Granted Patent B2

US 12,305,126 · App. 18/010,917 · Granted May 20, 2025

Inventors: Sibao Liu (Tianjin, CN); Dionisios G. Vlachos (Voorhees, NJ)

Assignee: UNIVERSITY OF DELAWARE

C10G47/18B01J23/30B01J23/42B01J29/068B01J35/643C10G2300/4006C10G2300/4012C10G2300/4025

Abstract

Claims (93)

1. A process for hydrocracking plastics, comprising contacting the plastics with a catalyst in a hydrogen atmosphere at a temperature between about 150° C. and about 800° C. for a period of time between about 0.1 hours and about 120 hours to form a fuel, a lubricant, or a mixture thereof; wherein

the catalyst is represented by formula:

X[(RO a )(QO b )]*Z  (I), and

wherein

X is a noble metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum;

R and Q independently are a transition metal;

O is oxygen;

a and b independently are 1, 2, 3, or 4;

Z is a zeolite or a mesoporous material; and

the symbol “*” means that the moiety X[(RO a )(QO b )] and the moiety Z are mechanically mixed; wherein the weight percentage of the moiety Z is about 1% to about 99% of the total weight of the catalyst.

2. The process of claim 1 , wherein

i) the plastics is selected from the group consisting of polyolefins, polyesters, polyethers, acrylic and methacrylic polymers, polyacetals, polyamides, polyurethanes, polyvinyl chloride, fluorinated polymers, polysulfide, polysulfones, copolymers, and a mixture thereof;

ii) the plastics is selected from the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), layered PP-PE-PS composites, and a mixture thereof; or

iii) the plastics is selected from the group consisting of high-density polyethylene (HDPE), low-density polyethylene (LDPE), isotactic polypropylene, polystyrene (PS), and a mixture thereof.

3. The process of claim 1 , wherein

i) the hydrogen atmosphere is at a pressure between about 1 bar to about 200 bar;

ii) the hydrogen atmosphere is at a pressure between about 20 bar to about 40 bar;

iii) the hydrogen atmosphere is at a pressure of about 30 bar;

iv) the temperature is between about 150° C. and about 400° C.;

v) the temperature is between about 190° C. and about 300° C.;

vi) the temperature is between about 200° C. and about 270° C.;

vii) the temperature is about 250° C.;

viii) the period of time is between about 0.5 hour and about 96 hours;

ix) the period of time is between about 1.5 hours and about 8 hours;

x) the period of time is between about 2 hours and about 6 hours; and/or

xi) the period of time is about 2 hours.

4. The process of claim 1 , wherein

i) the fuel is a mixture of liquid hydrocarbons;

ii) the fuel is selected from the group consisting of gasoline, jet fuel, kerosene fuel, diesel fuel, and a mixture thereof;

iii) the fuel has a carbon number distribution between about 5 and about 22;

iv) the fuel has a carbon number distribution between 5 and 12;

v) the fuel has a carbon number distribution between 9 and 22; or

vi) the lubricant is a mixture of hydrocarbons having a carbon number distribution between about 13 and about 60.

5. The process of claim 1 , wherein

i) the weight ratio between the plastics and the catalyst is about 200:1 to about 1:1;

ii) the weight ratio between the plastics and the catalyst is about 30:1 to about 5:1;

iii) the weight ratio between the plastics and the catalyst is about 20:1 to about 8:1; or

iv) the weight ratio between the plastics and the catalyst is about 10:1.

6. The process of claim 1 , wherein

i) the conversion of the plastics is at least about 85%;

ii) the conversion of the plastics is at least about 90%;

iii) the conversion of the plastics is at least about 95%; or

iv) the conversion of the plastics is at least about 99%.

7. The process of claim 1 , wherein

i) the yield of the fuel, the lubricant, or the mixture thereof is at least about 60%;

ii) the yield of the fuel, the lubricant, or the mixture thereof is at least about 75%; or

iii) the yield of the fuel, the lubricant, or the mixture thereof is at least about 85%.

8. The process of claim 1 , wherein

i) X is a noble metal selected from the group consisting of rhodium, palladium, and platinum; or

ii) X is platinum.

9. The process of claim 1 , wherein

i) R and Q are independently selected from a group consisting of tungsten, nickel, iron, cobalt, molybdenum, zinc, copper, manganese, chromium, titanium, vanadium, and zirconium; or

ii) R and Q are independently selected from a group consisting of tungsten, molybdenum, chromium, titanium, and zirconium.

10. The process of claim 9 , wherein

R is tungsten;

a is 3;

Q is zirconium; and

b is 2.

11. The process of claim 1 , wherein

i) the weight percentage of the component X is about 0.01% to about 50% of the weight of the moiety X[(RO a )(QO b )];

ii) the weight percentage of the component X is about 0.3% to about 5% of the weight of the moiety X[(RO a )(QO b )]; or

iii) the weight percentage of the component X is about 0.5% of the weight of the moiety X[(RO a )(QO b )].

12. The process of claim 1 , wherein

i) the weight percentage of the component (RO a ) is about 0.5% to about 99.9% of the weight of the moiety [(RO a )(QO b )];

ii) the weight percentage of the component (RO a ) is about 5% to about 20% of the weight of the moiety [(RO a )(QO b )]; or

iii) the weight percentage of the component (RO a ) is about 15% of the weight of the moiety [(RO a )(QO b )].

13. The process of claim 1 , wherein

i) Z is a zeolite; or

ii) Z is a mesoporous material.

14. The process of claim 13 , wherein

i) the zeolite has a silica to alumina molar ratio of about 0.1 to about 2000;

ii) the zeolite has a pore size of 5-8 Å;

iii) the zeolite has a pore size of 6-8 Å;

iv) the zeolite has a pore size of 5-6;

v) the zeolite is selected from the group consisting of HY, ZSM-5, HBEA, HMOR, SAPO-11, SAPO-34, and MCM-22;

vi) the zeolite is selected from the group consisting of HY(30), HY(60), HY(80), HZSM-5 (23), HBEA(25), and HMOR (20); wherein the number in the parenthesis indicates the silica to alumina molar ratio; or

vii) the zeolite is HY(30).

15. The process of claim 14 , wherein

i) the silica to alumina molar ratio of the zeolite is in the range of about 25 to about 60;

ii) wherein the silica to alumina molar ratio of the zeolite is in the range of about 25 to about 40; or

iii) wherein the silica to alumina molar ratio of the zeolite is about 30.

16. The process of claim 13 , wherein

i) the mesoporous material is a mesoporous zeolite;

ii) the mesoporous material is selected from the group consisting of microporous HY, microporous ZSM-5, microporous HBEA, and microporous HMOR; or

iii) the mesoporous material is an amorphous mesoporous material.

17. The process of claim 16 , wherein

i) the mesoporous zeolite comprises a crystal wall; or

ii) the mesoporous zeolite is HY(30)-M1, HY(30)-M2, HY(30)-M3, HY(30)-M4, mesoporous HY, mesoporous HZSM-5, mesoporous HBEA, mesoporous SAPO-11, mesoporous SAPO-34, or mesoporous MCM-22.

18. The process of claim 17 , wherein the crystal wall comprises a zeolite.

19. The process of claim 16 , wherein

i) the amorphous mesoporous material comprises an amorphous wall;

ii) the amorphous mesoporous material is selected from the group consisting of Al-MCM-41, Al-SBA-15, Al-SBA-16, Al-MCM-48, and Al-HMS; or

iii) the amorphous mesoporous material is Al-MCM-41.

Assignments (2)

Continuity (2)

References Cited (27)