Process for removing chloride from lipid feedstocks using rejuvenated catalyst

Patent metadata

Field	Value
Publication number	US-12286602-B2
Application number	US-202418433789-A
Country	US
Kind code	B2
Filing date	Feb 6, 2024
Priority date	Apr 27, 2023
Publication date	Apr 29, 2025
Grant date	Apr 29, 2025

Abstract

A process involves sequentially treating a plurality of lipid feedstocks comprising a set of lipid feedstocks each having a chloride content of at least about 2 ppm with a metal oxide catalyst on an oxide support under first treating conditions to produce respective treated streams of the set of lipid feedstocks having a chloride content less than 1 ppm until a given one of the respective treated streams has a chloride content greater than 1 ppm and the metal oxide catalyst is converted to a spent metal oxide catalyst, converting the spent metal oxide catalyst to a rejuvenated metal oxide catalyst, and treating one or more additional lipid feedstocks each having a chloride content of at least about 2 ppm with the rejuvenated metal oxide catalyst under second treating conditions to produce one or more respective treated streams each having a chloride content less than 1 ppm.

First claim

What is claimed is:

1. A process, comprising:
(a) sequentially treating a plurality of lipid feedstocks comprising a set of lipid feedstocks each having a chloride content of at least about 2 ppm with a metal oxide catalyst on an oxide support having a chloride removing activity under first treating conditions to produce respective treated streams of the set of lipid feedstocks having a chloride content less than 1 ppm until the chloride removing activity of the metal oxide catalyst on the oxide support produces a given one of the respective treated streams of the set of lipid feedstocks having a chloride content greater than 1 ppm and the metal oxide catalyst on the oxide support is converted to a spent metal oxide catalyst on the oxide support;
(b) re-activating the chloride removing activity of the spent metal oxide catalyst on the oxide support to produce a rejuvenated metal oxide catalyst on the oxide support, wherein the re-activating comprises contacting the spent metal oxide catalyst on the oxide support with a solution comprising a water-soluble metal salt; and
(c) treating one or more additional lipid feedstocks each having a chloride content of at least about 2 ppm with the rejuvenated metal oxide catalyst on the oxide support under second treating conditions to produce one or more respective treated streams each having a chloride content less than 1 ppm.

2. The process according to claim 1 , wherein the plurality of lipid feedstocks and the one or more additional lipid feedstocks independently comprise at least one fatty acid selected from the group consisting of an acidulated soap-stock, a fatty acid distillate from physical refining of plant oils or animal fats, a distiller corn oil from ethanol production, a waste cooking oil, lard, brown grease, yellow grease, trap grease, a waste fat, a low-grade oil, a supercritical water liquefaction oil, a plant oil, an animal fat, and any combination thereof.

3. The process according to claim 1 , wherein the sequentially treating the plurality of lipid feedstocks with the metal oxide catalyst on the oxide support under the first treating conditions comprises (i) treating one or more first lipid feedstocks with the metal oxide catalyst on the oxide support under the first treating conditions to produce a first treated stream having a chloride content less than 1 ppm; (ii) treating one or more second lipid feedstocks with the metal oxide catalyst on the oxide support under the first treating conditions to produce a second treated stream having a chloride content less than 1 ppm; (iii) treating one or more third lipid feedstocks with the metal oxide catalyst on the oxide support under the first treating conditions to produce a third treated stream having a chloride content less than 1 ppm; and (iv) treating one or more fourth lipid feedstocks with the metal oxide catalyst on the oxide support under the first treating conditions until the chloride removing activity of the metal oxide catalyst on the oxide support produces a fourth treated stream having a chloride content greater than 1 ppm.

4. The process according to claim 1 , wherein the first treating conditions and the second treating conditions independently include one or more of the following: a temperature in a range of from about 400° C. to about 700° C., a pressure in a range of from about 0.1 to about 10 MPa, and a liquid hourly space velocity in a range of from about 0.1 to about 10 h −1 .

5. The process according to claim 1 , wherein the metal oxide catalyst comprises a metal selected from the group consisting of Na, K, Mg, Ca, Ba, Sr, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, rare earth metals, and any combination thereof, and the oxide support is selected from the group consisting of alumina, silica, silica-alumina, titania, zirconia, and any combination thereof.

6. The process according to claim 1 , wherein the metal oxide catalyst comprises a metal selected from the group consisting of Ca, Mg, Ba and any combination thereof.

7. The process according to claim 1 , wherein the metal oxide catalyst comprises CaO and the oxide support comprises alumina.

8. The process according to claim 1 , wherein the metal of the water-soluble metal salt is one of calcium, magnesium or barium.

9. The process according to claim 1 , wherein contacting the spent metal oxide catalyst on the oxide support with the solution of the water-soluble metal salt comprises spraying a solution comprising one of a calcium nitrate, a calcium hydroxide, a calcium acetate or a calcium carboxylate onto the spent metal oxide catalyst on the oxide support, where the spent metal oxide catalyst comprises CaO.

10. The process according to claim 1 , wherein step (a) is carried out in a reactor system, and the re-activating the chloride removing activity of the spent metal oxide catalyst on the oxide support to produce the rejuvenated metal oxide catalyst on the oxide support is carried out without removing the spent metal oxide catalyst on the oxide support from the reactor system.

11. The process according to claim 10 , wherein the re-activating the chloride removing activity of the spent metal oxide catalyst on the oxide support to produce the rejuvenated metal oxide catalyst on the oxide support comprises spraying the solution comprising the water-soluble metal salt on the spent metal oxide catalyst on the oxide support and heating the reactor system.

12. The process according to claim 11 , wherein the solution comprising the water-soluble metal salt is a solution of calcium acetate and the spent metal oxide catalyst comprises CaO.

13. The process according to claim 1 , wherein the treating of step (a) and step (c) is carried out under flow of a carrier gas.

14. The process according to claim 13 , wherein the carrier gas is nitrogen, carbon dioxide, a C 1 to C 4 hydrocarbon, water, or a mixture thereof.

15. The process according to claim 1 , wherein the plurality of lipid feedstocks and the one or more additional lipid feedstocks independently exhibit at least one of the following properties:
(i) a total acid number of at least about 5 mg KOH/g, as determined by ASTM D664; and
(ii) about 2 ppm to about 100 ppm of chloride.

16. The process according to claim 1 , further comprising fractionating one or more of the respective treated streams of step (a) and the one or more respective treated streams of step (c) to obtain a gaseous fraction and a liquid fraction comprising a bio-oil.

17. The process according to claim 16 , further comprising subjecting the bio-oil to a catalytic hydroprocessing step to provide a hydroprocessed product.

18. The process according to claim 17 , wherein the catalytic hydroprocessing step comprises a hydrodeoxygenation step.

19. The process according to claim 1 , wherein at least one of the respective treated streams of step (a) and the one or more respective treated streams of step (c) has a chloride content equal to 0.

20. The process according to claim 1 , wherein the contacting the spent metal oxide catalyst on the oxide support with the solution comprising the water-soluble metal salt comprises injecting the solution comprising the water-soluble metal salt into the one or more additional lipid feedstocks.

Assignees

• Chevron Usa Inc

Inventors

• Hommeltoft Sven Ivar

Classifications

• C11C1/08

  Refining · CPC title

• C11C3/126

  using catalysts based principally on other metals or derivates · CPC title

• C11B3/06

  with bases · CPC title

• C11C3/123 Primary

  using catalysts based principally on nickel or derivates · CPC title

• B01J38/485

  Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements · CPC title