US4935566A — Dehydrocyclization and reforming process

Claim 1

Independent Claim 65 words

A process for reforming a naphtha feedstock of low octane value comprising contacting the feedstock, under reforming conditions, with a non-acidic catalyst composition consisting essentially of a reforming hydrogenation/dehydrogenation metal in combination with a non-acidic microporous crystalline material containing tin, and recovering a reformate having an octane value greater than that of the feedstock and having an aromatic content greater than that of the feed.

Claim 2

Dependent Claim 65 words

A process for reforming a naphtha feedstock of low octane value comprising contacting the feedstock, under reforming conditions, with a non-acidic catalyst composition consisting essentially of a reforming hydrogenation/dehydrogenation metal in combination with a non-acidic microporous crystalline material containing tin, and recovering a reformate having an octane value greater than that of the feedstock and having an aromatic content greater than that of the feed.

Claim 3

Dependent Claim 30 words

The process of claim 1, wherein said reforming metal comprises 0.1 to 20 weight percent of the catalyst and said tin comprises 0.05 to 20 weight percent of the combination.

Claim 4

Dependent Claim 16 words

The process of claim 1, wherein said reforming conditions further includes adding hydrogen to the feedstock.

Claim 5

Dependent Claim 23 words

The process of claim 1, wherein the naphtha feedstock comprises a light naphtha fraction of C 6 to 250° F. boiling range components.

Claim 6

Dependent Claim 33 words

The process of claim 1, wherein the naphtha feedstock is separated into at least two fractions including a fraction containing C 6 -C 7 paraffins wherein said fraction is contacted with said catalyst.

Claim 7

Dependent Claim 20 words

The process of claim 5, wherein a second fraction of said two fractions is contacted with a conventional reforming catalyst.

Claim 8

Dependent Claim 36 words

The process of claim 1, wherein said non-acidic crystalline material is a microporous material which is isostructural with a zeolite, selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-23, ZSM-48, ZSM-50, and zeolite beta.

Claim 9

Dependent Claim 13 words

The process of claim 1, wherein the microporous crystalline material zeolite is ZSM-5.

Claim 10

Dependent Claim 21 words

The process of claim 1, wherein the aluminum content of the non-acidic crystalline microporous material is less than 0.1 weight percent.

Claim 11

Dependent Claim 21 words

The process of claim 1, wherein the aluminum content of the non-acidic microporous crystalline material is less than 0.02 weight percent.

Claim 12

Dependent Claim 14 words

The process of claim 1, wherein the reforming metal is a Group VIII metal.

Claim 13

Dependent Claim 14 words

The process of claim 1, wherein the hydrogenation/dehydrogenation metal is a platinum group metal.

Claim 14

Dependent Claim 11 words

The process of claim 1, wherein the hydrogenation/dehydrogenation metal is platinum.

Claim 15

Dependent Claim 18 words

The process of claim 1, wherein the pressure of the reforming conditions ranges from 0 to 500 psig.

Claim 16

Dependent Claim 16 words

The process of claim 5 wherein the pressure of reforming ranges from 0 to 500 psig.

Claim 17

Dependent Claim 30 words

The process of claim 1, wherein the liquid yield exceeds the liquid yield of reforming undertaken in the presence of the tin free counterpart of the non-acidic crystalline microporous material.

Claim 18

Dependent Claim 30 words

The process of claim 5, wherein the liquid yield exceeds the liquid yield of reforming undertaken in the presence of the tin free counterpart of the non-acidic crystalline microporous material.

Claim 19

Dependent Claim 16 words

The process of claim 1, wherein the temperature of reforming ranges from 800° to 1100° F.

Claim 20

Dependent Claim 25 words

The process of claim 1, wherein the feedstock, prior to said contacting, is subjected to fractionation to remove the fraction boiling below about 150° F.

Claim 21

Dependent Claim 16 words

The process of claim 5, wherein the tmperature of reforming ranges from 800° to 1100° F.

Claim 22

Dependent Claim 16 words

The process of claim 15, wherein the temperature of reforming ranges from 800° to 1100° F.

Claim 23

Dependent Claim 17 words

The process of claim 1, wherein the feedstock is rich in C 6 -C 9 normal paraffins.

Claim 24

Dependent Claim 17 words

The process of claim 21, wherein the feedstock is rich in C 6 -C 9 normal paraffins.

Claim 25

Dependent Claim 139 words

A process for upgrading a naphtha comprising in combination: providing a feedstream which is a paraffin rich naphtha; contacting the feedstream with a non-acidic catalyst consisting essentially of a hydrogenation/dehydrogenation metal and a tin-containing non-acidic crystalline microporous material, under conditions including a temperature of from 800° F. to 1100° F., a pressure of about 0 to 500 psig, and LHSV of 0.1 to 20; and cofeeding with said feedstream a mixture of hydrogen and diluent which is inert to aromatization under the conditions of the process wherein the hydrogen:hydrocarbon (feed) ratio (molar) ranges from 0.1 to 20 and wherein the diluent:hydrocarbon (feed) ratio (molar) ranges from 1 to 20; and recovering a reformate of octane number and aromatic content greater than that of the feedstream and greater than that of the reformate produced in the absence of said diluent.

Claim 26

Dependent Claim 139 words

A process for upgrading a naphtha comprising in combination: providing a feedstream which is a paraffin rich naphtha; contacting the feedstream with a non-acidic catalyst consisting essentially of a hydrogenation/dehydrogenation metal and a tin-containing non-acidic crystalline microporous material, under conditions including a temperature of from 800° F. to 1100° F., a pressure of about 0 to 500 psig, and LHSV of 0.1 to 20; and cofeeding with said feedstream a mixture of hydrogen and diluent which is inert to aromatization under the conditions of the process wherein the hydrogen:hydrocarbon (feed) ratio (molar) ranges from 0.1 to 20 and wherein the diluent:hydrocarbon (feed) ratio (molar) ranges from 1 to 20; and recovering a reformate of octane number and aromatic content greater than that of the feedstream and greater than that of the reformate produced in the absence of said diluent.

Claim 27

Dependent Claim 19 words

The process of claim 24, wherein the diluent is at least one hydrocarbon of 1 to 5 carbon atoms.

Claim 28

Dependent Claim 11 words

The process of claim 24, wherein the diluent is an aromatic.

Claim 29

Dependent Claim 20 words

The process of claim 24, wherein at least a portion of the reformate is recycled as diluent in said cofeeding.

Claim 30

Dependent Claim 13 words

The process of claim 24, wherein the naphtha is hydrotreated prior to reforming.

Claim 31

Dependent Claim 29 words

The process of claim 24, wherein the crystalline microporous material is characterized by a pore size the average diameter of which ranges from about 5 to about 8 Angstroms.

Claim 32

Dependent Claim 14 words

The process of claim 24, wherein the crystalline microporous material is isostructural to ZSM-5.

Claim 33

Dependent Claim 10 words

The process of claim 24, wherein said metal is platinum.

Claim 34

Dependent Claim 10 words

The process of claim 30, wherein said metal is platinum.

Claim 35

Dependent Claim 15 words

The process of claim 24, wherein said crystalline microporous material is isostructural with a zeolite.

Claim 36

Dependent Claim 17 words

The process of claim 33, wherein said zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-23, ZSM-48 and ZSM-50.

Claim 37

Dependent Claim 16 words

The process of claim 24, wherein said crystalline microporous material is a SAPO or an ALPO.

Claim 38

Dependent Claim 14 words

The process of claim 24, wherein said crystalline microporous material is bound with silica.

Claim 39

Dependent Claim 13 words

The process of claim 24, wherein the diluent is nitrogen, helium, carbon dioxide.

Claim 40

Dependent Claim 32 words

The process of claim 24, wherein the diluent is predominantly propane and the hydrogen:hydrocarbon (feed) ratio (molar) is preferably less than 3:1 and the reactor total pressure is less than 150 psig.

Claim 41

Dependent Claim 59 words

A process for reforming naphthas comprising providing a feedstream which is a C 6 .spsb.+ paraffin rich naphtha; contacting the feedstream with a catalyst comprising a reforming hydrogenation/dehydrogenation metal and a tin containing non-acidic crystalline microporous material, in the presence of a diluent, under reforming conditions, and to increase the octane of the reformate produced and its aromatic content.

Claim 42

Dependent Claim 59 words

A process for reforming naphthas comprising providing a feedstream which is a C 6 .spsb.+ paraffin rich naphtha; contacting the feedstream with a catalyst comprising a reforming hydrogenation/dehydrogenation metal and a tin containing non-acidic crystalline microporous material, in the presence of a diluent, under reforming conditions, and to increase the octane of the reformate produced and its aromatic content.

Claim 43

Dependent Claim 14 words

The process of claim 39, wherein said diluent is C 1 -C 5 hydrocarbon.

Claim 44

Dependent Claim 23 words

The process of claim 39, wherein the diluent is methane, ethane, propane, butane, isobutane, pentane, C 1 -C 5 hydrocarbons and combinations thereof.

Claim 45

Dependent Claim 14 words

The process of claim 39, wherein the diluent is helium, nitrogen, or carbon dioxide.

Claim 46

Dependent Claim 13 words

The process of claim 39, wherein the naphtha is hydrotreated prior to reforming.

Claim 47

Dependent Claim 29 words

The process of claim 39, wherein the crystalline microporous material is characterized by a pore size the average diameter of which ranges from about 5 to about 8 Angstroms.

Claim 48

Dependent Claim 10 words

The process of claim 39, which further includes recovering hydrogen.

Claim 49

Dependent Claim 15 words

The process of claim 39, wherein said crystalline microporous material is isostructural with a zeolite.

Claim 50

Dependent Claim 10 words

The process of claim 46, wherein said zeolite is ZSM-5.

Claim 51

Dependent Claim 11 words

The process of claim 39, wherein the diluent is an aromatic.

Claim 52

Dependent Claim 16 words

The process of claim 39, wherein the diluent is reformate which is recycled during said cofeeding.

Claim 53

Independent Claim 120 words

A method for increasing the aromatic content of a reformate with a research octane in the range of 50 to 90 comprising providing said reformate of research octane of 50 to 90 containing C 6 .spsb.+ aliphatics and contacting said reformate with a non-acidic catalyst composition, at a temperature of at least about 800° F., at a pressure ranging from about 0 to about 500 psig, and at a liquid hourly space velocity (LHSV) ranging from 0.1 to 20; wherein said catalyst composition consisting essentially of a hydrogenation/dehydrogenation component and a tin containing non-acidic crystalline, microporous material; producing a product of research octane greater than that of the reformate and of aromatic components content greater than that of the reformate.

Claim 54

Independent Claim 120 words

A method for increasing the aromatic content of a reformate with a research octane in the range of 50 to 90 comprising providing said reformate of research octane of 50 to 90 containing C 6 .spsb.+ aliphatics and contacting said reformate with a non-acidic catalyst composition, at a temperature of at least about 800° F., at a pressure ranging from about 0 to about 500 psig, and at a liquid hourly space velocity (LHSV) ranging from 0.1 to 20; wherein said catalyst composition consisting essentially of a hydrogenation/dehydrogenation component and a tin containing non-acidic crystalline, microporous material; producing a product of research octane greater than that of the reformate and of aromatic components content greater than that of the reformate.

Claim 55

Dependent Claim 11 words

The method of claim 50, wherein the hydrogenation/dehydrogenation metal is platinum.

Claim 56

Dependent Claim 23 words

The method of claim 50, wherein the hydrogenation/dehydrogenation metal is selected from the group consisting of platinum, palladium, rhodium, rhenium, and mixtures thereof.

Claim 57

Dependent Claim 35 words

The method of claim 50, the reformate of research octane of 50 to 90 which contains C 6 and C 7 paraffins, which on contact with said catalyst are aromatized to C 6 .spsb.+ aromatics.

Claim 58

Dependent Claim 48 words

The method of claim 50, further including increasing the liquid yield of reforming, by subjecting a naphtha, under reforming conditions, with an acidic reforming catalyst to produce said reformate of research octane of 50 to 90 and containing said C 6 .spsb.+ aliphatics, and then undertaking said contacting.

Claim 59

Dependent Claim 33 words

The method of claim 50, wherein providing said reformate includes subjecting a naphtha with a reforming catalyst under reforming conditions until the research octane of the reformed product has reached 50 to 90.

Claim 60

Dependent Claim 44 words

The method of claim 50, wherein providing said reformate comprises contacting naphtha fraction under reforming conditions of temperature and pressure with a reforming catalyst which is effective to provide a reformate of 50 to 90 research octane containing a C 6 .spsb.+ paraffin fraction.

Claim 61

Dependent Claim 19 words

The process of claim 56, wherein said C 6 .spsb.+ paraffin fraction includes C 6 to C 10 paraffins.

Claim 62

Dependent Claim 19 words

The method of claim 50, wherein the non-acidic microporous crystalline material exhibits the X-ray diffraction pattern of a zeolite.

Claim 63

Dependent Claim 18 words

The process of claim 58, wherein the non-acidic, microporous crystalline material contains less than 0.1 weight percent aluminum.

Claim 64

Dependent Claim 18 words

The method of claim 50, wherein the non-acidic crystalline microporous material exhibits the X-ray diffraction pattern of ZSM-5.

Claim 65

Dependent Claim 14 words

The method of claim 50, wherein the dehydrogenation metal is a Group VIII metal.

Claim 66

Dependent Claim 14 words

The method of claim 50, wherein the dehydrogenation metal is a platinum group metal.

Claim 67

Dependent Claim 83 words

A process for manufacturing benzene, toluene, or mixtures thereof, said process comprising providing a feed comprising substantially isomer-free normal hexane, substantially isomer-free normal heptane, or mixtures thereof and contacting said feed under dehydrocyclization conditions of temperature, pressure and space velocity with a non-acidic dehydrogenation catalyst consisting essentially of a platinum group metal supported on a zeolite containing tin or indium, said zeolite having the crystal structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48, and recovering said benzene, toluene or mixture thereof.

Claim 68

Dependent Claim 83 words

A process for manufacturing benzene, toluene, or mixtures thereof, said process comprising providing a feed comprising substantially isomer-free normal hexane, substantially isomer-free normal heptane, or mixtures thereof and contacting said feed under dehydrocyclization conditions of temperature, pressure and space velocity with a non-acidic dehydrogenation catalyst consisting essentially of a platinum group metal supported on a zeolite containing tin or indium, said zeolite having the crystal structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48, and recovering said benzene, toluene or mixture thereof.

Claim 69

Dependent Claim 62 words

The process described in claim 1, wherein said conversion conditions include a temperature of about 400° C. to about 600° C., a pressure of 5 to about 500 psi (absolute) and a hexane and/or heptane WHSV of 0.1 to 10.0 and wherein said catalyst comprises 0.1 to 20 wt% of platinum group metal and 0.05 to 20 wt% of indium or tin.

Claim 70

Dependent Claim 15 words

The process of claim 64, wherein said zeolite contains less than about 0.1 wt% alumina.

Claim 71

Dependent Claim 34 words

The process of claim 63, wherein said feed contains one or more diluents selected from the group consisting of hydrogen gas, an inert gas, and an aliphatic hydrocarbon having one to five carbon atoms.

Claim 72

Dependent Claim 34 words

The process of claim 64, wherein said feed contains one or more diluents selected from the group consisting of hydrogen gas, an inert gas, and an aliphatic hydrocarbon having one to five carbon atoms.

Claim 73

Dependent Claim 33 words

The process of claim 65, wherein said feed contains one or morediluents selected from the group consisting of hydrogen gas, an inert gas, and an aliphatic hydrocarbon having one to five carbon atoms.

Claim 74

Dependent Claim 19 words

The process of claim 63, wherein said zeolite has the crystal structure of ZSM-5 and said metal is platinum.

Claim 75

Dependent Claim 19 words

The process of claim 64, wherein said zeolite has the crystal structure of ZSM-5 and said metal is platinum.

Claim 76

Dependent Claim 20 words

The process of claim 65, wherein said zeolite has the crystal structure of ZSM-5 and said group metal is platinum.

Claim 77

Dependent Claim 20 words

The process of claim 66, wherein said zeolite has the crystal structure of ZSM-5 and said group metal is platinum.

Claim 78

Dependent Claim 21 words

The process of claim 67, wherein said zeolite has the crystal structure of ZSM-5 and said platinum group metal is platinum.

Claim 79

Dependent Claim 21 words

The process of claim 68, wherein said zeolite has the crystal structure of ZSM-5 and said platinum group metal is platinum.

Claim 80

Dependent Claim 111 words

A process for manufacturing benzene or toluene or mixtures thereof, said process comprising, in combination: fractionally distilling a straight-run paraffinic gasoline and recovering a fraction rich in normal hexane or normal heptane or a mixture thereof; contacting said recovered fraction with a Type 5A molecular sieve whereby sorbing said normal paraffin or paraffins from said recovered fraction and recovering a substantially isomer-free normal paraffin or paraffins; and contacting under dehydrogenation conditions said substantially isomer-free normal paraffin or paraffins with a non-acidic dehydrogenation catalyst consisting essentially of a platinum group metal supported on a tin containing zeolite, said zeolite having the crystal structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48.

Claim 81

Dependent Claim 111 words

A process for manufacturing benzene or toluene or mixtures thereof, said process comprising, in combination: fractionally distilling a straight-run paraffinic gasoline and recovering a fraction rich in normal hexane or normal heptane or a mixture thereof; contacting said recovered fraction with a Type 5A molecular sieve whereby sorbing said normal paraffin or paraffins from said recovered fraction and recovering a substantially isomer-free normal paraffin or paraffins; and contacting under dehydrogenation conditions said substantially isomer-free normal paraffin or paraffins with a non-acidic dehydrogenation catalyst consisting essentially of a platinum group metal supported on a tin containing zeolite, said zeolite having the crystal structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1993-06-18	1993-12-18	1994-06-19	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1997-06-18	1997-12-18	1998-06-19	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2001-06-18	2001-12-18	2002-06-19	$7700.00	Window Closed / Lapsed

Dehydrocyclization and reforming process

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