Syngas production via supercritical water

Patent metadata

Field	Value
Publication number	US-12240757-B2
Application number	US-202217574310-A
Country	US
Kind code	B2
Filing date	Jan 12, 2022
Priority date	Jan 12, 2022
Publication date	Mar 4, 2025
Grant date	Mar 4, 2025

Abstract

A method to produce syngas from a feed oil comprising the steps of increasing a pressure of a slurry catalyst; increasing a temperature of the pressurized slurry stream; increasing a pressure of the feed oil; increasing a temperature of the pressurized feed stream; mixing the hot slurry stream and the hot oil stream; increasing a temperature of the mixed stream in a combined heater to produce a hot mixed stream; maintaining upgrading reactions of hydrocarbons in the supercritical reactor to produce a supercritical effluent; reducing a pressure of the supercritical effluent; separating the depressurized effluent in a separator to produce a gas stream; separating the gas stream to produce a light hydrocarbon stream; mixing the light hydrocarbon stream and a catalyst feed; introducing the hot feed to a steam reformer; maintaining water gas shift reactions of the light hydrocarbon gases in the steam reformer to produce a reformer effluent.

First claim

That which is claimed is:

1. A method to produce syngas from a feed oil, the method comprising the steps of:
increasing a pressure of a slurry catalyst in a catalyst pump to produce a pressurized slurry stream, where the slurry catalyst comprises catalyst particles dispersed in deionized water;
increasing a temperature of the pressurized slurry stream in a slurry heater to produce a hot slurry stream;
increasing a pressure of the feed oil in an oil pump to produce a pressurized feed stream, wherein the feed oil comprises a heavy oil;
increasing a temperature of the pressurized feed stream in an oil heater to produce a hot oil stream, where the temperature of the hot oil stream is between 100° C. and 380° C.;
mixing the hot slurry stream and the hot oil stream in a mixer to produce a mixed stream;
increasing a temperature of the mixed stream in a combined heater to produce a hot mixed stream, wherein the hot mixed stream comprises an oil-in-water emulsion comprising catalyst particles dispersed in the emulsion such that precipitation of the catalyst particles is minimized;
introducing the hot mixed stream to a supercritical reactor, wherein the supercritical reactor is at a temperature between 380° C. and 500° C. and a pressure between 22 MPa and 35 MPa;
maintaining upgrading reactions of hydrocarbons in the supercritical reactor to produce a supercritical effluent, wherein the catalyst particles catalyze the upgrading reactions, wherein a residence time in supercritical reactor is in the range of 0.01 minutes to 1.0 minute;
reducing a pressure of the supercritical effluent in a pressure let-down device to produce a depressurized effluent;
separating the depressurized effluent in a separator to produce a gas stream, a catalyst-containing water stream and a liquid hydrocarbon stream, wherein the gas stream comprises light hydrocarbon gases, syngas, carbon dioxide, and combinations of the same, where the light hydrocarbon gases are selected from the group consisting of methane, ethane, propane, butane, and combinations of the same;
separating the gas stream in a high pressure separator to produce a light gas stream and a light hydrocarbon stream, wherein the light hydrocarbon stream comprises the light hydrocarbon gases;
mixing the light hydrocarbon stream and a catalyst feed in a reformer mixer to produce a combined feed, wherein the combined comprises light hydrocarbon gases, water, and catalyst;
increasing a temperature of the combined feed in a reformer heater to produce a hot feed, wherein the hot feed is at a temperature between 500° C. and 800° C.;
introducing the hot feed to a steam reformer, wherein the steam reformer is at a temperature between 500° C. and 800° C. and a pressure between atmospheric pressure and 0.5 MPa;
maintaining water gas shift reactions of the light hydrocarbon gases in the steam reformer to produce a reformer effluent, wherein the catalyst from the catalyst feed catalyzes the water gas shift reactions; and
separating the reformer effluent in a product separator to produce a product gas, wherein the product gas comprises syngas.

2. The method of claim 1 , wherein the steam reformer is a fixed bed reactor.

3. The method of claim 1 , wherein the steam reformer is a moving bed reactor.

4. The method of claim 1 , further comprising the step of introducing an oxygen stream to the supercritical reactor, wherein the oxygen source is selected from the group consisting of oxygen gas, hydrogen peroxide, peroxides, air, and combinations of the same.

5. The method of claim 1 , wherein a mass flow ratio of water to oil in the hot mixed stream is in the range of 5 to 15.

6. The method of claim 1 , wherein the liquid hydrocarbon stream comprises liquid hydrocarbons, wherein the liquid hydrocarbons are selected from the group consisting of diesel, naphtha, distillates, heavy oils, and combinations of the same.

7. The method of claim 1 , wherein the catalyst in the supercritical reactor is the same catalyst in the steam reformer.

8. The method of claim 1 , wherein a temperature of the hot slurry is between 350° C. and 500° C.

9. The method of claim 1 , wherein a pressure of the depressurized effluent is between ambient pressure and 0.5 MPa.

10. The method of claim 1 , wherein the heavy oil of the feed oil is selected from the group consisting of whole range crude oil, distilled crude oil, residue oil, topped crude oil, product streams from oil refineries, product streams from steam cracking processes, liquefied coals, liquid products recovered from oil or tar sands, bitumen, oil shale, asphaltene, biomass hydrocarbons, liquids products from gas-to-liquid GTL) processes, and combinations of the same.

11. A system to produce syngas from a feed oil, the system comprising:
a catalyst pump configured to increase a pressure of a slurry catalyst to produce a pressurized slurry stream, where the slurry catalyst comprises catalyst particles dispersed in deionized water;
a slurry heater fluidly connected to the catalyst pump, the slurry heater configured to increase a temperature of the pressurized slurry stream to produce a hot slurry stream;
an oil pump configured to increase a pressure of the feed oil to produce a pressurized feed stream, wherein the feed oil comprises a heavy oil;
an oil heater fluidly connected to the oil pump, the oil heater configured to increase a temperature of the pressurized feed stream to produce a hot oil stream, where the temperature of the hot oil stream is between 100° C. and 380° C.;
a mixer fluidly connected to the slurry heater and the oil heater, the mixer configured to mix the hot slurry stream and the hot oil stream to produce a mixed stream;
a combined heater fluidly connected to the mixer, the combined heater configured to increase a temperature of the mixed stream to produce a hot mixed stream, wherein the hot mixed stream comprises an oil-in-water emulsion comprising catalyst particles dispersed in the emulsion such that precipitation of the catalyst particles is minimized;
a supercritical reactor fluidly connected to the combined heater, the supercritical reactor configured to maintain upgrading reactions of hydrocarbons in the hot mixed stream to produce a supercritical effluent, wherein the catalyst particles catalyze the upgrading reactions, wherein a residence time in supercritical reactor is in the range of 0.01 minutes to 1.0 minute, wherein the supercritical reactor is at a temperature between 380° C. and 500° C. and a pressure between 22 MPa and 35 MPa;
a pressure let-down device fluidly connected to the supercritical reactor, the pressure let-down device configured to reduce a pressure of the supercritical effluent to produce a depressurized effluent;
a separator fluidly connected to the pressure let-down device, the separator configured to separate the depressurized effluent to produce a gas stream, a catalyst-containing water stream and a liquid hydrocarbon stream, wherein the gas stream comprises light hydrocarbon gases, syngas, carbon dioxide, and combinations of the same, where the light hydrocarbon gases are selected from the group consisting of methane, ethane, propane, butane, and combinations of the same;
a high pressure separator fluidly connected to the separator, the high pressure separator configured to separate the gas stream to produce a light gas stream and a light hydrocarbon stream, wherein the light hydrocarbon stream comprises the light hydrocarbon gases;
a reformer mixer fluidly connected to the high pressure separator, the reformer mixer configured to mix the light hydrocarbon stream and a catalyst feed to produce a combined feed, wherein the combined comprises light hydrocarbon gases, water, and catal

Assignees

• Saudi Arabian Oil Co

Inventors

• Almulla Faisal
• Choi Ki-Hyouk
• Fathi Mazin

Classifications

• C01B2203/0283

  containing a CO-shift step, i.e. a water gas shift step · CPC title

• C01B2203/1235

  Hydrocarbons · CPC title

• C01B2203/1614

  Controlling the temperature · CPC title

• C01B2203/0805

  Methods of heating the process for making hydrogen or synthesis gas · CPC title

• B01J2208/065

  Heating or cooling the reactor · CPC title