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US4116995A Expired / Lapsed US ⏱️ 0.0 years remaining

Hydrocarbon synthesis using a rare earth promoted metal silicate

Assignee: Shell Internationale Research Maatschappij BV
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Filing: 1976-11-29
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Granted: 1978-09-26
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Expires: 1996-11-29
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Abstract

Abstract The conversion of carbon monoxide and hydrogen to produce a mixture of low molecular weight hydrocarbons which, on a methane-free basis, contain a predominance of C 2 -C 6 paraffins is achieved using as the catalyst a rare earth metal promoted layered complex metal silicate composition characterized as having repeating units of the structural formula [(1-x)Ni.sup.a + xRu.sup.6 ].sub.n (OH).sub.4 Si.sub.2 O.sub.5.wH.sub.2 O where x is a number from 0 to 1, this number expressing the atomic fraction of the metals nickel and ruthenium; a is the valence of nickel; b is the valence of ruthenium; n is a number equal in value to that defined by the ratio 6/[a(1-x) + bx] and w is a number ranging from 0 to 4. A rare earth promoted nickel chrysotile is the preferred catalyst.

Inventors

  • 👤 Thaddeus P. Kobylinski
  • 👤 Harold E. Swift

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-23 19:30
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/049; C; C07; C07C; C07C1/00; C07C1/02; C07C1/04; C07C1/0425; C07C1/043; C07C1/0435; C07C1/12; C07C2521/00; C07C2521/16; C07C2523/00; C07C2523/10; C07C2523/70; C07C2523/74; C07C2523/755

Claims Analysis

Total Claims: 35
Claim 1
Independent Claim 174 words
A process which comprises contacting a charge stock comprising hydrogen and at least one carbon oxide selected from the group consisting of CO and CO 2 wherein the molar ratio of hydrogen to combined carbon oxide is from 1:1 to 4:1 under reaction conditions including a temperature of from 300° F. to 500° F. with a catalyst consisting essentially of a rare earth promoted metal silicate characterized as having repeating units of the structural formula: [(1=x)Ni.sup.a + xRu.sup.b ].sub.n (OH).sub.4 Si.sub.2 O.sub.5.wH.sub.2 O where x is a number from 0 to 1, this number expressing the atomic fraction of the metals nickel and ruthenium; a is the valence of nickel; b is the valence of ruthenium; n is a number equal in value to that defined by the ratio 6/[a(1=x) + bx] and w is a number ranging from 0 to 4; and thereafter recovering a product, which product, on a methane-free hydrocarbon basis contains at least 60 mole percent of low molecular weight hydrocarbons having from 2 to 6 carbon atoms per molecule.
Claim 2
Dependent Claim 174 words
A process which comprises contacting a charge stock comprising hydrogen and at least one carbon oxide selected from the group consisting of CO and CO 2 wherein the molar ratio of hydrogen to combined carbon oxide is from 1:1 to 4:1 under reaction conditions including a temperature of from 300° F. to 500° F. with a catalyst consisting essentially of a rare earth promoted metal silicate characterized as having repeating units of the structural formula: [(1=x)Ni.sup.a + xRu.sup.b ].sub.n (OH).sub.4 Si.sub.2 O.sub.5.wH.sub.2 O where x is a number from 0 to 1, this number expressing the atomic fraction of the metals nickel and ruthenium; a is the valence of nickel; b is the valence of ruthenium; n is a number equal in value to that defined by the ratio 6/[a(1=x) + bx] and w is a number ranging from 0 to 4; and thereafter recovering a product, which product, on a methane-free hydrocarbon basis contains at least 60 mole percent of low molecular weight hydrocarbons having from 2 to 6 carbon atoms per molecule.
Claim 3
Dependent Claim 13 words
A process according to claim 1 wherein the metal silicate is nickel chrysotile.
Claim 4
Dependent Claim 24 words
A process according to claim 2 wherein the amount of rare earth metal is from 0.5 to 25 weight percent of the final catalyst.
Claim 5
Dependent Claim 13 words
A process according to claim 3 wherein the rare earth metal is thorium.
Claim 6
Dependent Claim 13 words
A process according to claim 3 wherein the rare earth metal is lanthanum.
Claim 7
Dependent Claim 13 words
A process according to claim 3 wherein the rare earth metal is cerium.
Claim 8
Dependent Claim 13 words
A process according to claim 3 wherein the rare earth metal is praesodymium.
Claim 9
Dependent Claim 18 words
A process according to claim 3 wherein the rare earth metal is a mixture of rare earth metals.
Claim 10
Dependent Claim 17 words
A process according to claim 8 wherein the mixture of rare earth metals is thorium and lanthanum.
Claim 11
Dependent Claim 17 words
A process according to claim 8 wherein the mixture of rare earth metals is thorium and praesodymium.
Claim 12
Dependent Claim 19 words
A process according to claim 3 wherein the rare earth metal is added to the nickel chrysotile by deposition.
Claim 13
Dependent Claim 23 words
A process according to claim 11 wherein the rare earth metal is deposited from an aqueous solution of a rare earth metal nitrate.
Claim 14
Dependent Claim 15 words
A process according to claim 12 wherein the rare earth metal nitrate is thorium nitrate.
Claim 15
Dependent Claim 15 words
A process according to claim 12 wherein the rare earth metal nitrate is praesodymium nitrate.
Claim 16
Dependent Claim 23 words
A process according to claim 3 wherein the rare earth metal is incorporated into the catalyst during the preparation of the nickel chrysotile.
Claim 17
Dependent Claim 46 words
A process according to claim 15 wherein the nickel chrysotile is a synthetic nickel chrysotile prepared by combining a hydrous silicate solution with a metal oxide or hydroxide solution containing a rare earth salt in an alkaline medium at a pH above 10; and thereafter calcining.
Claim 18
Dependent Claim 14 words
A process according to claim 16 wherein the rare earth salt is thorium nitrate.
Claim 19
Dependent Claim 14 words
A process according to claim 16 wherein the rare earth salt is lanthanum nitrate.
Claim 20
Dependent Claim 14 words
A process according to claim 16 wherein the rare earth salt is cerium nitrate.
Claim 21
Dependent Claim 14 words
A process according to claim 16 wherein the rare earth salt is praesodymium nitrate.
Claim 22
Dependent Claim 20 words
A process according to claim 16 wherein the rare earth metal salt is a mixture of rare earth metal salts.
Claim 23
Dependent Claim 21 words
A process according to claim 21 wherein the rare earth metal salt mixture is comprised of thorium nitrate and lanthanum nitrate.
Claim 24
Dependent Claim 21 words
A process according to claim 21 wherein the rare earth metal salt mixture is comprised of thorium nitrate and praesodymium nitrate.
Claim 25
Dependent Claim 13 words
A process according to claim 16 wherein the pH is 12 to 14.
Claim 26
Dependent Claim 27 words
A process according to claim 2 wherein the methane-free hydrocarbon product contains at least 70 mole percent of paraffins having 2 to 6 carbon atoms per molecule.
Claim 27
Dependent Claim 28 words
A process according to claim 2 wherein the methane-free hydrocarbon product contains at least 90 mole percent of paraffins having from 2 to 6 carbon atoms per molecule.
Claim 28
Dependent Claim 202 words
A process which comprises contacting a charge stock comprising hydrogen and at least one carbon oxide selected from the group consisting of CO and CO 2 wherein the molar ratio of hydrogen to combined carbon oxide is from 1.5:1 to 2.5:1 under reaction conditions including a temperature of from 350° F. to 450° F. with a catalyst consisting essentially of a rare earth metal promoted metal silicate characterized as having repeating units of the structural formula: [(1-x)Ni.sup.a + xRu.sup.b ].sub.n (OH).sub.4 SiO.sub.2 O.sub.5.wH.sub.2 O where x is a number from 0 to 1, this number expressing the atomic fraction of the metals nickel and ruthenium; a is the valence of nickel; b is the valence of ruthenium; n is a number equal in value to that defined by the ratio 6/[a(1-x) + bx] and w is a number ranging from 0 to 4; and thereafter recovering a hydrocarbon product consisting of at least about 50 weight percent on a methane free basis of paraffins having at least two carbon atoms per molecule and where in said hydrocarbon product the hydrocarbon distribution is such that at least 60 mole percent of said hydrocarbon product has from 2 to 6 carbon atoms per molecule.
Claim 29
Dependent Claim 202 words
A process which comprises contacting a charge stock comprising hydrogen and at least one carbon oxide selected from the group consisting of CO and CO 2 wherein the molar ratio of hydrogen to combined carbon oxide is from 1.5:1 to 2.5:1 under reaction conditions including a temperature of from 350° F. to 450° F. with a catalyst consisting essentially of a rare earth metal promoted metal silicate characterized as having repeating units of the structural formula: [(1-x)Ni.sup.a + xRu.sup.b ].sub.n (OH).sub.4 SiO.sub.2 O.sub.5.wH.sub.2 O where x is a number from 0 to 1, this number expressing the atomic fraction of the metals nickel and ruthenium; a is the valence of nickel; b is the valence of ruthenium; n is a number equal in value to that defined by the ratio 6/[a(1-x) + bx] and w is a number ranging from 0 to 4; and thereafter recovering a hydrocarbon product consisting of at least about 50 weight percent on a methane free basis of paraffins having at least two carbon atoms per molecule and where in said hydrocarbon product the hydrocarbon distribution is such that at least 60 mole percent of said hydrocarbon product has from 2 to 6 carbon atoms per molecule.
Claim 30
Dependent Claim 31 words
A process according to claim 27 wherein the rare earth metal is thorium and the amount of rare earth metal is from 0.5 to 10 weight percent of the final catalyst.
Claim 31
Dependent Claim 37 words
A process according to claim 27 wherein said rare earth metal is a mixture of rare earth metals and the amount of said rare earth metals is from 0.5 to 10 weight percent of the final catalyst.
Claim 32
Dependent Claim 36 words
A process according to claim 27 wherein the metal silicate is nickel chrysotile; the hydrogen to combined carbon oxide ratio is from 1.5:1 to about 2:1; the reaction temperature is from 375° F. to 425° F.
Claim 33
Dependent Claim 31 words
A process according to claim 30 wherein the rare earth metal is thorium and the amount of rare earth metal is from 0.5 to 10. weight percent of the final catalyst.
Claim 34
Dependent Claim 37 words
A process according to claim 30 wherein said rare earth metal is a mixture of rare earth metals and the amount of said rare earth metals is from 0.5 to 10 weight percent of the final catalyst.
Claim 35
Dependent Claim 32 words
A process according to claim 27 wherein the hydrocarbon distribution in said hydrocarbon product is such that more than 50% of said product has from 3 to 5 carbon atoms per molecule.

References Cited (Backward Citations)

US3947483A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1981-09-25 1982-03-27 1982-09-26 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1985-09-25 1986-03-27 1986-09-26 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1989-09-25 1990-03-27 1990-09-26 $7700.00 Window Closed / Lapsed

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