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JP-2026514471-A - Co-generation of high-purity isobutylene and high-purity isooctene

JP2026514471AJP 2026514471 AJP2026514471 AJP 2026514471AJP-2026514471-A

Abstract

A system and process for the production of high-purity isobutylene streams, high-purity isooctene streams, or co-production of high-purity isobutylene and high-purity isooctene. This system and process favorably processes mixed C4 hydrocarbon streams through etherification, decomposition, isomerization, and/or dimerization, as well as various separation systems, to produce desired high-purity streams. [Selection Diagram] Figure 1

Inventors

  • バリアス，ロゼット

Assignees

  • ルーマス テクノロジー エルエルシー

Dates

Publication Date
20260511
Application Date
20240417
Priority Date
20230420

Claims (18)

  1. A process for the co-production of high-purity isobutylene and high-purity isooctene, wherein the process comprises The process involves supplying ethanol and mixed C4 hydrocarbons to an ETBE converter, wherein the mixed C4 supply stream contains a mixture of hydrocarbons including 1-butene, 2-butene, n-butane, isobutane, and isobutylene. Within the ETBE conversion apparatus, the isobutylene is reacted with ethanol using a catalyst to form ethyl tert butyl ether; the ETBE reaction effluent is recovered; and the ETBE reaction effluent is separated to recover a first fraction containing the ethyl tert butyl ether and a second fraction containing 1-butene, 2-butene, isobutane, and n-butane. The first fraction containing ethyl tert butyl ether is supplied to the ETBE decomposition apparatus, In the ETBE decomposition apparatus, ethyl tert butyl ether is decomposed to form a decomposition reaction effluent containing isobutylene, ethanol, and unreacted ethyl tert butyl ether; and the reaction effluent is separated to recover an isobutylene fraction containing 95% by weight or more of isobutylene and a first oxygen-containing compound fraction containing the ethanol and unreacted ethyl tert butyl ether. The first portion of the isobutylene fraction is recovered as a high-purity isobutylene product fraction, The second portion of the isobutylene fraction is supplied to an isobutylene dimerizer, A portion of the first fraction containing ethyl tert butyl ether, a portion of the first oxygen-containing compound fraction, or both, is supplied to the isobutylene dimerizer as a reaction modifier. In the isobutylene dimerizer, the isobutylene is dimerized to form a dimerization reaction effluent containing isooctene, a reaction modifier, and by-products isobutylene trimer and oligomer; and the dimerization reaction effluent is separated to recover a heavy fraction containing isooctene, the by-products isobutylene trimer and oligomer, ethyl tert butyl ether, and ethanol, and a light fraction containing isobutylene and ethanol. The heavy fraction is supplied to an oxygen-containing compound separator to recover a first dimerization product fraction containing isooctene and the by-products isobutylene trimer and oligomer, and a second dimerization product fraction containing a reaction modifier. The first dimerization product fraction is supplied to the DIB purification apparatus, In the DIB purification apparatus, the first dimerization product fraction is separated to recover an isooctene fraction containing 95% by weight or more isooctene and a by-product fraction containing the isobutylene trimer and oligomer. A process that includes this.
  2. The process according to claim 1, further comprising supplying a portion of the second dimerization product fraction containing the reaction modifier to the isobutylene dimerizer as an additional reaction modifier.
  3. The process according to claim 1, further comprising supplying the second fraction to a C4 separator, separating the second fraction within the C4 separator to recover a light C4 fraction containing 1-butene and isobutane, and a heavy C4 fraction containing 2-butene and n-butane.
  4. The process according to claim 1, wherein one or both of the ETBE reaction effluent and the decomposition reaction effluent further comprise one or more of the by-products diisobutene, ethylsec butyl ether, tertiary butyl alcohol, or diethyl ether.
  5. The process according to claim 1, further comprising supplying a portion of the first oxygen-containing compound fraction to the ETBE converter.
  6. A process for the co-production of high-purity isobutylene and high-purity isooctene, wherein the process comprises The method involves supplying methanol and mixed C4 hydrocarbons to an MTBE converter, wherein the mixed C4 supply stream contains a mixture of hydrocarbons including 1-butene, 2-butene, n-butane, isobutane, and isobutylene. Within the MTBE conversion apparatus, isobutylene is reacted with ethanol using a catalyst to form methyl tert-butyl ether; the MTBE reaction effluent is recovered; and the MTBE reaction effluent is separated to recover a first fraction containing the methyl tert-butyl ether and a second fraction containing 1-butene, 2-butene, isobutane, and n-butane. The first fraction containing the methyl tert butyl ether is supplied to the MTBE decomposition apparatus. In the MTBE decomposition apparatus, methyl tert-butyl ether is decomposed to form a decomposition reaction effluent containing isobutylene, methanol, and unreacted methyl tert-butyl ether; and the reaction effluent is separated to recover an isobutylene fraction containing 95% by weight or more of isobutylene and a first oxygen-containing compound fraction containing methanol and unreacted methyl tert-butyl ether. The first portion of the isobutylene fraction is recovered as a high-purity isobutylene product fraction, The second portion of the isobutylene fraction is supplied to an isobutylene dimerizer, A portion of the first fraction containing methyl tert butyl ether, a portion of the first oxygen-containing compound fraction, or both, is supplied to the isobutylene dimerizer as a reaction modifier. In the isobutylene dimerizer, the isobutylene is dimerized to form a dimerization reaction effluent containing isooctene, a reaction modifier, and by-products isobutylene trimer and oligomer; and the dimerization reaction effluent is separated to recover a heavy fraction containing isooctene, the by-products isobutylene trimer and oligomer, methyl tert butyl ether, and methanol, and a light fraction containing isobutylene and methanol. The heavy fraction is supplied to an oxygen-containing compound separator to recover a first dimerization product fraction containing isooctene and the by-products isobutylene trimer and oligomer, and a second dimerization product fraction containing a reaction modifier. The first dimerization product fraction is supplied to the DIB purification apparatus, In the DIB purification apparatus, the first dimerization product fraction is separated to recover an isooctene fraction containing 95% by weight or more isooctene and a by-product fraction containing the isobutylene trimer and oligomer. A process that includes this.
  7. The process according to claim 6, further comprising supplying a portion of the second dimerization product fraction containing the reaction modifier to the isobutylene dimerizer as an additional reaction modifier.
  8. The process according to claim 6, further comprising supplying the second fraction to a C4 separator, separating the second fraction within the C4 separator, and recovering a light C4 fraction containing 1-butene and isobutane, and a heavy C4 fraction containing 2-butene and n-butane.
  9. The process according to claim 6, wherein one or both of the MTBE reaction effluent and the decomposition reaction effluent further comprise one or more of the by-products diisobutene, methylsec butyl ether, tertiary butyl alcohol, or dimethyl ether.
  10. The process according to claim 6, further comprising supplying a portion of the first oxygen-containing compound fraction to the MTBE conversion apparatus.
  11. A process for the co-production of high-purity isobutylene and high-purity isooctene, wherein the process comprises A mixed C4 stream containing a mixture of hydrocarbons including 1-butene, 2-butene, n-butane, isobutane, and isobutylene is supplied to the catalytic separator. Within the catalyst separation apparatus, a portion of 1-butene is converted to 2-butene, and the hydrocarbon mixture is separated to recover a first top fraction containing 1-butene, isobutane, and isobutene, and a bottom fraction containing n-butane and 2-butene. A portion of the first top fraction is recovered as a high-purity isobutylene product fraction containing at least 95% by weight of isobutylene, A second portion of the first top fraction is supplied to an etherification device, and an alcohol selected from ethanol or methanol is supplied to the etherification device. Within the etherification conversion apparatus, the process involves reacting an alcohol with isobutylene to form an alkyl tert butyl ether, and recovering the etherification reaction effluent containing the alkyl tert butyl ether and the alcohol. The aforementioned etherification reaction effluent is supplied to the isobutylene dimerizer as a reaction modifier, The second portion of the first top fraction is supplied to the isobutylene dimerizer, In the isobutylene dimerizer, the isobutylene is dimerized to form a dimerization reaction effluent containing isooctene, a reaction modifier, and by-products isobutylene trimer and oligomer; and the dimerization reaction effluent is separated to recover a heavy fraction containing isooctene, the by-products isobutylene trimer and oligomer, alkyl tert butyl ether, and alcohol, and a light fraction containing isobutylene and alcohol. The heavy fraction is supplied to an oxygen-containing compound separator to recover a first dimerization product fraction containing isooctene and the by-products isobutylene trimer and oligomer, and a second dimerization product fraction containing a reaction modifier. The first dimerization product fraction is supplied to the DIB purification apparatus, In the DIB purification apparatus, the first dimerization product fraction is separated to recover an isooctene fraction containing 95% by weight or more isooctene and a by-product fraction containing the isobutylene trimer and oligomer. A process that includes this.
  12. The process according to claim 11, wherein separating the mixture within the catalyst separation apparatus involves recovering a first top fraction containing at least 95% by weight of isobutylene and a side-draw fraction containing 1-butene, isobutane, and isobutylene, the side-draw fraction being supplied as a second fraction to the etherification conversion apparatus.
  13. The process according to claim 11, further comprising supplying a portion of the second dimerization product fraction to the isobutylene dimerizer.
  14. The process according to claim 11, wherein the alcohol is ethanol.
  15. The process according to claim 11, wherein the alcohol is methanol.
  16. A system for the co-production of high-purity isobutylene and high-purity isooctene, wherein the system is One or more fluid conduits for supplying ethanol and mixed C4 hydrocarbons to an ETBE converter, wherein the mixed C4 hydrocarbons contain a mixture of hydrocarbons including 1-butene, 2-butene, n-butane, isobutane, and isobutylene, The ETBE conversion apparatus includes one or more reactors configured to react isobutylene with ethanol using a catalyst to form ethyl tert butyl ether and to recover the ETBE reaction effluent, and a separation system configured to separate the ETBE reaction effluent and recover a first fraction containing the ethyl tert butyl ether and a second fraction containing 1-butene, 2-butene, isobutane, and n-butane, A channel for supplying the first fraction containing ethyl tert butyl ether to an ETBE decomposition apparatus, The ETBE decomposition apparatus includes one or more reactors configured to decompose ethyl tert butyl ether to form a decomposition reaction effluent containing isobutylene, ethanol, and unreacted ethyl tert butyl ether, and a separation system configured to separate the reaction effluent and recover an isobutylene fraction containing 95% by weight or more isobutylene and a first oxygen-containing compound fraction containing the ethanol and unreacted ethyl tert butyl ether, A channel for recovering the first portion of the isobutylene fraction as a high-purity isobutylene product fraction, A flow path for supplying the second portion of the isobutylene fraction to an isobutylene dimerizer, A flow path for supplying a portion of the first fraction containing ethyl tert butyl ether, a portion of the first oxygen-containing compound fraction, or both, to the isobutylene dimerizer as a reaction modifier, The isobutylene dimerizer includes one or more reactors configured to dimerize the isobutylene to form a dimerization reaction effluent containing isooctene, a reaction modifier, and by-products isobutylene trimer and oligomer; and a separation system for separating the dimerization reaction effluent to recover a heavy fraction containing isooctene, the by-products isobutylene trimer and oligomer, ethyl tert butyl ether, and ethanol, and a light fraction containing isobutylene and ethanol. A separator for oxygen-containing compounds for separating the heavy fraction and recovering a first dimerization product fraction containing isooctene and the by-products isobutylene trimer and oligomer, and a second dimerization product fraction containing a reaction modifier, A flow path for supplying the first dimerization product fraction to the DIB purification apparatus, The DIB purification apparatus includes a separation system for separating the first dimerization product fraction and recovering an isooctene fraction containing 95% by weight or more isooctene and a by-product fraction containing the isobutylene trimer and oligomer, A system equipped with these features.
  17. A system for the co-production of high-purity isobutylene and high-purity isooctene, wherein the system is One or more fluid conduits for supplying methanol and the mixed C4 hydrocarbon to an MTBE converter, wherein the mixed C4 hydrocarbon contains a mixture of hydrocarbons including 1-butene, 2-butene, n-butane, isobutane, and isobutylene, The MTBE conversion apparatus includes one or more reactors configured to react isobutylene with ethanol using a catalyst to form methyl tert butyl ether and to recover the MTBE reaction effluent, and a separation system for separating the MTBE reaction effluent to recover a first fraction containing the methyl tert butyl ether and a second fraction containing 1-butene, 2-butene, isobutane, and n-butane, A channel for supplying the first fraction containing the methyl tert butyl ether to an MTBE decomposition apparatus, The MTBE decomposition apparatus includes one or more reactors for decomposing methyl tert-butyl ether to form a decomposition reaction effluent containing isobutylene, methanol, and unreacted methyl tert-butyl ether, and a separation system configured to separate the reaction effluent and recover an isobutylene fraction containing 95% by weight or more isobutylene and a first oxygen-containing compound fraction containing the methanol and unreacted methyl tert-butyl ether, A channel for recovering the first portion of the isobutylene fraction as a high-purity isobutylene product fraction, A flow path for supplying the second portion of the isobutylene fraction to an isobutylene dimerizer, A flow path for supplying a portion of the first fraction containing methyl tert butyl ether, a portion of the first oxygen-containing compound fraction, or both, to the isobutylene dimerizer as a reaction modifier, The isobutylene dimerizer includes one or more reactors for dimerizing the isobutylene to form a dimerization reaction effluent containing isooctene, a reaction modifier, and by-products isobutylene trimer and oligomer, and a separation system for separating the dimerization reaction effluent to recover a heavy fraction containing isooctene, the by-products isobutylene trimer and oligomer, methyl tert butyl ether, and methanol, and a light fraction containing isobutylene and methanol. A separator for oxygen-containing compounds for separating the heavy fraction and recovering a first dimerization product fraction containing isooctene and the by-products isobutylene trimer and oligomer, and a second dimerization product fraction containing a reaction modifier, A flow path for supplying the first dimerization product fraction to the DIB purification apparatus, The DIB purification apparatus includes a separation system for separating the first dimerization product fraction and recovering an isooctene fraction containing 95% by weight or more isooctene and a by-product fraction containing the isobutylene trimer and oligomer, A system equipped with these features.
  18. A system for the co-production of high-purity isobutylene and high-purity isooctene, wherein the system is One or more channels for supplying a mixed C4 stream containing a mixture of hydrocarbons including 1-butene, 2-butene, n-butane, isobutane, and isobutylene to a catalytic separator, The catalyst separation apparatus includes a catalytic distillation column configured to convert a portion of the 1-butene to 2-butene and simultaneously separate the hydrocarbon mixture to recover a first top fraction containing 1-butene, isobutane, and isobutene, and a bottom fraction containing n-butane and 2-butene, A channel for recovering a portion of the first top fraction as a high-purity isobutylene product fraction containing at least 95% by weight of isobutylene, One or more channels for supplying an alcohol selected from ethanol or methanol and a second portion of the first top fraction to an etherification conversion device, The etherification conversion apparatus includes one or more reactors for reacting an alcohol with isobutylene to form an alkyl tert butyl ether and recovering an etherification reaction effluent containing the alkyl tert butyl ether and the alcohol, A channel for supplying the etherification reaction outflow to an isobutylene dimerizer as a reaction modifier, A flow path for supplying the second portion of the first top fraction to the isobutylene dimerizer, The isobutylene dimerizer includes one or more reactors for dimerizing the isobutylene to form a dimerization reaction effluent containing isooctene, a reaction modifier, and by-products isobutylene trimer and oligomer, and a separation system for separating the dimerization reaction effluent to recover a heavy fraction containing isooctene, the by-products isobutylene trimer and oligomer, alkyl tert butyl ether, and alcohol, and a light fraction containing isobutylene and alcohol. A separator for oxygen-containing compounds for separating the heavy fraction and recovering a first dimerization product fraction containing isooctene and the by-products isobutylene trimer and oligomer, and a second dimerization product fraction containing a reaction modifier, A flow path for supplying the first dimerization product fraction to the DIB purification apparatus, The DIB purification apparatus includes a separation system for separating the first dimerization product fraction and recovering an isooctene fraction containing 95% by weight or more isooctene and a by-product fraction containing the isobutylene trimer and oligomer, A system equipped with these features.

Description

Embodiments of this disclosure generally relate to systems and processes for the co-production of high-purity isooctene and high-purity isobutylene. High-purity isobutylene is used as a raw material for the production of butyl rubber, PIB (polyisobutylene), and MMA (methyl methacrylate), and is typically produced from a commercially proven MTBE decomposition process. High-purity isooctene is used as a raw material for octylphenol resins used as tackifiers in radial tires, octylated diphenylamine stabilizers for lubricants and rubber, isononyl derivatives used to produce polymerization initiators and compressor fluids, and comonomers in the production of elastomers and hydrocarbon resins, or chain stoppers for polycarbonate resins. A simplified process flow diagram of a system for co-producing high-purity isobutene and high-purity isooctene according to one or more embodiments disclosed herein is shown.A simplified process flow diagram of a system for co-producing high-purity isobutene and high-purity isooctene according to one or more embodiments disclosed herein is shown.A simplified process flow diagram of a system for co-producing high-purity isobutene and high-purity isooctene according to one or more embodiments disclosed herein is shown.A catalytic deisobutene apparatus useful in the embodiments described herein is illustrated.A general process block flow diagram of an isobutylene dimerizer according to one or more embodiments disclosed herein is shown.A simplified block flow diagram of an etherification apparatus according to one or more embodiments disclosed herein is shown. The embodiments of this disclosure generally relate to systems and processes for the co-production of high-purity isooctene and high-purity isobutylene. More specifically, the embodiments described herein are directed toward the production of high-purity isobutylene and high-purity isooctene from a mixed C4 stream. In the embodiments described herein, useful alcohol feed streams include methanol or ethanol. In other embodiments, alcohol feed streams may include propanol or butanol, as well as other C3 and C4 alcohols. To generate a C4 flow, various upstream production processes can be used, including fluid catalytic cracking (FCC) units, residual oil fluid catalytic cracking (RFCC) units, steam cracking units, pyrolysis units (pyrolysis using steam or pyrolysis without steam), and various other methods for producing mixed C4. The mixed C4 flow produced from these units may contain isobutene, isobutane, 1-butene, 2-butene, n-butane, and butadiene, as well as other components. Such upstream C4 production systems produce similar chemical compounds, but result in flows with different compositional mixtures of various C4 compounds. For example, FCC or RFCC mixed C4 may have a much higher isobutane concentration (e.g., over 20% or over 25% by weight) than raffinate-1 (e.g., less than 5% or less than 3% by weight) recovered from the butadiene production process of the vapor cracker. At the same time, the isobutylene concentration in the C4 of the FCC/RFCC is much lower than that of the C4 of the vapor cracker (e.g., less than 25% or less than 30% by weight in the RFCC, compared to over 35% or over 40% by weight in the vapor cracker C4). Similarly, there may also be differences in the 1-butene concentrations of each (FCC/RFCC vs. vapor cracker) (e.g., less than 20% or less than 15% by weight vs. over 35% or over 40% by weight). Furthermore, the diene content of the FCC/RFCC mixture C4 is much higher than that of Raffinate-1 from the vapor cracking unit (e.g., 0.3% by weight or 3,000 ppmw vs. 40 ppmw). The embodiments described herein can produce high-purity isobutylene and high-purity isooctene from any of these various flows, or from a mixture of two or more of these flows. Generally, the embodiments described herein first convert a C4 mixture with isobutylene into an oxygen-containing compound via etherification, and then decompose this oxygen-containing compound into a high-purity isobutylene (HPIB) stream and C1-C2 alcohols. The HPIB is then diluted with C4 paraffin to control the exothermic reaction in dimerization. The oxygen-containing compound from the decomposition step, along with the oxygen-containing compound recovered from a downstream separator, is used as a reaction modifier to control the oligomerization reaction and enhance selectivity to high-purity isooctene (HPIB). A variation of the HPIB preparation involves hydrogen isomerization. In the first embodiment, for example, the mixed C4 reacts with ethanol to produce ETBE, which is then decomposed (reverse decomposition) to produce high-purity isobutylene as part of the preparation of the feed for the high-purity isooctene production step. In the fully integrated configuration, all of the HPIB produced is diluted with C4 paraffin, which is assumed to be a semi-closed circulating system depending on the amount of HPIB produced. The recirculated paraffin forms an azeotrope