Flash chemical ionizing pyrolysis of hydrocarbons

• US 10,611,969 B2
• Filed: 10/25/2019
• Issued: 04/07/2020
• 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): McCaig, Brian A
• Application Number:
  US16/663,838
• Publication Number:
  US 20200056100A1
• Time in Patent Office: 165 Days
• 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
• CPC Class Codes: C10G 51/026 only catalytic cracking steps
• CPC Class Codes: C10G 51/04 including only thermal and catalytic cracking steps
• CPC Class Codes: C10G 57/005 with alkylation

Abstract

Flash chemical ionizing pyrolysis (FCIP) at 450° C.-600° C. forms liquid ionizing pyrolyzate (LIP) that can be blended in oil feedstock for thermal processes to promote conversion of heavier hydrocarbons to reduce resid/coke yields and/or increase yields of liquid hydrocarbons and isomerates. A front-end refinery process modifies crude oil with LIP for distillation to reduce resid/coke yields and/or increase liquid oil yields. A downstream process modifies a heavy oil stream such as resid with LIP and the LIP-modified stream can be thermally processed to reduce resid/coke yields and/or increase liquid oil yields. FCIP of the LIP blends also improves quality and/or yields of the liquid pyrolyzate product. Finely divided FCIP solids can contain FeCl₃ supported on NaCl-treated calcium bentonite. A process for preparing the FCIP solids treats iron with HCl and HNO₃ to form acidified FeCl₃ of limited solubility, loads the FeCl₃ on NaCl-treated bentonite, and heat-treats the material at 400° C.-425° C.

Claims

1. A hydrocarbon conversion process, comprising the steps of:

emulsifying water and an oil component with finely divided solids comprising a mineral support and an oxide and/or acid addition salt of a Group 3-16 metal;

introducing the emulsion into a flash chemical ionizing pyrolysis (FCIP) reactor maintained at a temperature greater than about 400°

C. up to about 600°

C. and a pressure up to about 1.5 atm to form a chemical ionizing pyrolyzate effluent;

condensing a liquid ionizing pyrolyzate (LIP) from the effluent;

combining a feedstock oil with the LIP to form a pyrolyzate-feedstock blend; and

thermally processing the blend at a temperature above about 100°

C.

2. The process of claim 1, wherein the solids comprise brine-treated clay and an acid addition salt of a Group 8-10 metal, wherein the brine comprises a salt that forms a eutectic with the acid addition salt of the Group 8-10 metal.

3. The process of claim 2, wherein the clay comprises bentonite, the brine comprises sodium chloride, and the acid addition salt comprises FeCl₃.

4. The process of claim 3, comprising preparing the solids by a method comprising the steps of:

(a) contacting bentonite with the sodium chloride brine;

(b) contacting an excess of iron with an aqueous mixture of hydrochloric and nitric acids to form FeCl₃ solids;

(c) loading the FeCl₃ solids on the brine-treated bentonite; and

(d) calcining the loaded bentonite at a temperature below the FCIP temperature.

5. The process of claim 1, further comprising the steps of:

wherein the emulsion comprises (i) 100 parts by weight of the oil component;

(ii) from about 1 to 100 parts by weight of water, and (iii) from about 1 to 20 parts by weight of the finely divided solids; and

spraying the emulsion into the reactor, wherein the reactor temperature is from about 425°

C. to about 600°

C.

6. The process of claim 5 wherein the finely divided solids comprise the product of the method comprising the steps of:

treating iron with an aqueous mixture of hydrochloric and nitric acids to form a solids mixture of FeCl₃ optionally with mixed valences of iron and iron chlorides, nitrites, nitrites, oxides, and/or hydroxides, wherein the solids mixture has limited solubility;

treating montmorillonite with NaCl brine and drying the treated montmorillonite;

combining a slurry of the solids mixture with the treated montmorillonite to load the FeCl₃ on the montmorillonite; and

heat treating the loaded montmorillonite at a temperature above 400°

C.

7. The process of claim 5, wherein the oil component comprises the pyrolyzate-feedstock blend.

8. The process of claim 5 wherein the reactor temperature is from 450°

C. to 500°

C.

9. The process of claim 1, wherein the feedstock oil comprises hydrocarbons boiling at a temperature equal to or greater than 562°

C., and further comprising the step of recovering a hydrocarbon product from the thermally processed blend, the hydrocarbon product having an enriched yield of liquid hydrocarbons boiling at a temperature below 562°

C., relative to separate thermal processing of the LIP and feedstock oil, as determined by atmospheric distillation in a 15-theoretical plate column at a reflux ratio of 5;

1, according to ASTM D2892-18 up to cutpoint 400°

C. AET, and by vacuum potstill method according to ASTM D5236-18a above the 400°

C. cutpoint to cutpoint 562°

C. AET.

10. The process of claim 9 wherein the feedstock oil comprises crude oil, gas oil, resid, or a mixture thereof.

11. The process of claim 1 wherein the thermal processing comprises pyrolysis, distillation, cracking, alkylation, visbreaking, coking, and combinations thereof.

12. The process of claim 11 wherein the feedstock oil comprises crude oil and further comprising washing the LIP blend with wash water, recovering a solute-enriched spent water from the water washing step, recovering a desalted LIP blend, and heating the desalted LIP blend in advance of distillation of the LIP blend.

13. The process of claim 1, further comprising supplying at least a portion of the pyrolyzate-feedstock blend as the oil component to the FCIP feed emulsion preparation step wherein the thermal processing step consists of or comprises the spraying of the FCIP feed emulsion into the flash pyrolysis reactor.

14. A flash chemical ionizing pyrolysis (FCIP) process comprising the steps of:

preparing a feed emulsion comprising (i) 100 parts by weight of an oil component comprising a liquid ionizing pyrolyzate (LIP) blend component and a feedstock oil at a weight ratio of from 1;

100 to 1;

1, (ii) from about 1 to 100 parts by weight of water, and (iii) from about 1 to 20 parts by weight finely divided solids comprising a mineral support and an oxide or acid addition salt of a Group 3-16 metal;

spraying the feed emulsion in a flash pyrolysis reactor at a temperature from about 425°

C. to about 600°

C.;

collecting an effluent from the reactor;

recovering a product LIP from the effluent; and

supplying a portion of the product LIP as the LIP blend component to the feed emulsion preparation step.

15. A hydrocarbon refinery process comprising the steps of:

combining a liquid ionizing pyrolyzate (LIP) blend component with a feedstock oil at a weight ratio from about 1;

100 to about 1;

1 to form an LIP blend;

preparing an emulsion comprising (i) a first portion of the LIP blend, (ii) water, and (iii) from finely divided solids comprising a mineral support and an oxide or acid addition salt of a Group 3-16 metal;

spraying the emulsion in a flash pyrolysis reactor at a temperature from about 425°

C. to about 600°

C. and a pressure from about 1 to about 1.5 atm;

collecting an effluent from the reactor;

recovering a product LIP from the effluent;

incorporating the product LIP as the LIP blend component in the LIP blend; and

distilling a second portion of the LIP blend.

16. The process of claim 15, wherein the feedstock oil comprises crude oil.

17. The process of claim 16, wherein the feedstock oil comprises un-desalted crude oil wherein the process further comprises water washing to desalt the second portion of the LIP blend, and distilling the desalted second portion of the LIP blend.

18. A hydrocarbon refinery process comprising the steps of:

preparing a feed emulsion comprising (i) 100 parts by weight of an oil component, (ii) from about 1 to 100 parts by weight of water, and (iii) from about 1 to 20 parts by weight finely divided solids comprising a mineral support and an oxide or acid addition salt of a Group 3-16 metal;

spraying the feed emulsion in a flash pyrolysis reactor at a temperature from about 425°

C. to about 600°

C.;

collecting an effluent from the flash pyrolysis reactor;

recovering a liquid ionizing pyrolyzate (LIP) from the effluent;

combining the recovered LIP with a feedstock oil comprising crude oil or a petroleum fraction selected from gas oil, resid, or a combination thereof to form a pyrolyzate-feedstock blend;

distilling, cracking, visbreaking, and/or coking a first portion of the blend; and

supplying a second portion of the blend as the oil component in the feed emulsion preparation step.

19. The process of claim 18, wherein the LIP exhibits a SARA analysis having higher saturates and aromatics contents and a lower asphaltenes content than the feedstock oil.

20. The process of claim 18 wherein a proportion of the LIP in the oil component in the flash pyrolysis is effective to improve yield of liquid hydrocarbons boiling at a temperature below 562°

C., relative to separate flash chemical ionizing pyrolysis of the LIP and feedstock oil, as determined by atmospheric distillation in a 15-theoretical plate column at a reflux ratio of 5;

1, according to ASTM D2892-18 up to cutpoint 400°

C. AET, and by vacuum potstill method according to ASTM D5236-18a above the 400°

C. cutpoint to cutpoint 562°

C. AET.

21. The process of claim 18 wherein a proportion of the LIP in the LIP blend in the distillation, cracking, visbreaking, and/or coking step, is effective to improve yield of liquid hydrocarbons boiling at a temperature below 562°

C., relative to separate distillation, cracking, visbreaking, and/or coking of the LIP and feedstock oil, as determined by atmospheric distillation in a 15-theoretical plate column at a reflux ratio of 5;

1, according to ASTM D2892-18 up to cutpoint 400°

C. AET, and by vacuum potstill method according to ASTM D5236-18a above the 400°

C. cutpoint to cutpoint 562°

C. AET.

22. A crude oil upgrading process, comprising:

flash chemical ionizing pyrolysis of an emulsion of oil, water, mineral support, and an oxide and/or acid addition salt of a Group 3-16 metal, to obtain a liquid ionizing pyrolyzate (LIP);

blending the LIP with a heavy oil; and

thermally processing the blend at a temperature above about 100°

C.