Emulsion and system for catalytic pyrolysis

• US 10,557,089 B2
• Filed: 06/06/2019
• Issued: 02/11/2020
• Est. Priority Date: 12/03/2014
• Status: Active Grant

• Current Assignee: Racional Energy & Environment Company
• Original Assignee: Racional Energy & Environment Company
• Inventors: Perez-Cordova, Ramon
• Primary Examiner(s): Mueller, Derek N
• Application Number:
  US16/433,021
• Publication Number:
  US 20190300796A1
• Time in Patent Office: 250 Days
• Field of Search: None
• CPC Class Codes: B01F 23/4145 Emulsions of oils, e.g. fuel, and water
• CPC Class Codes: C10G 11/02 characterised by the catalyst used
• CPC Class Codes: C10G 11/04 Oxides
• CPC Class Codes: C10G 11/08 Halides
• CPC Class Codes: C10G 11/16 according to the "moving bed" method

Abstract

An emulsion and system for catalytic pyrolysis can include a mixture of 100 parts by weight heavy oil, 5 to 100 parts by weight water, and 1 to 20 parts by weight solid catalyst particulates, which can include an oxide or acid addition salt of a Group 3-16 metal on a mineral support, such as ferric chloride on bentonite. Also, a pyrolysis system can include a charge of the emulsion, a transfer line to supply the emulsion to a pyrolysis chamber, a combustion gas source to supply a combustion gas to heat the pyrolysis chamber, a control system to maintain the pyrolysis chamber at a temperature, pressure and residence time to form a pyrolyzate vapor phase, and a vapor line to receive the pyrolyzate vapor phase from the pyrolysis chamber.

Claims

1. An emulsion having utility as a reactor feedstock, comprising:

100 parts by weight heavy oil;

from about 5 to about 100 parts by weight water; and

from about 1 to about 20 parts by weight solid catalyst particulates comprising ferric ions and chloride ions supported on clay.

2. The emulsion of claim 1 wherein the catalyst particulates comprise particulates recovered from a thermal desorption process in which an oil contaminated substrate comprising a peptizable matrix component selected from acid-reactive clays and minerals, has been contacted with an acidic reagent to form a peptizate, and the peptizate mixed with a combustion effluent gas comprising less than about 1 volume percent oxygen, under turbulent conditions at a temperature above 200°

C., to form a light phase comprising desorbed oil and a dense phase from which the catalyst particulates are recovered.

3. The emulsion of claim 1, wherein the catalyst particulates have been thermally treated at a temperature above 200°

C.

4. The emulsion of claim 1, wherein the clay comprises acid-treated clay.

5. The emulsion of claim 1, wherein the clay comprises bentonite.

6. The emulsion of claim 1, wherein the catalyst particulates comprise the product of:

recovering a solid reaction product from contacting excess iron shavings with an aqueous mixture of hydrochloric and nitric acids;

treating a clay with an aqueous sodium chloride brine;

drying the brine-treated clay;

combining the recovered solid reaction product, the dried, brine-treated clay, and water to form a mixture; and

thermally treating the mixture at a temperature above 200°

C.

7. The emulsion of claim 1, comprising from about 20 to about 50 parts by weight of the water, and from about 5 to about 10 parts by weight of the catalyst particulates.

8. The emulsion of claim 1, having an electrical stability of greater than 1600 V, when determined according to API 13B-2 at 130°

C.

9. The emulsion of claim 1, having an apparent viscosity at 30°

C. and 100 s<sup>−

1</sup> at least 30% lower than the heavy oil alone.

10. A reactor system, comprising:

a charge of the emulsion of claim 1;

a transfer line to supply the emulsion to a reaction chamber;

a combustion gas source to supply a combustion gas to heat the reaction chamber;

a control system to maintain the reaction chamber at a temperature, pressure and residence time to form a pyrolyzate vapor phase; and

a vapor line to receive the pyrolyzate vapor phase from the reaction chamber.

11. The reactor system of claim 10 wherein the absolute pressure in the reaction chamber is from about 1 to 1.5 atm and the pyrolyzate vapor phase exits from the reactor at a temperature above 200°

C.

12. The reactor system of claim 11 wherein the pyrolyzate vapor phase exits from the reaction chamber at a temperature above 400°

C. up to about 600°

C.

13. The reactor system of claim 11 wherein the pyrolyzate vapor phase exits from the reaction chamber at a temperature 400°

C. up to about 500°

C.

14. The reactor system of claim 10, further comprising a pump to pump the emulsion through a line to the reaction chamber.

15. The reactor system of claim 10, further comprising a spray nozzle for injecting the emulsion into the reaction chamber.

16. The reactor system of claim 10 wherein the catalyst particulates comprise particulates recovered from a thermal desorption process in which an oil contaminated substrate comprising a peptizable matrix component selected from acid-reactive clays and minerals, has been contacted with an acidic reagent to form a peptizate, and the peptizate mixed with a combustion effluent gas comprising less than about 1 volume percent oxygen, under turbulent conditions at a temperature above 200°

C., to form a light phase comprising desorbed oil and a dense phase from which the catalyst particulates are recovered.

17. The reactor system of claim 10, wherein the catalyst particulates have been thermally treated at a temperature above 200°

C.

18. The reactor system of claim 10, wherein the clay comprises bentonite.

19. The reactor system of claim 10, wherein the catalyst particulates comprise the product of:

recovering a solid reaction product from contacting excess iron shavings with an aqueous mixture of hydrochloric and nitric acids;

treating a clay with an aqueous sodium chloride brine;

drying the brine-treated clay;

combining the recovered solid reaction product, the dried, brine-treated clay, and water to form a mixture; and

thermally treating the mixture at a temperature above 200°

C.

20. The reactor system of claim 10, wherein the emulsion comprises from about 20 to about 50 parts by weight of the water, and from about 5 to about 10 parts by weight of the catalyst particulates.

21. The pyrolysis system of claim 10, wherein the emulsion has an electrical stability of greater than 1600 V, when determined according to API 13B-2 at 130°

C.

22. The pyrolysis system of claim 10, wherein the emulsion has an apparent viscosity at 30°

C. and 100 s<sup>−

1</sup> at least 30% lower than the heavy oil alone.