WO2003022827A1 - Process for synthesizing olefin oxides - Google Patents

Process for synthesizing olefin oxides Download PDF

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Publication number
WO2003022827A1
WO2003022827A1 PCT/US2002/020981 US0220981W WO03022827A1 WO 2003022827 A1 WO2003022827 A1 WO 2003022827A1 US 0220981 W US0220981 W US 0220981W WO 03022827 A1 WO03022827 A1 WO 03022827A1
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Prior art keywords
metal oxide
bromine
recycling
reacting
carried out
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PCT/US2002/020981
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French (fr)
Inventor
Xiao Ping Zhou
Galen D. Stucky
Jeffrey H. Sherman
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Grt, Inc.
The Regents Of The University Of California
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Priority claimed from US09/951,581 external-priority patent/US6403840B1/en
Application filed by Grt, Inc., The Regents Of The University Of California filed Critical Grt, Inc.
Publication of WO2003022827A1 publication Critical patent/WO2003022827A1/en

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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

Definitions

  • This invention relates generally to the synthesis of olefin oxides, and more particularly to an economical and safe process for synthesizing propylene oxide and other olefin oxides .
  • Co-pending application serial number 09/886,078 filed June 20, 2001 and assigned to the assignee hereof is incorporated herein by reference.
  • the co-pending application discloses and claims a process for synthesizing alcohols and ethers from alkanes .
  • the process involves reacting an alkane with bromine to form the corresponding alkyl bromide and hydrogen bromide.
  • the alkyl bromide and the hydrogen bromide are reacted with a metal oxide to produce the corresponding alcohol and/or ether, and metal bromide.
  • the metal bromide is oxidized to form the original metal oxide and bromine, both of which are recycled.
  • the present invention employs a similar procedure to synthesize olefin oxides, particularly propylene oxide.
  • Propylene oxide has heretofore been produced using a wide variety of procedures, none of which is particularly satisfactory.
  • propylene chlorohydrin The oldest and most widely used procedure for preparing propylene oxide is the propylene chlorohydrin process.
  • An early propylene chlorohydrin technique involved electrolyzation of propylene in aqueous potassium chloride to prepare propylene chlorohydrin which was then dehydrohalogenated to produce propylene oxide.
  • propylene oxide is prepared by reacting propylene with chlorine/water to prepare propylene chlorohydrin, then reacting the propylene chlorohydrin with aqueous calcium hydroxide, sodium hydroxide or calcium carbonate to obtain propylene oxide.
  • a major drawback to the propylene chlorohydrin process involves the fact that the manufacture of a given quantity of propylene oxide necessarily results in the manufacture of a like or greater quantity of various salts which have little commercial value.
  • a further disadvantage of the propylene chlorohydrin process is the fact that the propylene oxide product must be separated from large quantities of water, generally through steam stripping.
  • Propylene oxide can also be manufactured utilizing the ethylbenzene process.
  • the ethylbenzene process involves reacting ethylbenzene with oxygen to generate ethylbenzene hydroperoxide which is then reacted with propylene to obtain propylene oxide and alpha phenylethano1.
  • the alpha phenylethanol is then converted to styrene by dehydration.
  • the major drawbacks to the ethylbenzene process involves the production of styrene in equal quantities with the desired propylene oxide and the use of ethylbenzene hydroperoxide, which is both explosive and subject to decomposition. Cumene can also be used to manufacture propylene oxide.
  • the cumene is oxidized to produce cumene hydroperoxide which is then reacted with propylene to form propylene oxide and cumyl alcohol.
  • the cumyl alcohol is reduced to cumene by reaction with hydrogen over a catalyst and is recycled.
  • the drawbacks to the cumene process include the use of large amounts of cumene hydroperoxide which is highly explosive and the consumption of expensive hydrogen.
  • a fourth process for manufacturing propylene oxide is known as the tert-butane hydroperoxide process.
  • isobutane is oxidized by reaction with oxygen to obtain tertiary butane hydroperoxide, which is then reacted with propylene to form propylene oxide and tert-BuOH.
  • the drawbacks to the process include the direct reaction of butane with oxygen, the use of dangerous tert-butane hydroperoxide, and the production of tert-BuOH as a byproduct.
  • Still another process for producing propylene oxide is known as the hydrogen ⁇ peroxide process .
  • propylene is reacted with hydrogen peroxide in a solvent such as methanol over a catalyst.
  • Drawbacks to the process include the fact that the reaction rate is very slow and the fact that expensive hydrogen is necessarily consumed to form hydrogen peroxide .
  • a sixth method of synthesizing propylene oxide involves direct oxidation of propylene.
  • propylene is reacted with oxygen over a catalyst to generate propylene oxide.
  • safety considerations dictate that the process is very carefully controlled.
  • Other drawbacks include low conversion rates, typically below 10% and low selectivity, typically below 40%.
  • the present invention comprises a method of synthesizing propylene oxide and other olefin oxides which overcomes the foregoing and other difficulties that have long since characterized the prior art.
  • an olefin bromohydrin or an alkane dibromide is reacted with a metal oxide to form olefin oxide and metal bromide.
  • the metal bromide is converted to obtain the original metal oxide and bromine, both of which are recycled.
  • an olefin bromohydrin and/or an alkane dibromide (such as propylene bromohydrin and/or 1, 2-dibromopropane) is reacted with a metal oxide to synthesize olefin oxide
  • Cu(N0 3 ) 2 (0.5M, 6.8ml) solution was mixed with BaBr 2 (0.5M, 1.2ml). A clear solution was obtained. The solution was added into Zr solution (0.5M, 8.0ml) (as prepared above) . After stirring for a few seconds, a gel was obtained. The gel was dried at 110 2 C for 4 hours, then heated to 500 S C within 6 hours, and calcined at 500 2 C for 4 hours. BaBr 2 CuO/Zr0 2 metal oxide (M2) was obtained. M3 Cu(N0 3 ) 2 (0.5M, 7.6ml) solution was mixed with CaBr 2 (0.5M,
  • Propylene bromohydrin (1.00ml/hour) and helium (2.0ml/minute) were passed through a reactor that was packed with 3.0000 gram Ml, which was heated to 100 2 C.
  • Propylene bromohydrin (0.50ml/hour) and nitrogen (5. Oml/minute) were passed through a reactor that packed with 0.8286 gram M3, which was heated to 120 2 C. Within the first 1.5 hours, an average propylene bromohydrin conversion of 50%, with 41% propylene oxide average selectivity was obtained. 1,2-dibromopropane 1, 2-dibromopropane (1. OOml/hour) (0.50ml/hour) and nitrogen (5. Oml/minute) were passed through a reactor that packed with 0.8286 gram M3 , which was heated to 100 ⁇ C. Within the first 1.5 hours, an average propylene bromohydrin conversion of 40%, with 59% propylene oxide average selectivity was obtained.
  • the metal oxide can be an oxide of the following metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
  • the reactions can be carried out at a temperature range of between about 50 2 C to about 600 2 C.
  • the reactions pressure can be from about 1 to about 200 atm.
  • the reaction can be carried out with or without helium.
  • the metal bromide resulting from the process can be converted in oxygen or in air to obtain the original metal oxide and bromine, both of which are recycled.
  • the conversion reaction takes place at a temperature range of between about 50 to about 700 2 C and a pressure range from about 1 to 300atm.
  • the method of the present invention operates on ' a continuous or batch basis to convert olefin bromohydrins and/or alkane dibromides to olefins oxides.
  • the method of the present invention operates at relatively low temperatures and at low pressures and is therefore economical in use.
  • the favorable economics of the method also result from the fact that only the bromohydrin and/or dibromide reactants and oxygen are consumed. " The method does not involve direct contact between the reactants and oxygen and is therefore relatively safe.

Abstract

Olefin bromohydrins and/or alkane dibromides are reacted with metal oxide to form olefin oxides. The metal bromide is converted to form the original metal oxide and bromine, both of which are recycled.

Description

PROCESS FOR SYNTHESIZING OLEFIN OXIDES
CROSS REFERENCE TO RELATED APPLICATION
This is a continuation-in-part application under 37 C.F.R. §1.63 of Application Serial No. 09/886,078 filed June 20, 2001, currently pending.
TECHNICAL FIELD
This invention relates generally to the synthesis of olefin oxides, and more particularly to an economical and safe process for synthesizing propylene oxide and other olefin oxides .
BACKGROUND AND SUMMARY OF THE INVENTION
Co-pending application serial number 09/886,078 filed June 20, 2001 and assigned to the assignee hereof is incorporated herein by reference. The co-pending application discloses and claims a process for synthesizing alcohols and ethers from alkanes . The process involves reacting an alkane with bromine to form the corresponding alkyl bromide and hydrogen bromide. The alkyl bromide and the hydrogen bromide are reacted with a metal oxide to produce the corresponding alcohol and/or ether, and metal bromide. The metal bromide is oxidized to form the original metal oxide and bromine, both of which are recycled.
The present invention employs a similar procedure to synthesize olefin oxides, particularly propylene oxide. Propylene oxide has heretofore been produced using a wide variety of procedures, none of which is particularly satisfactory.
The oldest and most widely used procedure for preparing propylene oxide is the propylene chlorohydrin process. An early propylene chlorohydrin technique involved electrolyzation of propylene in aqueous potassium chloride to prepare propylene chlorohydrin which was then dehydrohalogenated to produce propylene oxide. At the present time propylene oxide is prepared by reacting propylene with chlorine/water to prepare propylene chlorohydrin, then reacting the propylene chlorohydrin with aqueous calcium hydroxide, sodium hydroxide or calcium carbonate to obtain propylene oxide. A major drawback to the propylene chlorohydrin process involves the fact that the manufacture of a given quantity of propylene oxide necessarily results in the manufacture of a like or greater quantity of various salts which have little commercial value. A further disadvantage of the propylene chlorohydrin process is the fact that the propylene oxide product must be separated from large quantities of water, generally through steam stripping.
Propylene oxide can also be manufactured utilizing the ethylbenzene process. As currently practiced the ethylbenzene process involves reacting ethylbenzene with oxygen to generate ethylbenzene hydroperoxide which is then reacted with propylene to obtain propylene oxide and alpha phenylethano1. The alpha phenylethanol is then converted to styrene by dehydration. The major drawbacks to the ethylbenzene process involves the production of styrene in equal quantities with the desired propylene oxide and the use of ethylbenzene hydroperoxide, which is both explosive and subject to decomposition. Cumene can also be used to manufacture propylene oxide. The cumene is oxidized to produce cumene hydroperoxide which is then reacted with propylene to form propylene oxide and cumyl alcohol. The cumyl alcohol is reduced to cumene by reaction with hydrogen over a catalyst and is recycled. The drawbacks to the cumene process include the use of large amounts of cumene hydroperoxide which is highly explosive and the consumption of expensive hydrogen. A fourth process for manufacturing propylene oxide is known as the tert-butane hydroperoxide process. In accordance therewith isobutane is oxidized by reaction with oxygen to obtain tertiary butane hydroperoxide, which is then reacted with propylene to form propylene oxide and tert-BuOH. The drawbacks to the process include the direct reaction of butane with oxygen, the use of dangerous tert-butane hydroperoxide, and the production of tert-BuOH as a byproduct.
Still another process for producing propylene oxide is known as the hydrogen ■ peroxide process . In accordance therewith, propylene is reacted with hydrogen peroxide in a solvent such as methanol over a catalyst. Drawbacks to the process include the fact that the reaction rate is very slow and the fact that expensive hydrogen is necessarily consumed to form hydrogen peroxide .
A sixth method of synthesizing propylene oxide involves direct oxidation of propylene. In accordance with the procedure, propylene is reacted with oxygen over a catalyst to generate propylene oxide. As will be apparent, safety considerations dictate that the process is very carefully controlled. Other drawbacks include low conversion rates, typically below 10% and low selectivity, typically below 40%.
The present invention comprises a method of synthesizing propylene oxide and other olefin oxides which overcomes the foregoing and other difficulties that have long since characterized the prior art. In accordance with the broader aspects of the invention, an olefin bromohydrin or an alkane dibromide is reacted with a metal oxide to form olefin oxide and metal bromide. The metal bromide is converted to obtain the original metal oxide and bromine, both of which are recycled.
DETAILED DESCRIPTION
In the process of the present invention an olefin bromohydrin and/or an alkane dibromide (such as propylene bromohydrin and/or 1, 2-dibromopropane) is reacted with a metal oxide to synthesize olefin oxide
(such as propylene oxide) , with the corresponding metal bromide being formed as a by product . The metal bromide is converted back to the original metal oxide and bromine, both of which are recycled. The process consumes nothing other than olefin and oxygen. There is no direct contact between oxygen and olefin, and the process does not result in large amounts of HCl or Cl2 in water as in the traditional olefin chlorohydrin process. A further benefit of the process results from the easy separation of olefin oxide from the alkane dibromide rather than the separation of the olefin oxide from aqueous alkaline waste.
EXAMPLE Zr solution preparation
Zr (OCH2CH2CH3)4 (70(w)% in isopropanol, 112.6 ml) was dissolved into acetic acid (275ml) under stirring. After stirring for 10 minutes, the solution was diluted by water to make a total volume of' 500ml. A solution with a Zr concentration of 0.5M was obtained. Preparation of metal oxide M Ml
Cu(N03)2 (0.5M, 64.0ml) solution was added .into Zr solution (0.5 , 64.0ml) (as prepared above). After stirring for a few seconds, a gel was obtained. The gel was dried at 1102C for 4 hours, then heated to 5002C within 6 hours, and calcined at 5002C for 4 hours. CuO/Zr02 metal oxide (Ml) was obtained. M2
Cu(N03)2 (0.5M, 6.8ml) solution was mixed with BaBr2(0.5M, 1.2ml). A clear solution was obtained. The solution was added into Zr solution (0.5M, 8.0ml) (as prepared above) . After stirring for a few seconds, a gel was obtained. The gel was dried at 1102C for 4 hours, then heated to 500SC within 6 hours, and calcined at 5002C for 4 hours. BaBr2CuO/Zr02 metal oxide (M2) was obtained. M3 Cu(N03)2 (0.5M, 7.6ml) solution was mixed with CaBr2(0.5M,
0.4ml). A clear solution was obtained. The solution was added into Zr solution (0.5M, 8.0ml) (as prepared above) . After stirring for a few seconds, a gel was obtained. The gel was dried at 110SC for 4 hours, then heated to 500aC within 6 hours, and calcined at 5002C for 4 hours. CaBr2CuO/Zr02 metal oxide (M3) was obtained.
M4
Cu(N03)2 (0.5M, 7.6ml) solution was mixed with SrBr2(0.5M, 0.4ml) . A clear solution was obtained. The solution was added into Zr solution (0.5M, 8.0ml) (as prepared above) . After stirring for a few seconds, a gel was obtained. The gel was dried at 1102C for 4 hours, then heated to 500aC within 6 hours, and calcined at 5002C for 4 hours. SrBr2CuO/Zr02 metal oxide (M4) was obtained.
Testing
Reaction on Ml
Propylene bromohydrin (1.00ml/hour) and helium (2.0ml/minute) were passed through a reactor that was packed with 3.0000 gram Ml, which was heated to 1002C.
Within the first 2 hours, an average propylene bromohydrin conversion of 35%, with 50% propylene oxide average selectivity and 50% acetone selectivity was obtained. In the second hour, only propylene oxide was obtained.
1,2-dibro opropane
1, 2-dibromopropane (1. OOml/hour) and helium (2. Oml/minute) were passed through a reactor packed with M at 1002C. Within the first 2 hours, an average 1,2- dibromopropane conversion of 40%, with 30% propylene oxide average selectivity and 70% acetone selectivity was obtained. Reaction on M2
Propylene bromohydrin (1. OOml/hour) and helium
(2. Oml/minute) were passed through a reactor that was packed with 1.1784 gram M2 , which was heated to 1002C.
Within the first 2 hours, an average propylene bromohydrin conversion of 50%, with 67% propylene oxide average selectivity and 33% acetone selectivity was obtained.
When running M2 at 802C, 40% propylene bromohydrin conversion with 75% propylene oxide selectivity was obtained.
1, 2-dibromopropane
1, 2-dibromopropane (1. OOml/hour) and helium
(2. Oml/minute) were passed through a reactor packed with
M2 at 1002C. Within the first 2 hours, an average 1,2- ' dibromopropane conversion of 42%, with 62% propylene oxide average selectivity was obtained. Reaction on M3
Propylene bromohydrin (0.50ml/hour) and nitrogen (5. Oml/minute) were passed through a reactor that packed with 0.8286 gram M3, which was heated to 1202C. Within the first 1.5 hours, an average propylene bromohydrin conversion of 50%, with 41% propylene oxide average selectivity was obtained. 1,2-dibromopropane 1, 2-dibromopropane (1. OOml/hour) (0.50ml/hour) and nitrogen (5. Oml/minute) were passed through a reactor that packed with 0.8286 gram M3 , which was heated to 100ΞC. Within the first 1.5 hours, an average propylene bromohydrin conversion of 40%, with 59% propylene oxide average selectivity was obtained.
Reaction on M4
Propylene bromohydrin (0.50ml/hour) and nitrogen
(5. Oml/minute) were passed through a reactor that packed with 0.8836 gram M4, which was heated to 1202C. Within the first 2 hours, an average propylene bromohydrin conversion of 40%, with 56% propylene oxide average selectivity was obtained.
In the above reactions, the metal oxide can be an oxide 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, Al, Ga, In, Tl, Ge, Sn, Pb, P, Sb, Bi, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, , La, Ce, Pr, Nd, S , Eu, Gd, Tb, Er, Yb, Lu, and Cs, or mixtures thereof. The reactions can be carried out at a temperature range of between about 502C to about 6002C. The reactions pressure can be from about 1 to about 200 atm. The reaction can be carried out with or without helium. The metal bromide resulting from the process can be converted in oxygen or in air to obtain the original metal oxide and bromine, both of which are recycled. The conversion reaction takes place at a temperature range of between about 50 to about 7002C and a pressure range from about 1 to 300atm.
The method of the present invention operates on ' a continuous or batch basis to convert olefin bromohydrins and/or alkane dibromides to olefins oxides. The method of the present invention operates at relatively low temperatures and at low pressures and is therefore economical in use. The favorable economics of the method also result from the fact that only the bromohydrin and/or dibromide reactants and oxygen are consumed. " The method does not involve direct contact between the reactants and oxygen and is therefore relatively safe.
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

THE CLAIMS
1. A method for synthesizing olefin oxides comprising: providing a quantity of a reactant selected from the group including bromohydrins and alkane dibromides ; reacting the selected reactant with a metal oxide and thereby forming olefin oxide and a metal bromide; converting 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 reacting step is carried out at a pressure of between about 1 and about 300 ATM.
3. The method according to claim 1 wherein the reacting step is carried out at a temperature of between about 50°C and about 600°C.
4. The process according to claim 1 wherein • the reacting step is carried out continuously.
5. The process according to claim 1 wherein the reacting step is carried out in a batch reaction.
6. The method according to claim 1 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out continuously.
7. The method according to claim 1 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out in a batch reaction.
8. A method for converting an olefin to is corresponding olefin oxide comprising: providing a quantity of an olefin; providing a quantity of bromine; providing a quantity of water reacting the olefin with bromine/H20 and thereby forming the corresponding olefin bromohydrin; reacting the olefin bromohydrin with a metal oxide and thereby forming the corresponding olefin oxide; converting the metal bromide to form the original metal oxide and bromine; recycling the metal oxide; and recycling the bromine .
9. The method according to claim 8 wherein the step of reacting the olefin bromohydrin with the metal oxide is carried out a pressure of between about 1 to about 300 ATM.
10. The method according to claim 8 wherein' the step reacting the olefin bromohydrin with the metal oxide is carried out at a temperature of between about 50°C and about 600°C.
11. The method according to claim 8 wherein the metal oxide includes an oxide of at least one of the following metals :
Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co,
5 Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Ge, Sn, Pb, P, Sb, Bi, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs .
12. The process according to claim 8 wherein the 10. step of reacting the olefin bromohydrin with the metal oxide is carried out continuously.
13. The process according to claim 8 wherein the step of reacting the olefin bromohydrin with the metal
15 oxide is carried out in a batch reaction.
14. The method according to claim 8 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling
20 the metal oxide, and the step of recycling the bromine are carried out continuously.
15. The method according to claim 8 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out in a batch reaction.
16. A method for converting an olefin to its corresponding olefin oxide comprising: providing a quantity of an olefin; providing a quantity of bromine; reacting the olefin with the bromine and thereby forming the corresponding alkane dibromide; reacting the alkane dibromide with a metal oxide and thereby forming the corresponding olefin oxide; converting the metal bromide to form the original metal oxide and bromine; recycling the metal oxide; and recycling the bromine.
17. The method according to claim 16 wherein the step of reacting the alkane dibromide with the metal oxide is carried out at a pressure of between about 1 to about 300 ATM.
18. The method according to claim 16 wherein the step of reacting the alkane dibromide with the metal oxide is carried out at a temperature of between about 50°C and about 600°C.
19. The process according to claim 16 wherein the step of reacting the alkane dibromide with the metal oxide is carried out continuously.
20. The process according to claim 16 wherein the step of reacting the alkane dibromide with the metal oxide is carried out in a batch reaction.
21. The method according to claim 16 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out continuously.
22. The method according to claim 16 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out in a batch reaction.
23. The method according to claim 16 wherein the metal oxide includes an oxide of at least one of the following metals :
Ti, Zr, Hf, V, b, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Ge, Sn, Pb, P, Sb, Bi, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs .
24. A method for synthesizing olefin oxides from alkanes comprising: providing a quantity of an alkane selected from the group including ethane, propane, butane, isobutane, pentanes, cyclohexane and hexanes; providing a quantity of bromine; reacting the selected alkane and the bromine and thereby forming the corresponding alkane dibromide; reacting the alkane dibromide with a metal oxide and thereby forming olefin oxide and a metal bromide; recovering the thus formed olefin oxide; converting the metal bromide to form the original metal oxide and bromine; recycling the metal oxide; and recycling the bromine.
25. The method according to claim 24 wherein the step of reacting the alkane dibromide with the metal oxide is carried out at a pressure of between about 1 and about 300 ATM.
26. The method according to claim 24 wherein the step of reacting the alkane dibromide with the metal oxide is carried out at a temperature of between about 50°C and about 600°C.
27. The process according to claim 24 wherein the steps of forming the alkane dibromide and reacting the alkane dibromide with a metal oxide are carried out continuously.
28. The process according to claim 24 wherein the steps forming the alkane dibromide and the step of reacting the alkane dibromide with a metal oxide are carried out in a batch reaction.
29. The method according to claim 24 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out continuously.
30. The method according to claim 24 wherein the step of oxidizing the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out in batch reactions .
31. The method according to claim 24 wherein the metal oxide includes an oxide of at least one 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, Al , Ga, In, Tl,
Ge, Sn, Pb, P, Sb, Bi, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs .
32. The method according to claim further characterized by forming 1,2 dibromopropane over a brominating catalyst.
33. The method according to claim 32 wherein the step of forming 1,2 dibromopropane is practiced using heat.
34. The method according to claim 32 wherein the step of forming 1,2 dibromopropane is practiced using electromagnetic radiation.
35. The method according to claim 32 wherein the step of forming 1,2 dibromopropane is practiced using a combination of a brominating catalyst, heat and electromagnetic radiation.
36. A method for synthesizing olefin oxides from olefins comprising: providing a quantity of an olefin selected from the group including ethylene, propylene butylene, pentenes, cyclohexene and hexenes; providing a quantity of bromine; providing a quantity of water reacting the selected olefin and bromine/H20 and thereby forming the corresponding olefin bromohydrin; reacting the olefin bromohydrin with a metal oxide and thereby forming olefin oxide and a metal bromide; recovering the thus formed olefin oxide; converting the metal bromide to form the original metal oxide and bromine; recycling the metal oxide catalyst; and recycling the bromine.
37. The method according to claim 36 wherein the step of reacting the bromohydrin with the metal oxide is carried out at a pressure of between about 1 and about 300 ATM.
38. The method according to claim 36 wherein the step of reacting the bromohydrin with the metal oxide is carried out at a temperature of between about 50°C and
about 600°C.
39. The process according to claim 36 wherein the steps of forming the bromohydrin and reacting the bromohydrin with a metal oxide are carried out continuously.
40. The process according to claim 36 wherein the step forming the bromohydrin and the step of reacting the bromohydrin with a metal oxide are carried out in a batch reaction.
41. The method according to claim 36 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out continuously.
42. The method according to claim 36 wherein the step of converting the metal bromide to form the original metal oxide and bromine, the step of recycling the metal oxide, and the step of recycling the bromine are carried out in batch reactions .
43. The method according to claim 36 wherein the metal oxide includes an oxide of at least one 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, Al, Ga, In, Tl,
Ge, Sn, Pb, P, Sb, Bi, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs .
44. A method for synthesizing propylene oxide from propane comprising: providing a quantity of propane; providing a quantity of bromine; reacting the propane and the bromine and thereby forming 1, 2-dibromopropane; reacting the 1, 2-dibromopropane with a metal oxide and thereby forming propylene oxide and a metal bromide; recovering the thus formed propylene oxide; converting the metal bromide to form the original metal oxide and bromine; recycling the metal oxide catalyst; and recycling the bromine.
45. The method according to claim 44 wherein the step of reacting the 1, 2-dibromopropane with the metal oxide is carried out at a pressure of between about 1 and about 300 ATM.
46. The method according to claim 41 wherein the step of reacting the 1, 2-dibromopropane with the metal oxide is carried out at a temperature of between about 50°C and about 600°C.
47. The process according to claim 44 wherein the step of forming the 1, 2-dibromopropane and the step of reacting the 1, 2-dibromopropane with a metal oxide are carried out continuously.
48. The process according to claim 44 wherein the step forming the 1, 2-dibromopropane and the step of reacting the 1, 2-dibromopropane with a metal oxide are carried out in a batch reaction.
49. The method according to claim 44 wherein the step of converting the metal bromide to form the original metal oxide catalyst and bromine, the step of recycling the metal oxide catalyst, and the step of recycling the bromine are carried out continuously.
50. The method according to claim 44 wherein the step of converting 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 batch reactions .
51. The method according to claim 44 wherein the metal oxide (s) is the oxide or oxide mixtures 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, Al, Ga, In, TI,
Ge, Sn, Pb, P, Sb, Bi, Sc, Y, Mg, Ca, Sr, Ba, Na, Li, K, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb, Lu, and Cs .
52. The method according to claim 44 wherein the step of forming 1,2 dibromopropane is practiced over a brominating catalyst.
53. The method according to claim 44 wherein the step of forming 1,2 dibromopropane is practiced using heat.
54. The method according to claim 44 wherein the step of forming 1,2 dibromopropane is practiced using electromagnetic radiation.
55. The method according to claim 44 wherein the step of forming 1,2 dibromopropane is practiced using a combination of a brominating catalyst, heat and electromagnetic radiation.
PCT/US2002/020981 2001-09-11 2002-06-10 Process for synthesizing olefin oxides WO2003022827A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7148390B2 (en) 2001-06-20 2006-12-12 Grt, Inc. Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
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
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes 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
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
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
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides

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* Cited by examiner, † Cited by third party
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US7019182B2 (en) 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7361794B2 (en) 2001-04-18 2008-04-22 Grt, Inc. Zone reactor
US7838708B2 (en) 2001-06-20 2010-11-23 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
US7161050B2 (en) 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US8415512B2 (en) 2001-06-20 2013-04-09 Grt, Inc. Hydrocarbon conversion process improvements
US7847139B2 (en) 2003-07-15 2010-12-07 Grt, Inc. Hydrocarbon synthesis
US7964764B2 (en) 2003-07-15 2011-06-21 Grt, Inc. Hydrocarbon synthesis
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
US7348464B2 (en) 2004-04-16 2008-03-25 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes 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
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US7883568B2 (en) 2006-02-03 2011-02-08 Grt, Inc. Separation of light gases from halogens
US8053616B2 (en) 2006-02-03 2011-11-08 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
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
US8415517B2 (en) 2008-07-18 2013-04-09 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US8273929B2 (en) 2008-07-18 2012-09-25 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc 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
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