WO2018203179A1 - Production efficace de mtbe, d'oxyde d'éthyle et d'éthylène glycol à partir de charges d'alimentation d'isobutane, d'éthylène et d'oxygène - Google Patents

Production efficace de mtbe, d'oxyde d'éthyle et d'éthylène glycol à partir de charges d'alimentation d'isobutane, d'éthylène et d'oxygène Download PDF

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WO2018203179A1
WO2018203179A1 PCT/IB2018/052812 IB2018052812W WO2018203179A1 WO 2018203179 A1 WO2018203179 A1 WO 2018203179A1 IB 2018052812 W IB2018052812 W IB 2018052812W WO 2018203179 A1 WO2018203179 A1 WO 2018203179A1
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reactor
mtbe
tba
tbhp
isobutylene
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PCT/IB2018/052812
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English (en)
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Guillermo LEAL
Mohammed Bismillah ANSARI
Vijay Dinkar BODAS
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Sabic Global Technologies B.V.
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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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • 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
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • 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
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/025—Sulfonic acids
    • 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

Definitions

  • the present invention generally relates to the production of methyl tert-butyl ether (MTBE) and ethylene oxide from crude C 4 streams.
  • the inventive method involves production of a tert-butyl hydroperoxide (TBHP) intermediate product by oxidation of isobutane and reacting the TBHP intermediate with ethylene to produce tert-butyl alcohol (TBA) as the main product and ethylene oxide as a by-product.
  • TBHP tert-butyl hydroperoxide
  • MTBE is used as a gasoline blending component.
  • Commercial MTBE synthesis plants typically have three major units: an isomerization unit that converts a crude C 4 stream into isobutane, a dehydrogenation unit that converts isobutane to isobutylene, and an MTBE synthesis unit that reacts isobutylene with methanol to produce MTBE.
  • the dehydrogenation process that is typically used in commercial plants is the CATOFIN process, which has been in use for many decades and which uses a chromium catalyst that has been associated in some instances with potentially negative environmental impacts if not handled properly.
  • This process also suffers from a lack of efficiency in that the stream flowing from the dehydrogenation unit to the MTBE unit contains a large amount of isobutane, which cannot be used in the MTBE unit and must be recycled back to the dehydrogenation unit.
  • the above-mentioned needs are met by the integrated synthesis process described herein.
  • the process is an integrated method that includes oxidizing isobutane to form TBHP in an oxidation reactor; flowing the TBHP to an epoxidation reactor, where it reacts with ethylene to form mainly TBA and ethylene oxide; flowing the TBA into a dehydration reactor, where the TBA is dehydrated to form isobutylene, for example high purity isobutylene; and flowing the high purity isobutylene to an MTBE synthesis unit, where it reacts with methanol to form MTBE.
  • the process can use two of the three units already present in conventional MTBE synthesis plants: the isomerization unit and the MTBE synthesis unit.
  • the process can bypass the dehydrogenation unit, as the isobutylene feed for the MTBE synthesis unit is produced by dehydration of TBA rather than by dehydrogenation of isobutane.
  • the isobutylene stream into the MTBE synthesis unit is highly pure, in contrast to the stream produced by CATOFIN dehydrogenation units, which includes a mixture of isobutane and isobutylene (50/50 % weight correlation).
  • the high purity isobutylene stream increases the yield of MTBE as compared to standard MTBE synthesis processes employing a dehydrogenation step and enhances the overall efficiency of the system.
  • MMA methyl methacrylate
  • HPIC4 high purity isobutylene
  • butyl rubber polyisobutylenes
  • BHT butylated hydroxytoluene
  • tert-butyl amines 2,6-di-tert-butyl phenol, tert-butyl amine, tert-butyl mercaptan
  • isobutyl aluminum compounds isoprene, among other products, all from the same feedstock.
  • Embodiments of the invention include an integrated method for producing
  • the method may include reacting ethylene with TBHP to form TBA in an epoxidation reactor; flowing the TBA from the epoxidation reactor into a dehydration reactor; dehydrating the TBA to form isobutylene, for example high purity isobutylene, in the dehydration reactor; flowing the high purity isobutylene from the dehydration reactor into an MTBE synthesis unit; and reacting the high purity isobutylene with methanol to form MTBE in the MTBE synthesis unit.
  • “high purity” refers to a purity of at least 99.3 wt. %.
  • the isobutylene that is fed into the MTBE synthesis unit may also have a purity of between about 90.0 and 99.9 wt. %.
  • the yield of MTBE from the reaction of the isobutylene stream with methanol in the MTBE synthesis unit may be between about 98.0 and 99.9%. This high yield is made possible in part by the highly pure isobutylene feed from the dehydration reactor into the MTBE synthesis unit and by the optimum operation conditions used in the method, including lower temperature cooling and optimum pressure in the system.
  • the TBHP may be produced by oxidizing isobutane in an oxidation reactor, which may include bubbling a gas composition comprising oxygen through liquid isobutane or may use fixed bed reactor technology.
  • the gas composition may be air.
  • the isobutane used in producing TBHP in the oxidation reactor may be produced by isomerization of normal butane (n-butane) in an isomerization unit.
  • the feedstock for the isomerization unit may be at least a portion of effluent from refinery streams comprising n-butane and isobutane.
  • TBA may also be produced in the oxidation reactor, and the TBA can flow from the oxidation reactor to the dehydration reactor, so that the dehydration reactor receives TBA from both the oxidation reactor and the epoxidation reactor.
  • ethylene oxide may be produced by the epoxidation reaction of TBHP with ethylene.
  • the ethylene oxide produced may be used in a process of making ethylene glycol.
  • the reaction between ethylene and TBHP may take place in the presence of, and be catalyzed by, a catalyst comprising a transition metal that associates with the TBHP to form an active catalyst having a peroxy ligand.
  • the transition metal may be molybdenum, and the catalyst may have the formula M0O2L2, wherein L represents an NO-type ligand.
  • the TBHP fed into the epoxidation reactor may not be entirely consumed in the epoxidation reaction, and any unreacted TBHP can be recycled to the oxidation reactor.
  • the amount of TBHP recycled to the oxidation reactor can be varied to adjust the relative amounts of ethylene oxide and TBA produced in the epoxidation reactor. This provides a distinct advantage relative to known processes, as it allows the process to adjust to market conditions to produce the desired relative amounts of the products.
  • the process of making MTBE disclosed herein may be performed without the use of chromium as a catalyst and/or without the use of chromium-containing catalysts. It may also be performed without dehydrogenation of isobutane, either by the CATOFIN process or by other processes currently available in the market.
  • Embodiments of the invention include an integrated method for producing
  • the method including oxidizing isobutane to form TBHP in an oxidation reactor; flowing the TBHP from the oxidation reactor into an epoxidation reactor; reacting ethylene with TBHP to form TBA in the epoxidation reactor; flowing the TBA from the epoxidation reactor into a dehydration reactor; dehydrating the TBA to form isobutylene, for example high purity isobutylene, in the dehydration reactor; flowing the high purity isobutylene from the dehydration reactor into an MTBE synthesis unit; and reacting the high purity isobutylene with methanol to form MTBE in the MTBE synthesis unit.
  • TBA may also be produced in the oxidation reactor, and the TBA can flow from the oxidation reactor to the dehydration reactor, so that the dehydration reactor receives TBA from both the oxidation reactor and the epoxidation reactor. Any unreacted TBHP in the epoxidation reactor may be recycled to the oxidation reactor.
  • Embodiments of the invention include an integrated method for producing MTBE, the method including oxidizing isobutane to form TBHP in an oxidation reactor; flowing the TBHP from the oxidation reactor into an epoxidation reactor; reacting ethylene with TBHP to form TBA, ethyl oxide, and ethylene glycol in the epoxidation reactor; flowing the TBA from the epoxidation reactor into a dehydration reactor; dehydrating the TBA to form isobutylene, for example high purity isobutylene, in the dehydration reactor; flowing the high purity isobutylene from the dehydration reactor into an MTBE synthesis unit; and reacting the high purity isobutylene with methanol to form MTBE in the MTBE synthesis unit.
  • TBA may also be produced in the oxidation reactor, and the TBA can flow from the oxidation reactor to the dehydration reactor, so that the dehydration reactor receives TBA from both the oxidation reactor and the epoxidation reactor.
  • embodiments disclosed herein can be used to supplement the existing production of isobutylene by the dehydrogenation unit. In such embodiments, isobutane produced in the isomerization unit would flow to both an oxidation reactor for production of TBHP and TBA and to a dehydrogenation reactor for production of isobutylene.
  • the isobutylene produced by dehydration of TBA can be combined with the isobutane/isobutylene stream flowing from the dehydrogenation unit to the MTBE synthesis unit. This can increase the relative amount of isobutylene in the feed and enhance the yield of MTBE relative to facilities whose only source of isobutylene is a dehydrogenation unit.
  • Embodiments of the invention also include repurposing the existing dehydrogenation unit in an MTBE synthesis facility to produce propylene.
  • Methods of the present invention do not require dehydrogenation of isobutane to produce isobutylene, which frees the dehydrogenation unit to be used for another purpose.
  • a fixed bed or fluidized bed dehydrogenation unit can be modified by known methods to dehydrogenate propane to produce propylene. This further increases the range of products that can be produced at an existing MTBE synthesis facility.
  • All of the features described for the embodiments disclosed above can be incorporated into the other embodiments. For example, each of the embodiments may produce a yield of MTBE between 98.0 and 99.9%. All of the other features described for one embodiment may likewise be incorporated into any other embodiment.
  • the terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.
  • the terms “wt. %”, “vol. %” or “mol. %” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol. % of component.
  • the term “substantially” and its variations are defined to include ranges within
  • Embodiment 1 is an integrated method for producing methyl tert-butyl ether (MTBE).
  • the method of embodiment 1 includes the steps of reacting ethylene with tert-butyl hydroperoxide (TBHP) to form tert-butyl alcohol (TB A) in an epoxidation reactor; flowing the TBA from the epoxidation reactor into a dehydration reactor; dehydrating the TBA to form isobutylene, for example high purity isobutylene, in the dehydration reactor; flowing the high purity isobutylene from the dehydration reactor into an MTBE synthesis unit; and reacting the high purity isobutylene with methanol to form MTBE, in the MTBE synthesis unit.
  • Embodiment 2 is the method of embodiment 1, wherein the TBHP is produced by oxidizing isobutane in an oxidation reactor.
  • Embodiment 3 is the method of embodiment 2, wherein oxidizing isobutane includes bubbling air through liquid isobutane.
  • Embodiment 4 is the method of embodiment 2 or 3, wherein oxidizing isobutane in the oxidation reactor additionally produces TBA, and wherein the TBA produced in the oxidation reactor flows from the oxidation reactor into the dehydration reactor.
  • Embodiment 5 is the method of any one of embodiments 1 to 4, wherein unreacted TBHP from the epoxidation reactor is recycled to the oxidation reactor.
  • Embodiment 6 is the method of any one of embodiments 1 to 5, wherein reacting ethylene with TBHP in the epoxidation reactor additionally produces ethylene oxide.
  • Embodiment 7 is the method of embodiment 6, wherein the ethylene oxide is used to produce monoethylene glycol.
  • Embodiment 8 is the method of any one of embodiments 1 to 7, wherein the isobutane is produced by isomerization of n-butane in an isomerization unit.
  • Embodiment 9 is the method of embodiment 8, wherein feedstock for the isomerization unit is at least a portion of effluent from refinery streams containing n-butane and iso-butane.
  • Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the high purity isobutylene has a purity of between about 99.3 and 99.90 wt. %.
  • Embodiment 11 is the method of any one of embodiments 1 to 10, wherein reacting ethylene with TBHP takes place in the presence of a catalyst containing a transition metal that associates with the TBHP to form an active catalyst having a peroxy ligand.
  • Embodiment 12 is the method of embodiment 11, wherein the transition metal is molybdenum.
  • Embodiment 13 is the method of any one of embodiments 1 to 12, wherein the method does not include use of chromium as a catalyst.
  • Embodiment 14 is the method of any one of embodiments 1 to 13, wherein the method does not include dehydrogenation of isobutane.
  • Embodiment 15 is the method of any one of embodiments 1 to 14, wherein the MTBE yield is between about 98.0 and 99.9 wt. %.
  • Embodiment 16 an integrated method for producing methyl tert-butyl ether
  • MTBE tert-butyl hydroperoxide
  • This method includes the steps of oxidizing isobutane to form tert-butyl hydroperoxide (TBHP) in an oxidation reactor; flowing the TBHP from the oxidation reactor into an epoxidation reactor; reacting ethylene with TBHP to form tert-butyl alcohol (TBA) in the epoxidation reactor; flowing the TBA from the epoxidation reactor into a dehydration reactor; dehydrating the TBA to form isobutylene, for example high purity isobutylene, in the dehydration reactor; flowing the high purity isobutylene from the dehydration reactor into an MTBE synthesis unit; and reacting the high purity isobutylene with methanol to form MTBE in the MTBE synthesis unit.
  • TBHP tert-butyl hydroperoxide
  • TBA tert-butyl alcohol
  • Embodiment 17 is the method of embodiment 16, wherein oxidizing isobutane in the oxidation reactor additionally produces TBA, and wherein the TBA produced in the oxidation reactor flows from the oxidation reactor into the dehydration reactor.
  • Embodiment 18 is the method of embodiment 17, wherein unreacted TBHP from the epoxidation reactor is recycled to the oxidation reactor.
  • Embodiment 19 is an integrated method for producing methyl tert-butyl ether (MTBE).
  • the method of embodiment 19 includes the steps of oxidizing isobutane to form tert- butyl hydroperoxide (TBHP) in an oxidation reactor; flowing the TBHP from the oxidation reactor into an epoxidation reactor; reacting ethylene with TBHP to form tert-butyl alcohol (TBA) and ethylene oxide in the epoxidation reactor; flowing the TBA from the epoxidation reactor into a dehydration reactor; dehydrating the TBA to form isobutylene, for example high purity isobutylene, in the dehydration reactor; flowing the high purity isobutylene from the dehydration reactor into an MTBE synthesis unit; and reacting the high purity isobutylene with methanol to form MTBE in the MTBE synthesis unit.
  • Embodiment 20 is the method of embodiment 19, wherein oxidizing isobutane in the
  • FIG. 1 is an illustration of a system that can be used to carry out embodiments of the inventive method of producing MTBE and ethylene oxide described herein;
  • FIG. 2 is an illustration of an oxidation reaction by which isobutane is reacted with oxygen to form TBHP and TBA (main product); and
  • FIG. 3 is an illustration of an epoxidation reaction by which ethylene reacts with TBHP to create TBA (main product) and ethylene oxide (by-product).
  • Embodiments of the invention involve a TBHP intermediate, which reacts with ethylene in an epoxidation reaction to yield TBA and ethylene oxide.
  • the TBA is fed into a dehydration reactor, where it is converted into isobutylene, for example highly pure isobutylene, which is fed into an MTBE synthesis unit.
  • the ethylene oxide produced in the epoxidation reaction can be used for production of monoethylene glycol.
  • Embodiments of the invention can be carried out at a modified MTBE production facility.
  • Conventional MTBE production facilities typically have three primary units: an isomerization unit, a dehydrogenation unit, and an MTBE synthesis unit.
  • the process of making MTBE typically starts with a crude C 4 stream, which may be provided from a refinery stream, such as from a steam cracker that produces olefins.
  • the crude C 4 stream typically includes a mixture of at least n-butane and isobutane.
  • the isomerization unit separates the n- butane from the isobutane and isomerizes the n-butane to form isobutane.
  • the outflow stream from the isomerization unit comprises primarily isobutane.
  • the isobutane then flows into the dehydrogenation unit, which dehydrogenates the isobutane to form isobutylene.
  • a common dehydrogenation process in commercial use is the CATOFIN process, which employs a chromium-containing catalyst.
  • the outflow from the dehydrogenation unit includes both isobutylene and an approximately equal amount of unreacted isobutane.
  • This mixture is fed along with methanol into the MTBE synthesis unit, where the isobutylene reacts with methanol to form MTBE.
  • the unreacted isobutane is recycled from the MTBE synthesis unit back to the dehydrogenation unit.
  • Embodiments of the methods of the invention can be carried out using two of the three primary units typically used in conventional MTBE production facilities: the isomerization unit and the MTBE synthesis unit. Additional units that may be used to carry out embodiments of the methods include an oxidation reactor, an epoxidation reactor, and a dehydration reactor.
  • a system 10 that may be used to make MTBE and monoethylene glycol is illustrated in FIG. 1.
  • a crude stream of mixed C 4 compounds flows through line 12 to isomerization reactor 14.
  • the mixed C 4 stream may include both n-butane and isobutane.
  • n-butane is isomerized to isobutane and the net isobutane is separated and passed via line 16 to oxidation reactor 20.
  • Oxygen also flows via line 18 into the oxidation reactor 20.
  • isobutane and oxygen react to form TBA and TBHP, as illustrated in FIG. 2.
  • the oxidation reaction can be a liquid/liquid reaction in which oxygen, which may be provided in the form of air, is bubbled through liquid isobutylene.
  • additional products of the oxidation reaction may include acetone, methanol, formic acid, and CO2 (not shown). These additional products are separated from the TBHP and TBA and flow out of oxidation reactor 20.
  • the oxidation reaction can be performed using known methods, such as those described in U.S. Patent No. 2,845,461 to Winkler et al., U.S. Patent No. 3,478, 108 to Grane, and U.S. Patent No. 4,408,081 to Foster et al., each of which is incorporated by reference in its entirety.
  • the TBHP produced in the oxidation reactor 20 flows via line 22 to the epoxidation reactor 26.
  • Ethylene also flows via line 24 into epoxidation reactor 26.
  • the TBHP reacts with ethylene to produce ethylene oxide and TBA, as illustrated in FIG. 3.
  • This reaction may be catalyzed by a transition metal catalyst that associates with the hydroperoxide group of TBHP, forming an active catalyst with a peroxide ligand as in the formula M-0-0-C(CH3)3, wherein M is a transition metal.
  • This active catalyst reacts with ethylene, transferring an oxygen from TBHP to ethylene, and creating an epoxide group to form ethylene oxide and TBA.
  • the catalyst used is Mo02(8-hydroxyquinoline), but other catalysts may be used.
  • the transition metal in the catalyst may be molybdenum, tungsten, titanium, niobium, tantalum, rhenium, selenium, zirconium, or tellurium.
  • the catalyst may be provided in the form of a compound containing the transition metal, such as, for example, a compound having the formula MOxLy, wherein M is a transition metal, and L is an N-O-type ligand, 0-0 type ligand, S-0 type ligand, or a ligand comprising a heterocyclic macrocycle organic compound.
  • Suitable N-0 type ligands include, for example, 8-hydroxyquinoline, 5-nitroso-8-hydroxyquinoline, salen, pyridine 2-carbinol, salphen, salicylaldoxime, and salicylimino phenol.
  • Suitable 0-0 type ligands include, for example, acac, CF3CO4, OCH2CH2OH, and C2O4.
  • Suitable S-0 type ligands include, for example, SCH2C02.
  • Suitable heterocyclic macrocycle organic compound ligands include, for example, pthalocyanine and 5,10, 15,20-tetraphenylporphyrinato (TPP) ligands.
  • Suitable catalysts may include, for example, M0O2 (8-hydroxyquinoline)2, M0O2 (5- nitroso-8-hydroxyquinoline)2, M0O2 (salen), Mo02(pyridine 2-carbinol)2, M0O2 (salphen), M0O2 (salicylaldoxime)2, M0O2 (salicylimino phenol)2, Mn (salen) acylperoxo complexes, M0O2 (acac) 2 , VO (acac) 2 , Ni(acac) 2 , M0O2 (CF 3 C0 4 ) 2 , M0O2 (OCH 2 CH 2 OH)2, [M0O2 (C 2 0 4 )]x, [M0O2 (SCH 2 C0 2 )]x, Mo(CO)e, [cyclopentadienyl Mo(CO) 3 ] 2 , (5,10, 15,20- tetraphenylpo hyrinato
  • ethylene glycol including monoethylene glycol
  • line 44 can flow into a reactor (not shown) to produce ethylene glycol, including monoethylene glycol, from the ethylene oxide.
  • This can be accomplished via conventional methods, such as by reacting ethylene oxide with CO2 to form ethylene carbonate, which can then be hydrolyzed to form monoethylene glycol and CO2.
  • Unreacted TBFIP from the epoxidation reactor 26 can be recycled via line 28 back to the oxidation reactor, from where it can flow via line 22 back into the epoxidation reactor 26.
  • the relative amounts of ethylene oxide and TBA produced during operation of the system 10 can be adjusted by altering the amount of TBFIP that is recycled back to the oxidation reactor 20 via line 28.
  • Increasing the amount of TBHP recycled back to oxidation reactor 20 reduces the amount of TBHP available in the epoxidation reactor 26 to react with ethylene to produce ethylene oxide, thus reducing the amount of ethylene oxide produced.
  • the concentration of TBHP in the oxidation reactor 20 favors the production of TBA relative to TBHP via the oxidation of isobutane.
  • the amount of TBA flowing via line 30 from the oxidation reactor 20 to the dehydration reactor 34 can be increased by recycling greater amounts of TBHP to the oxidation reactor 20. This would ultimately result in more MTBE being produced and less ethylene oxide being produced.
  • the ability to adjust the relative levels of ethylene oxide and TBA/MTBE produced through manipulation of the TBHP recycle volume is a particular advantage of embodiments of the invention. This allows the operator to respond to a changing market and use its resources efficiently.
  • the TBA produced in the epoxidation reactor 26 flows via line 32 to combine with the TBA flowing via line 30 from the oxidation reactor 20 to the dehydration reactor 34.
  • the TBA is dehydrated to form isobutylene using conventional processes, which may include heat treatment without a catalyst or with a catalyst such as para- toluene sulfonic acid, as described in U.S. Patent No. 4,165,343, which is incorporated by reference in its entirety.
  • the TBA can be collected from lines 30 and 32 as the final product in the process rather than being used for production of MTBE.
  • Isobutylene produced in the dehydration reactor 34 flows via line 36 to the MTBE synthesis unit.
  • methanol flows via line 38 into the MTBE synthesis unit 40.
  • the reaction between isobutylene and methanol is performed according to well-known methods to produce MTBE, which is collected via line 42.
  • the isobutylene stream flowing via line 36 from the dehydration reactor 34 to the MTBE synthesis reactor 40 can be between about 90 and 99.90 wt. %.
  • the purity is about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99.0, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.90, 99.99 wt. % or is between any two of these values.
  • the isobutylene stream can be highly pure isobutylene having a purity of at least 99.0 wt. %. The purity of the isobutylene contrasts with conventional MTBE production processes, which typically have a large amount of isobutane flowing into the MTBE synthesis unit along with the isobutylene that is actually used in the reaction.
  • the yield of MTBE is between about 98.0 and 99.6%. In some embodiments, the yield is about 95.0, 95.5, 96.0, 96.5, 97.0, 97.5, 98.0, 98.5, 98.6, 98.7, 98.8, 98.9, 99.0, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, or 99.9% or is between any two of these values.
  • the efficiency of the system also allows for higher volume production of MTBE than conventional MTBE plants using the same amounts of raw material inputs.
  • embodiments of the inventive method described herein can achieve specific consumption of butanes/MTBE below 0.68, whereas with conventional MTBE processing, butanes/MTBE specific consumption is in the range of 0.74 to 0.75 for UOP (Oleflex) and 0.76 to 0.82 for CATOFIN (CB&I), depending on the operational cycle of the unit (start of run, middle of run, or end of run).
  • the specific consumption of butanes/MTBE is about 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, or 0.73 or is below any of these values or is between any two of these values.
  • Specific consumption of butanes/MTBE is calculated by dividing the amount (by weight) of MTBE produced by the amount (by weight) of mixed butanes fed into the isomerization unit.

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  • Epoxy Compounds (AREA)

Abstract

La présente invention concerne un procédé intégré pour produire du MTBE et EO/MEG à partir de flux d'isobutane, d'oxygène et d'éthylène. L'isobutane est oxydé pour produire du TBHP, qui est ensuite utilisé dans une réaction d'époxydation avec de l'éthylène pour produire de l'oxyde d'éthyle et de l'éthylène glycol avec le TBA. Le TBA est ensuite déshydraté pour générer de l'isobutylène, qui est introduit avec du méthanol dans une unité de synthèse de MTBE pour produire du MTBE.
PCT/IB2018/052812 2017-05-03 2018-04-23 Production efficace de mtbe, d'oxyde d'éthyle et d'éthylène glycol à partir de charges d'alimentation d'isobutane, d'éthylène et d'oxygène WO2018203179A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021021366A1 (fr) * 2019-08-01 2021-02-04 Exxonmobil Research And Engineering Company Procédé et système permettant de produire des époxydes d'oléfine
US11827613B2 (en) 2019-08-01 2023-11-28 ExxonMobil Technology and Engineering Company Process and system to make olefin epoxides

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US2845461A (en) 1956-04-12 1958-07-29 Shell Dev Non-catalytic liquid phase isobutane oxidation
US3351635A (en) 1966-03-14 1967-11-07 Halcon International Inc Epoxidation process
US3478108A (en) 1966-02-21 1969-11-11 Atlantic Richfield Co Isobutane oxidation
US4165343A (en) 1978-07-28 1979-08-21 Cities Service Conmpany Dehydration of tertiary butyl alcohol
US4408081A (en) 1981-10-05 1983-10-04 Shell Oil Company Process for oxidation of isobutane
US5424458A (en) * 1994-03-08 1995-06-13 Arco Chemical Technology, L.P. Integrated production of propylene oxide and methyl T-butyl ether
US20130096328A1 (en) * 2011-10-17 2013-04-18 Shell Oil Company Process for preparing an epoxide from an oxygenate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2845461A (en) 1956-04-12 1958-07-29 Shell Dev Non-catalytic liquid phase isobutane oxidation
US3478108A (en) 1966-02-21 1969-11-11 Atlantic Richfield Co Isobutane oxidation
US3351635A (en) 1966-03-14 1967-11-07 Halcon International Inc Epoxidation process
US4165343A (en) 1978-07-28 1979-08-21 Cities Service Conmpany Dehydration of tertiary butyl alcohol
US4408081A (en) 1981-10-05 1983-10-04 Shell Oil Company Process for oxidation of isobutane
US4408081B1 (fr) 1981-10-05 1986-05-13
US5424458A (en) * 1994-03-08 1995-06-13 Arco Chemical Technology, L.P. Integrated production of propylene oxide and methyl T-butyl ether
US20130096328A1 (en) * 2011-10-17 2013-04-18 Shell Oil Company Process for preparing an epoxide from an oxygenate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021021366A1 (fr) * 2019-08-01 2021-02-04 Exxonmobil Research And Engineering Company Procédé et système permettant de produire des époxydes d'oléfine
CN114144403A (zh) * 2019-08-01 2022-03-04 埃克森美孚研究工程公司 制备烯烃环氧化物的方法和系统
US11827613B2 (en) 2019-08-01 2023-11-28 ExxonMobil Technology and Engineering Company Process and system to make olefin epoxides
US11919876B2 (en) 2019-08-01 2024-03-05 ExxonMobil Technology and Engineering Company Process and system to make olefin epoxides

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