US5100533A — Process for production of iso-olefin and ether

Claim 1

Independent Claim 119 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh naphtha feedstock stream containing a major amount of C7+ alkanes and naphthenes with medium pore acid cracking catalyst having the structure of MCM-22 under low pressure selective cracking conditions effective to produce at least 10 wt% total C4-C5 isoalkene and at least 10 wt% total C4-C5 isoalkane, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components and having an acid cracking activity less than 15; separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction of enhanced octane value; and etherifying the C4-C5 isoalkene fraction by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product.

Claim 2

Dependent Claim 119 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh naphtha feedstock stream containing a major amount of C7+ alkanes and naphthenes with medium pore acid cracking catalyst having the structure of MCM-22 under low pressure selective cracking conditions effective to produce at least 10 wt% total C4-C5 isoalkene and at least 10 wt% total C4-C5 isoalkane, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components and having an acid cracking activity less than 15; separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction of enhanced octane value; and etherifying the C4-C5 isoalkene fraction by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product.

Claim 3

Dependent Claim 96 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 1 wherein the fresh feedstock contains about 15 to 50 wt% C7-C12 alkanes, about 15 to 50 wt% C7+ cycloaliphatic hydrocarbons, and less than 40% aromatics; the cracking conditions include total pressure up to about 500 kPa, space velocity greater than 1/hr WHSV, and reaction temperature of about 425° to 650° C.; the cracking catalyst comprises metallosilicate zeolite having a constraint index of about 1.5; and wherein the cracking reaction produces less than 5% C2- light paraffin gas based on fresh naphtha feedstock.

Claim 4

Dependent Claim 67 words

A process for upgrading naphtha comprising predominantly alkanes and/or naphthenes according to claim 2 wherein the cracking catalyst consists essentially of aluminosilicate MCM-22; the cracking reaction is maintained at about 450° to 540° C. and weight hourly space velocity of about 1 to 100/hr; and wherein the fresh feedstock consists essentially of C7+ paraffinic virgin petroleum naphtha boiling in the range of about 65° to 175° C.

Claim 5

Dependent Claim 59 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 1 wherein at least a portion of the C6+ fraction from cracking effluent is recycled with fresh feedstock for further conversion under cracking conditions; and wherein isobutene and isoamylene recovered from naphtha cracking are etherified with methanol to produce methyl t-butyl ether and methyl t-amyl ether.

Claim 6

Dependent Claim 94 words

A process for upgrading paraffinic naphtha to high octane fuel by contacting a fresh virgin naphtha feedstock stream containing C7-C12 alkanes and naphthenes with a fluidized bed of medium pore acid zeolite cracking catalyst containing MCM-22 under low pressure selective cracking conditions effective to produce at least 10 wt% C4-C5 isoalkene and increased isoparaffin, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components; and separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction of enhanced octane value containing less than 20 wt% aromatic hydrocarbons.

Claim 7

Dependent Claim 94 words

A process for upgrading paraffinic naphtha to high octane fuel by contacting a fresh virgin naphtha feedstock stream containing C7-C12 alkanes and naphthenes with a fluidized bed of medium pore acid zeolite cracking catalyst containing MCM-22 under low pressure selective cracking conditions effective to produce at least 10 wt% C4-C5 isoalkene and increased isoparaffin, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components; and separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction of enhanced octane value containing less than 20 wt% aromatic hydrocarbons.

Claim 8

Dependent Claim 66 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 5 wherein the fresh feedstock contains at least 15 wt% C7+ cycloaliphatic hydrocarbons and less than 20% aromatics; the cracking conditions include total pressure up to about 500 kPa and reaction temperature of about 425° to 650° C.; the cracking catalyst comprises aluminosilicate zeolite MCM-22 having an acid cracking activity less than 15.

Claim 9

Dependent Claim 39 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 5 wherein petroleum naphtha containing aromatic hydrocarbon is hydrotreated to convert aromatic components to cycloaliphatic hydrocarbons to provide fresh feedstock containing less than 10 wt% aromatics.

Claim 10

Dependent Claim 34 words

The process of claim 5 wherein the fluidized bed catalyst is contacted with the feedstock in a vertical riser reactor during a short contact period in a transport regime and separated for catalyst recycle.

Claim 11

Dependent Claim 27 words

The process of claim 8 wherein the contact period is less than 10 seconds, and the space velocity is about 1-10, based on active zeolite catalyst solids.

Claim 12

Dependent Claim 125 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh paraffinic petroleum naphtha feedstock stream having a normal boiling range of about 65° to 175° C. for about 0.5 to 10 seconds with a first fluidized bed of medium pore acid cracking catalyst comprising MCM-22 zeolite under low pressure selective cracking conditions effective to produce at least 28 wt% total C4-C5 branched aliphatic hydrocarbons containing isobutene, isoamylenes, isobutane and isopentanes; separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 tertiary alkenes; and etherifying the C4-C5 isoalkene fraction by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product; and recovering isobutane and isopentanes from cracking effluent and further converting said isobutane and isopentane to high octane fuel components.

Claim 13

Dependent Claim 125 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh paraffinic petroleum naphtha feedstock stream having a normal boiling range of about 65° to 175° C. for about 0.5 to 10 seconds with a first fluidized bed of medium pore acid cracking catalyst comprising MCM-22 zeolite under low pressure selective cracking conditions effective to produce at least 28 wt% total C4-C5 branched aliphatic hydrocarbons containing isobutene, isoamylenes, isobutane and isopentanes; separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 tertiary alkenes; and etherifying the C4-C5 isoalkene fraction by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product; and recovering isobutane and isopentanes from cracking effluent and further converting said isobutane and isopentane to high octane fuel components.

Claim 14

Dependent Claim 81 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 10 wherein the fresh feedstock contains about C7-C10 alkanes cycloaliphatic hydrocarbons, and is substantially free of aromatics; the cracking conditions include total pressure up to about 500 kPa and reaction temperature of about 425° to 650° C.; the cracking catalyst comprises aluminosilicate zeolite having a constraint index of about 1.5; and wherein the cracking reaction produces less than 5% C2- light paraffin gas based on fresh naphtha feedstock.

Claim 15

Dependent Claim 64 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 11 wherein the cracking catalyst consists essentially of MCM-22, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components and having an acid cracking activity less than 15; and wherein the cracking reaction is maintained at about 450° to 540° C. and weight hourly space velocity of about 1 to 50.

Claim 16

Dependent Claim 59 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 10 wherein at least a portion of the C6+ fraction from cracking effluent is recycled with fresh feedstock for further conversion under cracking conditions; and wherein isobutene and isoamylene recovered from naphtha cracking are etherified with methanol to produce methyl t-butyl ether and methyl t-amyl ether.

Claim 17

Dependent Claim 123 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh naphtha feedstock stream containing a major amount of C7+ alkanes and naphthenes with medium pore acid MCM-22 cracking catalyst under low pressure selective cracking conditions effective to produce at least 20 wt% selectivity to isomeric C4-C5 aliphatics containing C4-C5 isoalkene and at least 10 wt% C4-C5 isoalkane, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components and having an acid cracking activity less than 15; separating cracking effluent to obtain an olefinic fraction rich in C4-C5 isoalkene and a C6+ fraction; etherifying the olefinic C4-C5 fraction by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product; and converting residual C4-C5 isoalkane to provide high octane fuel components.

Claim 18

Dependent Claim 123 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh naphtha feedstock stream containing a major amount of C7+ alkanes and naphthenes with medium pore acid MCM-22 cracking catalyst under low pressure selective cracking conditions effective to produce at least 20 wt% selectivity to isomeric C4-C5 aliphatics containing C4-C5 isoalkene and at least 10 wt% C4-C5 isoalkane, said cracking catalyst being substantially free of hydrogenation-dehydrogenation metal components and having an acid cracking activity less than 15; separating cracking effluent to obtain an olefinic fraction rich in C4-C5 isoalkene and a C6+ fraction; etherifying the olefinic C4-C5 fraction by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product; and converting residual C4-C5 isoalkane to provide high octane fuel components.

Claim 19

Dependent Claim 80 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 14 wherein the fresh feedstock contains at least 20 wt% C7-C12 alkanes, at least 15 wt% C7+ cycloaliphatic hydrocarbons, and less than 40% aromatics; the cracking conditions include total pressure up to about 500 kPa, space velocity greater than 1/hr WHSV, and reaction temperature of about 425° to 650° C.; and wherein the cracking reaction produces less than 5% C2- light gas based on fresh naphtha feedstock.

Claim 20

Dependent Claim 68 words

A process for upgrading naphtha comprising predominantly alkanes and/or naphthenes according to claim 14 wherein the cracking catalyst consists essentially of aluminosilicate MCM-22 zeolite; the cracking reaction is maintained at about 450° to 540° C. and weight hourly space velocity of about 0.5 to 100/hr; and wherein the fresh feedstock consists essentially of C7+ paraffinic virgin petroleum naphtha boiling in the range of about 65° to 175° C.

Claim 21

Dependent Claim 52 words

A process for upgrading paraffinic naphtha to high octane fuel by contacting a fresh virgin naphtha feedstock stream containing predominantly C7-C12 alkanes and naphthenes with acid MCM-22 zeolite cracking catalyst under low pressure selective cracking conditions effective to produce at least 10 wt% C4-C5 isoalkene and increased yield of isobutane and isopentanes.

Claim 22

Dependent Claim 52 words

A process for upgrading paraffinic naphtha to high octane fuel by contacting a fresh virgin naphtha feedstock stream containing predominantly C7-C12 alkanes and naphthenes with acid MCM-22 zeolite cracking catalyst under low pressure selective cracking conditions effective to produce at least 10 wt% C4-C5 isoalkene and increased yield of isobutane and isopentanes.

Claim 23

Dependent Claim 65 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 17 wherein the fresh feedstock contains at least 15 wt% C7+ cycloaliphatic hydrocarbons and less than 20% aromatics; the cracking conditions include total pressure up to about 500 kPa and reaction temperature of about 425° to 650° C.; the cracking catalyst comprises aluminosilicate zeolite having an acid cracking activity less than 15.

Claim 24

Dependent Claim 39 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 18 wherein petroleum naphtha containing aromatic hydrocarbon is hydrotreated to convert aromatic components to cycloaliphatic hydrocarbons to provide fresh feedstock containing less than 5 wt% aromatics.

Claim 25

Dependent Claim 94 words

The process of claim 17 wherein fluidized bed catalyst is contacted with the feedstock in a vertical riser reactor during a short contact period which is sufficient to produce said at least 10% C4-C5 isoalkene in a transport regime and therefor, wherein said catalyst is separated from said isoalkylene and is recycled to said upgrading step; wherein said cracking reaction is carried out in the substantial absence of added hydrogen; wherein the contact period is less than 10 seconds; and wherein the space velocity is greater than 1, based on active zeolite catalyst solids.

Claim 26

Dependent Claim 125 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh paraffinic petroleum naphtha feedstock stream having a normal boiling range of about 65° to 175° C. with a first fluidized bed of medium pore acid zeolite cracking catalyst under low pressure selective cracking conditions effective to produce at least 10 wt% selectivity C4--C5 isoalkene and at lest 10 wt% selectivity C4-C5 isoalkane, said cracking catalyst being substantially free of hydrogenation metal components and having an acid cracking activity less than 15; separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction; and etherifying the C4-C5 isoalkene fraction and additional isobutene and isopentene by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product.

Claim 27

Dependent Claim 125 words

A process for upgrading paraffinic naphtha to high octane fuel comprising: contacting a fresh paraffinic petroleum naphtha feedstock stream having a normal boiling range of about 65° to 175° C. with a first fluidized bed of medium pore acid zeolite cracking catalyst under low pressure selective cracking conditions effective to produce at least 10 wt% selectivity C4--C5 isoalkene and at lest 10 wt% selectivity C4-C5 isoalkane, said cracking catalyst being substantially free of hydrogenation metal components and having an acid cracking activity less than 15; separating cracking effluent to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction; and etherifying the C4-C5 isoalkene fraction and additional isobutene and isopentene by catalytic reaction with lower alkanol to produce tertiary-alkyl ether product.

Claim 28

Dependent Claim 81 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 21 wherein the fresh feedstock contains about C7-C10 alkanes cycloaliphatic hydrocarbons, and is substantially free of aromatics; the cracking conditions include total pressure up to about 500 kPa and reaction temperature of about 425° to 650° C.; the cracking catalyst comprises metallosilicate MCM-22 zeolite having a constraint index of about 1.5; and wherein the cracking reaction produces less than 5% C2- light gas based on fresh naphtha feedstock.

Claim 29

Dependent Claim 85 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 22 wherein the cracking catalyst comprises medium pore zeolite; the cracking reaction is maintained at about 450° to 540° C. and weight hourly space velocity of about 1 to 10; and including the additional step of recovering volatile unreacted isoalkene and alkanol from etherification effluent and contacting the volatile effluent with a second fluidized bed of medium pore acid zeolite catalyst under olefin upgrading reaction conditions to produce additional gasoline range hydrocarbons.

Claim 30

Dependent Claim 73 words

A process for upgrading paraffinic naphtha to high octane fuel according to claim 21 wherein cracking effluent is fractionated to obtain a C 6 + fraction, and at least a portion of the C 6 + fraction from cracking effluent is recycled with fresh feedstock for further conversion under cracking conditions; and wherein isobutene and isoamylene recovered from naphtha cracking are etherified with methanol to produce methyl t-butyl ether and methyl t-amyl ether.

Claim 31

Dependent Claim 78 words

A process for partially converting paraffinic naphtha feedstock olefin to branched aliphatic hydrocarbon product rich in isoalkenes and isoalkanes, which comprises contacting a feedstock containing C7-C12 naphtha range hydrocarbon with a catalyst composition under elevated temperature, short contact time partial conversion conditions to provide at least 10 wt% selectivity to isoalkene product, said catalyst comprising a synthetic porous crystalline material characterized by an X-ray diffraction pattern including values substantially as set forth in Table I of the specification.

Claim 32

Dependent Claim 78 words

A process for partially converting paraffinic naphtha feedstock olefin to branched aliphatic hydrocarbon product rich in isoalkenes and isoalkanes, which comprises contacting a feedstock containing C7-C12 naphtha range hydrocarbon with a catalyst composition under elevated temperature, short contact time partial conversion conditions to provide at least 10 wt% selectivity to isoalkene product, said catalyst comprising a synthetic porous crystalline material characterized by an X-ray diffraction pattern including values substantially as set forth in Table I of the specification.

Claim 33

Dependent Claim 65 words

The process of claim 25 wherein the synthetic porous crystalline material is characterized by an X-ray diffraction pattern including values substantially as set forth in Table II of the specification; and wherein the synthetic porous crystalline material has a composition comprising the molar relationship X.sub.2 O.sub.3 :(n)YO.sub.2, wherein n is at least about 10, X is a trivalent element and Y is a tetravalent element.

Claim 34

Dependent Claim 68 words

The process of claim 26 wherein the synthetic porous crystalline material has a composition comprising the molar relationship: X.sub.2 O.sub.3 :(n)YO.sub.2, wherein n is at least about 10, X is a trivalent element and Y is a tetravalent element; and wherein the synthetic porous crystalline material possesses equilibrium adsorption capacities of greater than about 4.5 wt.% for cyclohexane vapor and greater than about 10 wt.% for n-hexane vapor.

Claim 35

Dependent Claim 18 words

The process according to claim 26 wherein X consists essentially of aluminum and Y consists essentially of silicon.

Claim 36

Dependent Claim 28 words

The process according claim 25, said synthetic porous crystalline material being thermally treated at a temperature up to about 925° C. in the presence or absence of steam.

Claim 37

Dependent Claim 98 words

In the process for upgrading paraffinic naphtha to high octane fuel according to claim 25 wherein the fresh feedstock contains about 15 to 50 wt% C7-C12 alkanes, about 15 to 50 wt% C7+ cycloaliphatic hydrocarbons, and less than 40% aromatics; the cracking conditions include total pressure up to about 500 kPa, space velocity greater than 1/hr WHSV, and reaction temperature of about 425° to 650° C.; the cracking catalyst comprises metallosilicate porous crystalline zeolite having a constraint index of about 1.5; and wherein the cracking reaction produces less than 5% C2-light paraffin gas based on fresh naphtha feedstock.

Claim 38

Dependent Claim 55 words

In a process for partially converting naphtha feedstock to iso-alkene rich product by shape selective catalysis at elevated temperature and low pressure, the improvement which comprises: reacting the naphtha feedstock for less than 10 seconds in contact with MCM-22 zeolite catalyst under partial reaction conditions sufficient to provide increased yield of C4-C5 isoalkanes and isoalkenes.

Claim 39

Dependent Claim 55 words

In a process for partially converting naphtha feedstock to iso-alkene rich product by shape selective catalysis at elevated temperature and low pressure, the improvement which comprises: reacting the naphtha feedstock for less than 10 seconds in contact with MCM-22 zeolite catalyst under partial reaction conditions sufficient to provide increased yield of C4-C5 isoalkanes and isoalkenes.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1995-03-31	1995-09-30	1996-03-31	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1999-03-31	1999-09-30	2000-03-31	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2003-03-31	2003-09-30	2004-03-31	$7700.00	Window Closed / Lapsed

Process for production of iso-olefin and ether

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