US4543435A — Multistage process for converting oxygenates to l…

Claim 1

Independent Claim 203 words

An integrated continuous process for converting oxygenated organic feedstock to liquid hydrocarbons comprising the steps of (a) contacting feedstock with zeolite catalyst in a primary catalyst stage at elevated temperature and moderate pressure to convert at least a portion of the feedstock oxygenate to hydrocarbons containing a major fraction of C 2 -C 4 olefins and a minor fraction containing C 5 + hydrocarbons; (b) cooling and separating effluent from step (a) to provide an aqueous liquid byproduct stream, a heavy hydrocarbon liquid stream and a light hydrocarbon vapor stream rich in C 2 -C 4 olefins; (c) compressing at least a portion of the olefinic light hydrocarbon stream to condense a liquid olefinic hydrocarbon stream rich in C 3 + olefins and recovering an ethene-rich gaseous stream; (d) further pressurizing and contacting substantially all of the condensed liquid olefinic hydrocarbon stream from step (c) in a secondary catalytic stage with oligomerization catalyst comprising medium-pore shape selective acidic zeolite at substantially increased pressure and moderate temperature to convert at least a portion of olefins to a heavier liquid hydrocarbon product stream comprising olefinic gasoline and distillate range liquids; and (e) recovering ethene in a gaseous stream for recycle to the primary catalytic stage.

Claim 2

Dependent Claim 203 words

An integrated continuous process for converting oxygenated organic feedstock to liquid hydrocarbons comprising the steps of (a) contacting feedstock with zeolite catalyst in a primary catalyst stage at elevated temperature and moderate pressure to convert at least a portion of the feedstock oxygenate to hydrocarbons containing a major fraction of C 2 -C 4 olefins and a minor fraction containing C 5 + hydrocarbons; (b) cooling and separating effluent from step (a) to provide an aqueous liquid byproduct stream, a heavy hydrocarbon liquid stream and a light hydrocarbon vapor stream rich in C 2 -C 4 olefins; (c) compressing at least a portion of the olefinic light hydrocarbon stream to condense a liquid olefinic hydrocarbon stream rich in C 3 + olefins and recovering an ethene-rich gaseous stream; (d) further pressurizing and contacting substantially all of the condensed liquid olefinic hydrocarbon stream from step (c) in a secondary catalytic stage with oligomerization catalyst comprising medium-pore shape selective acidic zeolite at substantially increased pressure and moderate temperature to convert at least a portion of olefins to a heavier liquid hydrocarbon product stream comprising olefinic gasoline and distillate range liquids; and (e) recovering ethene in a gaseous stream for recycle to the primary catalytic stage.

Claim 3

Dependent Claim 44 words

The process of claim 1 further comprising the step of fractionating gaseous effluent from separation step (b) to recover a recycle gas stream containing at least 90% of ethene from the primary catalytic stage and an olefinic stream rich in C 3 + olefins.

Claim 4

Dependent Claim 45 words

The process of claim 1 wherein the primary and secondary stage catalyst comprises ZSM-5 type zeolite and ethene is recycled to the primary stage at a rate of about 1 to 20 parts ethene per 100 parts by weight of methanol equivalent in the feedstock.

Claim 5

Dependent Claim 46 words

The process of claim 1 wherein primary stage feedstock comprising methanol and/or dimethyl ether and recycled ethene are converted over HZSM-5 catalyst to provide a light olefinic hydrocarbon vapor stream comprising a major amount of C 3 -C 4 olefins and a minor amount of ethene.

Claim 6

Dependent Claim 61 words

The process of claim 4 wherein olefin production is optimized by employing fluid bed primary stage conditions in the temperature range of about 425° C. to 550° C., a pressure range of about 100 to 800 kPa and weight hourly space velocity range of about 0.5 to 3.0 based on ZSM-5 equivalent catalyst and methanol equivalent in the primary stage feedstock.

Claim 7

Dependent Claim 36 words

The process of claim 5 wherein at least 90% of feedstock is converted per reactor pass and wherein water diluent is cofed with methanol and/or dimethyl ether in a molar ratio of about 0.01:1 to 2:1.

Claim 8

Dependent Claim 28 words

The process of claim 4 wherein primary stage hydrocarbon effluent contains about 1 to 10 wt.% ethene and about 10 to 60 wt.% C 3 -C 4 olefins.

Claim 9

Dependent Claim 18 words

The process of claim 4 wherein ethene is recovered from the primary stage effluent vapor stream by fractionation.

Claim 10

Dependent Claim 37 words

The process of claim 1 wherein the secondary stage effluent is cooled and separated to provide a light hydrocarbon stream containing unconverted ethene and wherein said unconverted ethene is expanded to about primary stage pressure for recycle.

Claim 11

Dependent Claim 18 words

The process of claim 9 wherein compressed light hydrocarbon vapor is recompressed to recover an ethene-rich recycle stream.

Claim 12

Dependent Claim 28 words

The process of claim 1 wherein the secondary stage process conditions are maintained to produce heavy liquid hydrocarbons having a normal boiling point greater than about 175° C.

Claim 13

Dependent Claim 38 words

The process of claim 11 wherein the secondary stage employs a fixed bed of ZSM-5 type catalyst to oligomerize olefins at a temperature of about 190° C. to 315° C. and pressure of about 4200 to 7000 kPa.

Claim 14

Dependent Claim 148 words

A continuous multi-stage catalytic system for converting oxygenated feedstock to liquid hydrocarbons comprising primary stage catalytic reactor means containing acidic zeolite catalyst for converting oxygenate to olefinic hydrocarbons rich in C 2 -C 4 alkenes; interstage separation means for recovering water and light hydrocarbon vapor from the primary stage effluent stream; including means for pressurizing the primary stage hydrocarbon liquid stream rich in C 3 + components and an ethene-rich vapor stream; secondary stage catalytic oligomerization reactor means containing medium pore shape selective acidic zeolite oligomerization catalyst for converting C 3 + olefinic hydrocarbons to heavier liquid hydrocarbons; fractionation means for separating secondary stage effluent into a light hydrocarbon stream containing C 2 -C 4 aliphatic hydrocarbons, a C 5 + gasoline stream and distillate range stream; means for recovering and recycling at least a portion of the ethene to the primary stage for combining with oxygenated feedstock.

Claim 15

Dependent Claim 148 words

A continuous multi-stage catalytic system for converting oxygenated feedstock to liquid hydrocarbons comprising primary stage catalytic reactor means containing acidic zeolite catalyst for converting oxygenate to olefinic hydrocarbons rich in C 2 -C 4 alkenes; interstage separation means for recovering water and light hydrocarbon vapor from the primary stage effluent stream; including means for pressurizing the primary stage hydrocarbon liquid stream rich in C 3 + components and an ethene-rich vapor stream; secondary stage catalytic oligomerization reactor means containing medium pore shape selective acidic zeolite oligomerization catalyst for converting C 3 + olefinic hydrocarbons to heavier liquid hydrocarbons; fractionation means for separating secondary stage effluent into a light hydrocarbon stream containing C 2 -C 4 aliphatic hydrocarbons, a C 5 + gasoline stream and distillate range stream; means for recovering and recycling at least a portion of the ethene to the primary stage for combining with oxygenated feedstock.

Claim 16

Dependent Claim 173 words

A process for converting feedstock consisting essentially of methanol, dimethyl ether or mixtures thereof to liquid hydrocarbons comprising the steps of contacting the feedstock with zeolite catalyst in a primary catalyst stage at elevated temperature and moderate pressure to convert feedstock to hydrocarbons comprising C 2 -C 4 olefins and C 5 + hydrocarbons; cooling and separating effluent from the primary stage to recover a liquid hydrocarbon stream and a light hydrocarbon vapor stream rich in C 2 -C 4 olefins; compressing the olefinic light hydrocarbon stream to condense a liquid olefinic hydrocarbon stream rich in C 3 + olefins and recovering an ethene-rich gaseous stream; further pressurizing and contacting the condensed liquid olefinic hydrocarbon stream in a secondary catalytic stage with oligomerization catalyst comprising medium-pore shape selective acidic zeolite at substantially increased pressure and moderate temperature to convert at least a portion of olefins to a heavier liquid hydrocarbon product stream comprising olefinic gasoline and distillate range liquids; and recovering ethene in a gaseous stream for recycle to the primary catalytic stage.

Claim 17

Dependent Claim 173 words

A process for converting feedstock consisting essentially of methanol, dimethyl ether or mixtures thereof to liquid hydrocarbons comprising the steps of contacting the feedstock with zeolite catalyst in a primary catalyst stage at elevated temperature and moderate pressure to convert feedstock to hydrocarbons comprising C 2 -C 4 olefins and C 5 + hydrocarbons; cooling and separating effluent from the primary stage to recover a liquid hydrocarbon stream and a light hydrocarbon vapor stream rich in C 2 -C 4 olefins; compressing the olefinic light hydrocarbon stream to condense a liquid olefinic hydrocarbon stream rich in C 3 + olefins and recovering an ethene-rich gaseous stream; further pressurizing and contacting the condensed liquid olefinic hydrocarbon stream in a secondary catalytic stage with oligomerization catalyst comprising medium-pore shape selective acidic zeolite at substantially increased pressure and moderate temperature to convert at least a portion of olefins to a heavier liquid hydrocarbon product stream comprising olefinic gasoline and distillate range liquids; and recovering ethene in a gaseous stream for recycle to the primary catalytic stage.

Claim 18

Dependent Claim 38 words

The process of claim 14 wherein primary stage feedstock is converted over HZSM-5 catalyst to provide a light olefinic hydrocarbon vapor stream comprising a major amount of C 3 -C 4 olefins and a minor amount of ethene.

Claim 19

Dependent Claim 45 words

The process of claim 14 further comprising the step of fractionating gaseous effluent separated from primary stage effluent to recover a recycle gas stream containing at least 90% of ethene from the primary catalytic stage and an olefinic stream rich in C 3 + olefins.

Claim 20

Dependent Claim 45 words

The process of claim 14 wherein the primary and secondary stage catalyst comprises ZSM-5 type zeolite and ethene is recycled to the primary stage at a rate of about 1 to 10 parts ethene per 100 parts by weight of methanol equivalent in the feedstock.

Claim 21

Dependent Claim 51 words

The process of claim 14 wherein the light hydrocarbon vapor stream separated from the primary stage effluent is compressed in a plurality of compression stages to condense liquid olefinic hydrocarbons, and wherein uncondensed compressed light hydrocarbons are further fractionated to recover a recycle stream containing at least 90 mole percent ethene.

Claim 22

Dependent Claim 31 words

The process of claim 18 wherein the compressed light hydrocarbon gaseous stream is further fractionated by selectively absorbing C 3 + components in a C 5 + liquid hydrocarbon sorbent stream.

Claim 23

Dependent Claim 25 words

The process of claim 19 wherein a fraction of the secondary stage liquid hydrocarbon product stream comprising olefinic gasoline is recycled as the sorbent stream.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1988-09-23	1989-03-25	1989-09-24	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1992-09-23	1993-03-25	1993-09-24	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1996-09-23	1997-03-25	1997-09-24	$7700.00	Window Closed / Lapsed

Multistage process for converting oxygenates to liquid hydrocarbons with ethene recycle

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