Nanocatalysts for hydrocracking and methods of their use

1. A catalyst comprising:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 500;

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers;

wherein the catalyst does not further comprise silver nanoparticles supported on the alumina nanoparticles; and

wherein the alumina nanoparticles are present in an amount of at least 99% by weight of catalyst.

2. A catalyst according to claim 1 , wherein the ratio is in a range of from about 99 to about 400.

3. A catalyst according to claim 1 , wherein the nickel oxide (NiO) nanoparticles are present in an amount of about 0.2% to about 1% by weight of catalyst.

4. A catalyst according to claim 3 , wherein the nickel oxide (NiO) nanoparticles are present in an amount of about 0.2% to about 0.6% by weight of catalyst.

5. A catalyst according to claim 1 , further comprising nanoparticles of at least one Group VIIIB metal oxide supported on the alumina nanoparticles;

wherein:

the Group VIIIB metal is selected from the group consisting of Pd and Pt, or combination thereof; and

the alumina nanoparticle to Group VIIIB metal oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 500.

6. A catalyst according to claim 1 , wherein the S BET surface area is from about 17 to about 70 m 2 /g.

7. A method for upgrading heavy oil fractions in a well, comprising:

contacting the heavy oil in a well producing heavy oil with a catalyst according to claim 1 for a time and under conditions sufficient to increase the H/C ratio.

8. A method according to claim 7 further comprising contacting the heavy oil with a hydrogen transfer agent.

9. A method according to claim 8 , wherein the hydrogen transfer agent comprises 1,2,3,4-tetrahydronaphthalene.

10. A method for upgrading heavy oil fractions in a well, comprising:

contacting the heavy oil in a well producing heavy oil with a catalyst according to claim 5 for a time and under conditions sufficient to increase the H/C ratio.

11. A method according to claim 10 further comprising contacting the heavy oil with a hydrogen transfer agent.

12. A method according to claim 11 , wherein the hydrogen transfer agent comprises 1,2,3,4-tetrahydronaphthalene.

13. A process for preparing a catalyst comprising:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein:

the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers;

the catalyst does not further comprise nanoparticles of silver supported on the alumina nanoparticles; and

the nickel oxide (NiO) nanoparticles are present in an amount of about 0.2% to about 0.6% by weight of catalyst;

wherein the alumina nanoparticles are present in an amount of at least 99% by weight of catalyst;

said process comprising:

dry impregnating an amorphous dried sodium aluminate precipitate with an aqueous solution of a water-soluble nickel salt; and

drying the nickel impregnated precipitate;

wherein the dry impregnating and drying steps are each carried out for a time and under conditions sufficient to provide the dried nickel impregnated precipitate catalyst.

14. A process according to claim 13 , wherein the dried nickel impregnated precipitate is calcined in the presence of oxygen or air for a time and under conditions sufficient to provide the calcined catalyst.

15. A process according to claim 14 , wherein the nickel impregnated precipitate is dried at a temperature in the range of from about 100 to about 140° C. for from about 3 to about 8 hours.

16. A process according to claim 15 , wherein the dried nickel impregnated precipitate is calcined at a temperature in the range of from about 400 to about 500° C. for from about 3 to about 8 hours.

17. A process according to claim 13 , wherein the nickel salt comprises nickel nitrate, nickel chloride or nickel sulfate.

18. A process according to claim 13 , wherein the nickel salt comprises nickel nitrate.

19. A process for preparing a catalyst according to claim 13 , wherein the catalyst consists essentially of nickel oxide nanoparticles, or an oxide thereof, supported on alumina nanoparticles.

20. A catalyst prepared by the process of claim 14 .

21. A process for preparing a catalyst comprising:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein:

the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers;

the catalyst does not further comprise nanoparticles of silver supported on the alumina nanoparticles; and

the nickel oxide (NiO) nanoparticles are present in an amount of about 0.2% to about 0.6% by weight of catalyst; and

nanoparticles of at least one Group VIIIB metal oxide nanoparticles supported on the alumina nanoparticles;

wherein:

the Group VIIIB metal is selected from the group consisting of Pd and Pt, or combination thereof; and

the alumina nanoparticle to Group VIIIB metal oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

said process comprising:

dry impregnating an amorphous dried sodium aluminate precipitate with an aqueous solution of a water-soluble nickel salt; and

drying the nickel impregnated precipitate;

wherein the dry impregnating and drying steps are each carried out for a time and under conditions sufficient to provide the dried nickel impregnated precipitate catalyst;

dry impregnating the dried nickel impregnated precipitate with an aqueous solution of a water-soluble Group VIIIB metal salt;

drying the nickel and Group VIIIB metal impregnated precipitate; and

calcining the dried nickel and Group VIIIB metal impregnated precipitate in the presence of oxygen or air;

wherein:

each of the dry impregnating, drying, and calcining are carried out for a time and under conditions sufficient to provide the calcined catalyst.

22. A process for preparing a catalyst according to claim 21 , wherein the catalyst consists essentially of nickel oxide nanoparticles, or an oxide thereof, and Group VIIIB metal nanoparticles, or an oxide thereof, each independently supported on alumina nanoparticles.

23. A catalyst prepared by the process of claim 21 .

24. A catalyst consisting essentially of:

nickel oxide nanoparticles supported on alumina nanoparticles; and

optionally, metal oxide nanoparticles of Pd or Pt, or combination thereof, said metal oxide nanoparticles supported on the alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

wherein the catalyst does not further contain silver nanoparticles supported on the alumina nanoparticles;

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers; and

wherein the alumina nanoparticles are present in an amount of at least 99% by weight of catalyst.

25. A catalyst according to claim 24 , wherein the catalyst consists essentially of:

nickel oxide nanoparticles supported on alumina nanoparticles; and

metal oxide nanoparticles of Pd supported on the alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500; and

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers.

26. A catalyst according to claim 24 , wherein the catalyst consists essentially of:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500; and

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers.

27. A process for preparing a catalyst comprising:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein:

the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers;

the catalyst does not further comprise nanoparticles of silver supported on the alumina nanoparticles; and

the alumina nanoparticles are present in an amount of at least 99% by weight of catalyst;

said process comprising:

providing an aqueous alkaline solution of an aluminum compound;

acidifying the aqueous alkaline solution with gaseous carbon dioxide to precipitate an amorphous sodium aluminate precipitate;

isolating and drying the sodium aluminate precipitate;

dry impregnating the amorphous dried sodium aluminate precipitate with an aqueous solution of a water-soluble nickel salt; and

drying the nickel impregnated precipitate;

wherein the dry impregnating and drying steps are each carried out for a time and under conditions sufficient to provide the dried nickel impregnated precipitate catalyst.

28. A catalyst comprising:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 500;

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers;

wherein the catalyst does not further comprise silver nanoparticles supported on the alumina nanoparticles; and

wherein the S BET surface area is from about 17 to about 70 m 2 /g.

29. A catalyst according to claim 28 , wherein the ratio is in a range of from about 99 to about 400.

30. A catalyst according to claim 28 , wherein the nickel oxide (NiO) nanoparticles are present in an amount of about 0.2% to about 1% by weight of catalyst.

31. A catalyst according to claim 30 , wherein the nickel oxide (NiO) nanoparticles are present in an amount of about 0.2% to about 0.6% by weight of catalyst.

32. A catalyst according to claim 28 , further comprising nanoparticles of at least one Group VIIIB metal oxide supported on the alumina nanoparticles;

wherein:

the Group VIIIB metal is selected from the group consisting of Pd and Pt, or combination thereof;

the alumina nanoparticle to Group VIIIB metal oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 500.

33. A catalyst according to claim 32 ; wherein the alumina nanoparticles are present in an amount of at least 99% by weight of catalyst.

34. A method for upgrading heavy oil fractions in a well, comprising:

contacting the heavy oil in a well producing heavy oil with a catalyst according to claim 28 for a time and under conditions sufficient to increase the H/C ratio.

35. A method according to claim 34 further comprising contacting the heavy oil with a hydrogen transfer agent.

36. A method according to claim 35 , wherein the hydrogen transfer agent comprises 1,2,3,4-tetrahydronaphthalene.

37. A method for upgrading heavy oil fractions in a well, comprising:

contacting the heavy oil in a well producing heavy oil with a catalyst according to claim 32 for a time and under conditions sufficient to increase the H/C ratio.

38. A method according to claim 37 further comprising contacting the heavy oil with a hydrogen transfer agent.

39. A method according to claim 38 , wherein the hydrogen transfer agent comprises 1,2,3,4-tetrahydronaphthalene.

40. A catalyst consisting essentially of:

nickel oxide nanoparticles supported on alumina nanoparticles; and

optionally, metal oxide nanoparticles of Pd or Pt, or combination thereof, said metal oxide nanoparticles supported on the alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

wherein the catalyst does not further contain silver nanoparticles supported on the alumina nanoparticles;

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers; and

wherein the S BET surface area is from about 17 to about 70 m 2 /g.

41. A catalyst according to claim 40 , wherein the catalyst consists essentially of:

nickel oxide nanoparticles supported on alumina nanoparticles; and

metal oxide nanoparticles of Pd supported on the alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500; and

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers.

42. A catalyst according to claim 40 , wherein the catalyst consists essentially of:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500; and

wherein the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers.

43. A process for preparing a catalyst comprising:

nickel oxide nanoparticles supported on alumina nanoparticles;

wherein:

the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 80 to about 500;

the particle size of the alumina nanoparticle is in the range of from about 30 to about 100 nanometers;

the catalyst does not further comprise nanoparticles of silver supported on the alumina nanoparticles; and

wherein the S BET surface area is from about 17 to about 70 m 2 /g;

said process comprising:

providing an aqueous alkaline solution of an aluminum compound;

acidifying the aqueous alkaline solution with gaseous carbon dioxide to precipitate an amorphous sodium aluminate precipitate;

isolating and drying the sodium aluminate precipitate;

dry impregnating the amorphous dried sodium aluminate precipitate with an aqueous solution of a water-soluble nickel salt; and

drying the nickel impregnated precipitate;

wherein the dry impregnating and drying steps are each carried out for a time and under conditions sufficient to provide the dried nickel impregnated precipitate catalyst.