Method of decomposing polymer

• US 20050148487A1
• Filed: 12/17/2004
• Published: 07/07/2005
• Est. Priority Date: 12/19/2003
• Status: Abandoned Application

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Brownscombe, Thomas Fairchild, Wellington, Scott Lee
• Application Number:
  US11/014,932
• Publication Number:
  US 20050148487A1
• Time in Patent Office: Days
• US Class Current: 510/446
• CPC Class Codes: C10G 1/10 from rubber or rubber waste
• CPC Class Codes: C10G 2300/1003 Waste materials
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2300/308 Gravity, density, e.g. API

Abstract

Inventions described herein generally relate a process for contacting a polymeric feed with one or more inorganic salt catalysts to produce a total product comprising a liquid product and, in some embodiments, non-condensable gas. In some embodiments, the inorganic salt catalyst exhibits an emitted gas inflection of an emitted gas in a temperature range between 50° C. and 500° C., as determined by Temporal Analysis of Products. In some embodiments, the inorganic salt catalyst has a heat transition in a temperature range between 200° C. and 500° C., as determined by differential scanning calorimetry (DSC), at a rate of 10° C. per minute. Inventions described herein also generally relate to compositions that have novel combinations of components therein.

Claims

39. A process for decomposing a polymeric feed composition comprising:

contacting a polymeric feed composition with an inorganic salt catalyst to produce a total product that includes liquid product mixture which is a liquid at 25°

C. and 0.101 MPa, the inorganic salt catalyst wherein the inorganic salt catalyst has a heat transition in a temperature range between 200°

C. and 500°

C., as determined by differential scanning calorimetry (DSC), at a rate of 10°

C. per minute; and

,

controlling contacting condition such that during the contacting at most 0.25 grams of hydrocarbons that are not condensable at 25°

C. and 0.101 MPa are formed per gram of polymeric feed, as determined by mass balance.

40. The process of claim 39 wherein the DSC temperature of the inorganic salt catalyst is in a temperature range between 250°

C. and 450°

C.

41. The process of claim 39 wherein the inorganic salt catalyst comprises at least two inorganic metal salts, and the inorganic salt catalyst has ionic conductivity that is at least, or particularly at least twice, the ionic conductivity of at least one of the inorganic salts of the inorganic salt catalyst at a temperature in a range from 300°

C. to 500°

C.

42. The process of claim 39 wherein the inorganic salt catalyst comprises one or more alkaline-earth metal carbonates.

43. The process of claim 39 further comprising contacting the polymeric feed composition and inorganic salt catalyst with a hydrogen source.

44. The process of claim 39 wherein the polymeric feed is selected from the group comprising polyolefins, polyethylene, polypropylene, epoxy resins, methyl methacrylate, polyurethanes, furan resins, rubber, polymeric wastes, paper, and municipal plastic wastes.

45. The process of claim 39 wherein the polymeric feed comprises tires.

46. The process of claim 39 wherein the polymeric feed comprises high density polyethylene.

47. The process of claim 39 wherein the polymeric feed comprises polyethyleneterephthalate.

48-1. The hydrocarbon composition of claim 48 further comprising between 0.05 and 0.5% of each of styrene, ethyl benzene, propyl benzene, and butyl benzene;

with a ratio of ethyl benzene to styrene of less than one, a ratio of propyl benzene to butyl benzene of greater than one;

a ratio of propyl benzene to ethyl benzene of grater than one.

50. A hydrocarbon composition comprising:

at least 45% by weight olefins;

30 to 48% by weight paraffins;

0.5 to 7% by weight aromatics; and

less than 2% by weight polynuclear aromatics, wherein the olefins are at least 60% alpha olefins with a ratio of internal distributed olefins to vinylidene olefins, on a mole basis, of from 2.5 to 4.5.

51. The hydrocarbon composition of claim 50 wherein the alpha olefin to paraffin ration in the range of 1.1 to 1.9 for the C10 molecular fraction, 0.7 to 1.22 for the C8 fraction, 0.7 and 1.27 for the C9 fraction.

52. The hydrocarbon composition of claim 50 wherein there is a peak in the olefin content as a function of carbon number in the carbon number range of 6 to 20

53. A hydrocarbon composition comprising:

between 45% and 85% by weight aromatics;

a ratio of aromatics to alpha plus vinylidene olefins of at least 100;

1;

an amount of diphenylketone of between 0.00001% and 4% by weight;

an amount of benzoic acid between 0.1% and 30% by weight;

an amount of toluic acid between 0.05% and 5% by weight; and

with at least 20% of the hydrogen contained in the hydrocarbon composition being aliphatic hydrogen

54. The hydrocarbon composition of claim 53 wherein the composition has an API gravity of 10 to 20;

a microcarbon residue of less than 0.3 weight percent; and

a sulfur content of less than 0.4%.

55. A liquid product, wherein the liquid product has, per gram of liquid product:

at most 0.05 grams of residue, as determined by ASTM Method D5307;

at least 0.001 grams of hydrocarbons with a boiling range distribution of at most 204°

C. (400°

F.) at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 204°

C. and 300°

C. at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 300°

C. and 400°

C. at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 400°

C. and 538°

C. (1,000°

F.) at 0.101 MPa; and

wherein the hydrocarbons in a boiling range distribution between 20°

C. and 204°

C. comprise olefins having terminal double bonds and olefins having internal double bonds with a molar ratio of olefins having terminal double bonds to olefins having internal double bonds of at most 0.9 as determined by proton nuclear magnetic resonance;

56. The liquid product as claimed in claim 55, wherein the hydrocarbons in a boiling range distribution between 20°

C. and 204°

C. have from 0.001 to 0.5 grams of olefins per gram of hydrocarbons in a boiling range distribution between 20°

C. and 204°

C.

57. A liquid product comprising per gram of liquid product:

at least 0.001 grams of styrene, as determined by flame ionization gas chromatography;

less than 0.005 grams of ethylbenzene, as determined by GC/MS;

at least 0.002 grams of limonene, as determined by GC/MS;

at least 0.000001 grams of octadecanenitrile, as determined by GC/MS

at least 0.001 grams of paraffins, as determined by ASTM Method D6730;

at least 0.001 grams of olefins, as determined by ASTM Method D6730, and

olefins wherein the olefins have at least 0.001 grams of terminal olefins per gram of olefins, as determined by ASTM Method D6730;

at most 0.05 grams of residue, as determined by ASTM Method D5307; and

at least 0.001 grams of a mixture of hydrocarbons that have a boiling range distribution between 20°

C. and 538°

C. (1,000°

F.), as determined by ASTM Method D5307, and the hydrocarbon mixture has, per gram of hydrocarbon mixture;

at least 0.001 grams of naphtha;

at least 0.001 grams of kerosene, and

at least 0.001 grams of vacuum gas oil.

58. The liquid product of claim 57, wherein a weight ratio of atomic hydrogen to atomic carbon (H/C) of the liquid product is at most 1.8.

59. The liquid product of claim 57, wherein the liquid product has an API gravity in a range from 13 to 30 at 15.5°

C., wherein API gravity is as determined by ASTM Method D6822.

60. The liquid product of claim 57, wherein the liquid product has from 0.00001-0.03 grams or from 0.0001-0.01 grams of coke per gram of liquid product.

61. A liquid product, wherein the liquid product has, per gram of liquid product:

at most 0.05 grams of residue, as determined by ASTM Method D5307;

at least 0.001 grams of hydrocarbons with a boiling range distribution of at most 204°

C. (400°

F.) at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 204°

C. and 300°

C. at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 300°

C. and 400°

C. at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 400°

C. and 538°

C. (1,000°

F.) at 0.101 MPa;

wherein the hydrocarbons in a boiling range distribution between 20°

C. and 204°

C. comprise olefins having terminal double bonds and olefins having internal double bonds with a molar ratio of olefins having terminal double bonds to olefins having internal double bonds of at least 3.0, as determined by ASTM Method D6730; and

wherein the hydrocarbons having a boiling range distribution between about 20°

C. and about 300°

C. comprise compounds with a carbon number of 8 to 15, each of said compounds having at least a ratio of alpha olefins to paraffins of 1.0 to 1.

62. The liquid product as claimed in claim 61, wherein the hydrocarbons in a boiling range distribution between 20°

C. and 204°

C. have from 0.001 to 0.5 grams of olefins per gram of hydrocarbons in a boiling range distribution between −

10°

C. and 204°

C.

63. A liquid product comprising per gram of liquid product:

at least 0.1 grams of alpha olefins, as determined by FID GC;

at most 0.001 grams of isobutene, as determined by FID GC;

at least 0.001 grams of paraffins, as determined by ASTM Method D6730;

at least 0.001 grams of olefins, as determined by ASTM Method D6730, and the olefins have at least 0.001 grams of terminal olefins per gram of olefins, as determined by ASTM Method D6730;

at most 0.05 grams of residue, as determined by ASTM Method D5307; and

at least 0.001 grams of a mixture of hydrocarbons that have a boiling range distribution between 20°

C. and 538°

C. (1,000°

F.), as determined by ASTM Method D5307, and the hydrocarbon mixture has, per gram of hydrocarbon mixture;

at least 0.001 grams of naphtha;

at least 0.001 grams of kerosene;

at least 0.001 grams of diesel; and

at least 0.001 grams of vacuum gas oil.

64. The hydrocarbon products of claims 63 wherein the carbon number distribution is peaked.

65. The liquid product of claims 63, wherein a weight ratio of atomic hydrogen to atomic carbon (H/C) of the liquid product is at most 1.8.

66. The liquid product of claim 63, wherein the liquid product has an API gravity in a range from 15 to 30 at 15.5°

C., wherein API gravity is as determined by ASTM Method D6822.

67. The liquid product of claim 63, wherein the liquid product has from 0.00001 to 0.03 grams of coke per gram of liquid product.

68. A liquid product comprising per gram of liquid product:

at least 0.001 double bonds to olefins having internal double bonds of at least 0.1, grams of paraffins, as determined by ASTM Method D6730;

at least 0.001 grams of olefins, as determined by ASTM Method D6730, and the olefins have at least 0.001 grams of terminal olefins per gram of olefins, as determined by ASTM Method D6730;

at most 0.05 grams of residue, as determined by ASTM Method D5307;

at least 0.001 grams of a mixture of hydrocarbons that have a boiling range distribution between 20°

C. and 538°

C. (1,000°

F.), as determined by ASTM Method D5307, and the hydrocarbon mixture has, per gram of hydrocarbon mixture;

at least 0.001 grams of naphtha;

at least 0.001 grams of kerosene, the kerosene having at least 0.1 grams of aromatics per gram of kerosene, as determined by ASTM Method D5186;

at least 0.001 grams of diesel, the diesel having at least 0.3 grams of aromatics per gram of diesel, as determined by IP Method 368/90; and

at least 0.001 grams of vacuum gas oil (VGO), the VGO having at least 0.1 grams of aromatics per gram of VGO, as determined by IP Method 368/90.

70. The liquid product of claim 68, wherein the hydrocarbons in a boiling range distribution between 20°

C. and 204°

C. have from 0.001-0.5 grams of olefins per gram of hydrocarbons in a boiling range distribution between 20°

C. and 204°

C.

69. A liquid product, wherein the liquid product has, per gram of liquid product:

at most 0.05 grams of residue, as determined by ASTM Method D5307;

at least 0.001 grams of hydrocarbons with a boiling range distribution of at most 204°

C. (400°

F.) at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 204°

C. and 300°

C. at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 300°

C. and 400°

C. at 0.101 MPa;

at least 0.001 grams of hydrocarbons with a boiling range distribution between 400°

C. and 538°

C. (1,000°

F.) at 0.101 MPa; and

wherein the hydrocarbons in a boiling range distribution between 20°

C. and 50°

C. comprise olefins having terminal double bonds and olefins having internal double bonds with a molar ratio of olefins having terminal particularly at least 0.4 as determined by FID GC.

71. A liquid product comprising per gram of liquid product:

at least 0.000001 grams of diphenyl ketone, as determined by GC/MS;

at least 0.001 grams of paraffins, as determined by ASTM Method D6730;

at least 0.001 grams of olefins, as determined by ASTM Method D6730, and the olefins have at least 0.001 grams of terminal olefins per gram of olefins, as determined by ASTM Method D6730;

at most 0.05 grams of residue, as determined by ASTM Method D5307; and

at least 0.001 grams of a mixture of hydrocarbons that have a boiling range distribution between 20°

C. and 538°

C., as determined by ASTM Method D5307, and the hydrocarbon mixture has, per gram of hydrocarbon mixture;

at least 0.001 grams of naphtha;

at least 0.001 grams of kerosene, the kerosene having at least 0.05 grams of aromatics per gram of kerosene, as determined by ASTM Method D5186;

at least 0.001 grams of diesel, the diesel having at least 0.05 grams of aromatics per gram of diesel, as determined by IP Method 368/90; and

at least 0.001 grams of vacuum gas oil (VGO), the VGO having at least 0.05 grams of aromatics per gram of VGO, as determined by IP Method 368/90.

72. The liquid product of claim 71, wherein a weight ratio of atomic hydrogen to atomic carbon (H/C) of the liquid product is at most 1.8.

73. The liquid product of claim 71, wherein the liquid product has an API gravity in a range from 15 to 30 at 15.5°

C., wherein API gravity is as determined by ASTM Method D6822.

74. The liquid product of claim 71, wherein the liquid product has from 0.00001 to 0.03 grams of coke per gram of liquid product.