide and bromine. After regeneration the metal oxide is sent to theconverter 110 and thereactor 114, while bromine is sent to thevaporizer 102. If air is used to provide the oxygen for metal oxide regeneration nitrogen may be purged from the system through theseparator 122. - 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 andvaporizer 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 abromination reactor 204, which contains an appropriate solid catalyst. After the reaction the mixture is directed to acondenser 206. The heavier alkane multibromides (below 1%) are separated other uses, such as solvent or intermediates for other organic synthesis at anoutlet 208, while the alkane monobromide, HBr, and unreacted alkane are sent to areactor 210. - In the
reactor 210 HBr reacts with metal oxide to form metal bromide and water. The metal bromide is sent to aregenerator 220 to be regenerated back to metal oxide. From theconverter 210 the water, alkane monobromide, and alkane are separated in aseparator 212. Unreacted alkane is recycled to avaporizer 202, while the alkane monobromide is sent to areactor 214. Water is easily separated from the alkane monobromide in theseparator 212 as a by product. - In the
reactor 214 alkane monobromide reacts with metal oxide to generate olefin and metal bromide. Metal bromide is sent to theregenerator 220 for regeneration back to metal oxide. The mixture of olefin and unreacted alkane monobromide from thereactor 214 is sent to aseparator 216 where they are easily separated due to their wide different boiling points. Unreacted alkane monobromide, if any, is recycled to thereactor 214, while olefin is obtained as a product. - In the
regenerator 220 metal bromide from theconverter 210 and therector 214 reacts with air or oxygen to regenerate metal oxide and bromine. After regeneration metal oxide is sent to thereactor 210 and thereactor 214, while bromine is sent to thevaporizer 202. If air is used as the source of oxygen for regeneration of the metal oxide nitrogen may be purged from the system by aseparator 222. - Reaction 1:
- Catalyst Preparation
- 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.
- 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.
- Testing
- Reaction Conditions:
- 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)
- Reaction 2:
- Reaction on M1
- 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.
- Zr Solution Preparation
- 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.
- Preparation of M2
- 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.
- 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%.
- Preparation of M3
- 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.
- Testing
- 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).
- 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)
- Possible variations of Reaction 2:
- 2HBr+CuO>H2O+CuBr2 (2a)
- 2CH3Br+CuO>CH3OCH3+CuBr2 (2b)
- Reaction 3:
- 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. - Summarizing the overall process in Reaction 3:
- CuBr2/ZrO2+½O2>Br2+CuO/ZrO2 (3)
- Overall:
- CH4+½O2>CH3OH (A)
- Possible variation:
- CH4+½O2>½CH3OCH3+½H2O (B)
- 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, and3. 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.
- 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.
- Part A. Ethane Bromination Reaction
- 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.
- 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.
- Part B. The Reaction of Bromoethane with Metal Oxides. Zr Solution Metal Oxide Preparation
- 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.
- Preparation of M4
- 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.
- Testing
- 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%.
- 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.
- 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.
- 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.
- 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.
- 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.
- Propane is currently used as fuel, since there presently exists no efficient process that can convert propane to propylene.
- 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.
- 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.
- Part A. Alkane Bromination Reaction
- Propane Bromination Reaction
- 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.
- Bromination of Isobutane
- 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.
- 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.
- Part B. The Reaction of Alkane Bromides with Metal Oxides
- Preparation of Zr Solution Metal Oxide
- 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.
- Preparation of M5
- 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.
- Preparation of M6
- 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.
- Preparation of M7
- 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.
- Testing on M5
- 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%.
- 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.
- 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.
- 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.
- Testing on M6
- 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.
- Testing on M7
- 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.
- 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.
- 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.
- 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)
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US10/054,004 US6486368B1 (en) | 2001-06-20 | 2002-01-24 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
JP2003562057A JP4309283B2 (en) | 2002-01-24 | 2002-07-17 | Integrated process for the synthesis of alcohols, ethers and olefins from alkenes |
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EP02748199A EP1474371B1 (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
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AU2002318266A AU2002318266B2 (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
CA2471295A CA2471295C (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
EP10176682A EP2277847A3 (en) | 2002-01-24 | 2002-07-17 | Integrated Process for Synthesizing Alcohols, Ethers, and Olefins from Alkanes |
MXPA04006785A MXPA04006785A (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes. |
US10/298,440 US20030069452A1 (en) | 2001-06-20 | 2002-11-19 | Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics |
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US10/365,087 US6713655B2 (en) | 2001-06-20 | 2003-02-12 | Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes |
US10/365,346 US20030120121A1 (en) | 2001-06-20 | 2003-02-12 | Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics |
US10/375,464 US7148390B2 (en) | 2001-06-20 | 2003-02-27 | Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes |
US10/430,240 US7161050B2 (en) | 2001-06-20 | 2003-08-19 | Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes |
ZA200405085A ZA200405085B (en) | 2002-01-24 | 2004-06-25 | Integrated process for synthesizing alchols, ethers and olefins from alkanes |
US11/098,997 US20050192468A1 (en) | 2001-06-20 | 2005-04-05 | Hydrocarbon conversion process improvements |
US12/692,831 US7838708B2 (en) | 2001-06-20 | 2010-01-25 | Hydrocarbon conversion process improvements |
US12/904,030 US8415512B2 (en) | 2001-06-20 | 2010-10-13 | Hydrocarbon conversion process improvements |
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