Hydrogen-enhanced delayed coking process

Patent metadata

Field	Value
Publication number	US-11312912-B2
Application number	US-202016885157-A
Country	US
Kind code	B2
Filing date	May 27, 2020
Priority date	May 29, 2019
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

A method is described for treating a hydrocarbon oil feedstream to a delayed coking unit to maximize the ratio of the yield of liquids-to-gases, and to minimize the formation of coke which includes:a. mixing an oil-soluble catalyst with the hydrocarbon oil feedstream to produce a uniform mixture;b. contacting the catalyst-containing hydrocarbon oil feedstream with an excess of hydrogen under predetermined conditions that are favorable to maximizing the solubility of the hydrogen in the feedstream in a hydrogen distribution zone that is upstream of the coking unit;c. introducing the feedstream containing the solubilized catalyst and dissolved hydrogen, and the excess hydrogen gas into a flashing zone;d. recovering from the flashing zone a hydrogen gas stream and a single-phase hydrocarbon oil feedstream containing dissolved hydrogen and catalyst;e. maintaining the hydrocarbon oil feedstream containing dissolved hydrogen and catalyst under single-phase conditions to promote the reaction of the dissolved hydrogen with free radicals formed in the feedstream and to promote the catalyzed hydrodesulfurization of any sulfur-containing compounds present in the feedstream;f. introducing the catalyst-containing feedstream into a coking furnace upstream of the coking unit to heat the feedstream to a predetermined coking temperature;g. introducing the hot feedstream into the coking unit; andh. recovering a coking unit product stream that is free of catalyst and forming a coke product that contains the catalyst.

First claim

The invention claimed is:

1. A method of treating a hydrocarbon oil feedstream to a delayed coking unit to maximize the ratio of yield of liquids-to-light gases, and to minimize formation of coke, the method characterized by:
a. mixing an oil-soluble catalyst with the hydrocarbon oil feedstream to provide a uniform mixture;
b. contacting the uniform mixture with an excess of hydrogen under predetermined conditions of temperature and pressure that are favorable to maximizing the solubility of the hydrogen in the feedstream in a hydrogen distribution zone that is upstream of the delayed coking unit;
c. introducing the feedstream containing the solubilized catalyst and dissolved hydrogen, and the excess hydrogen gas into a flashing zone;
d. recovering from the flashing zone a hydrogen gas stream and a single-phase hydrocarbon oil feedstream containing dissolved hydrogen and catalyst;
e. maintaining the hydrocarbon oil feedstream containing dissolved hydrogen and catalyst under single-phase conditions to promote reaction of the dissolved hydrogen with free radicals formed in the feedstream and to promote catalyzed hydrodesulfurization of any sulfur-containing compounds present in the feedstream;
f. introducing the catalyst and dissolved hydrogen-containing feedstream into a coking unit furnace upstream of the coking unit to heat the feedstream to a predetermined coking temperature;
g. introducing the catalyst and dissolved hydrogen-containing feedstream that is heated to the predetermined coking temperature into a drum of the coking unit; and
h. recovering a coking unit product stream that is free of catalyst and forming a coke product that contains the catalyst in the coking unit drum.

2. The method of claim 1 in which the oil-soluble catalyst is first solubilized in a diluent hydrocarbon oil that is lighter than the feedstream that is to be treated before it is added to the hydrocarbon oil feedstream.

3. The method of claim 2 in which the hydrocarbon oil is added to the catalyst and diluent oil mixture while the addition of hydrogen is continued until the mixed solution is saturated with hydrogen.

4. The method of claim 2 in which the diluent oil containing the catalyst is contacted with an excess of hydrogen before the catalyst and diluent oil are added to the hydrocarbon oil feedstream.

5. The method of claim 4 in which the hydrogen is introduced into the diluent oil containing catalyst at a pressure in the range of from 1 to 60 bar.

6. The method of claim 1 in which the hydrocarbon oil feedstream comprises bottoms recovered from an initial fractionation step to reduce light hydrocarbons in a fresh hydrocarbon oil feedstream.

7. The method of claim 1 in which the oil-soluble catalyst is an organometal complex selected from the group consisting of compounds containing metals from the elements of IUPAC groups 4-12 of the Periodic Table, and combinations thereof.

8. The method of claim 7 in which the metals are selected from the group consisting of Mo, Fe, Ni, Co, W, and combinations thereof.

9. The method of claim 1 in which the hydrogen is introduced into the hydrocarbon oil feed stream at a pressure in the range of from 1 to 60 bar.

10. The method of claim 1 in which the hydrogen is contacted with the catalyst-containing hydrocarbon oil feedstream at a gaseous hydrogen-to-oil volumetric ratio that ranges from 10-to-1 to 5000-to-1.

11. The method of claim 1 in which the temperature of the uniform mixture is less than the temperature of the catalyst and dissolved hydrogen containing feedstream that is heat to the predetermined coking temperature.

12. The method of claim 11 in which the temperature of the catalyst and dissolved hydrogen containing feedstream that is heated to the predetermined temperature is in the range of from 425° C. to 650° C.

13. The method of claim 1 in which the pressure of the hydrogen gas in the flashing zone is in the range of from 1 to 60 bar.

14. The method of claim 1 wherein the catalyst is dissolved in the hydrocarbon oil feedstream in an amount in the range of 1 ppm to 5000 ppm by weight of a metal component of the catalyst to the hydrocarbon oil feedstream.

15. The method of claim 1 in which the molal amount of the hydrogen dissolved in the hydrocarbon oil feedstream recovered from the flashing zone is approximately one-third of the hydrogen originally contacting the hydrocarbon oil feedstream.

16. The method of claim 1 in which the hydrocarbon oil feedstream is selected from the group consisting of crude oil, bitumen, tar sands, coal liquid, bio derived oil, and shale oil, residual oil bottoms from atmospheric distillation and vacuum distillation, coking heavy oil products, visbreaker and FCC bottoms, and mixtures thereof.

17. The method of claim 16 in which the coking unit product stream is introduced into a coking unit product fractionator and a portion of fractionator bottoms are mixed as a fractionator recycle stream with the hydrocarbon oil feed stream.

18. The method of claim 17 in which at least a portion of the hydrocarbon oil feedstream is introduced into the coking unit product fractionator for mixing with the fractionator bottoms.

19. The method of claim 1 in which the oil-soluble catalyst is mixed with a diluent hydrocarbon oil and the diluent oil/catalyst mixture is added to the feedstream.

20. The method of claim 19 in which the diluent oil is selected from the group consisting of vacuum gas oil, decant oil, cycle oil, light gas oil, and mixtures thereof.

21. The method of claim 19 in which the diluent oil is recovered from a coking unit product stream fractionator.

22. A method of treating a hydrocarbon oil feedstream to a delayed coking unit to maximize the ratio of yield of liquids-to-light gases, and to minimize formation of coke, the method characterized by:
a. mixing an oil-soluble catalyst with the hydrocarbon oil feedstream to provide a uniform mixture, wherein the oil-soluble catalyst is an organometal complex selected from the group consisting of compounds containing metals from the elements of IUPAC groups 4-12 of the Periodic Table, and combinations thereof;
b. contacting the uniform mixture with a predetermined amount of hydrogen from a source of pressurized hydrogen under predetermined conditions of temperature and pressure to saturate the feedstream with the hydrogen in a hydrogen distribution zone that is upstream of the delayed coking unit, wherein the hydrogen distribution zone comprises a mixing column or vessel having a plurality of manifolds each connected to the source of pressurized hydrogen, and wherein each of the manifolds comprise spaced-apart nozzles, jets or orifices, wherein hydrogen is discharged through the nozzles, jets or orifices, and creates zones of turbulence that promote absorption of hydrogen in the feedstream to form a single-phase hydrocarbon oil feedstream containing dissolved hydrogen and catalyst;
c. recovering from the hydrogen distribution zone a-the single-phase hydrocarbon oil feedstream containing dissolved hydrogen and catalyst;
d. maintaining the hydrocarbon oil feedstream containing dissolved hydrogen and catalyst under single-phase conditions to promote reaction of the dissolved hydrogen with free radicals formed in the feedstream and to promote catalyzed hydrodesulfurization of any sulfur-containing compounds present in the feedstream;
e. introducing the catalyst and dissolved hydrogen-containing feedstream into a coking unit furnace upstream of the coking uni

Assignees

• Saudi Arabian Oil Co

Inventors

• Koseoglu Omer Refa

Classifications

• C10G9/005 Primary

  Coking (in order to produce liquid products mainly) · CPC title

• C10B57/14

  Features of low-temperature carbonising processes · CPC title

• C10B57/12

  Applying additives during coking · CPC title

• C10B57/06 Primary

  containing additives · CPC title

• C10B55/00 Primary

  Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material (cracking oils C10G) · CPC title