Method of crude oil analysis

Patent metadata

Field	Value
Publication number	US-10690605-B1
Application number	US-201715843839-A
Country	US
Kind code	B1
Filing date	Dec 15, 2017
Priority date	Dec 15, 2016
Publication date	Jun 23, 2020
Grant date	Jun 23, 2020

Abstract

A method of directly analyzing an environmental sample, such as a crude oil sample, to simultaneously determine distillation ranges, identify elements therein, and/or identify impurities. The method includes performing multi-element scanning thermal analysis (MESTA) on the crude oil sample to obtain a thermogram of the elements within the crude oil sample, wherein peak information within the thermogram indicates presence of the elements, compounds, and/or impurities within the crude oil sample.

First claim

What is claimed is:

1. A method of analyzing a crude oil sample directly using multi-element scanning thermal analysis, the method comprising the steps of:
heating the crude oil sample within a sample compartment furnace fed by oxygen,
disposing a carrier gas through the sample compartment furnace to a combustion furnace, thereby carrying volatile from the sample compartment furnace during heating of the crude oil sample to the combustion furnace, such that one or more elements within the crude oil sample are oxidized, wherein the one or more elements includes a sulfur species, such that the sulfur species is oxidized into sulfur dioxide;
quantifying the sulfur dioxide using a sulfur dioxide chemiluminescent detector;
utilizing a multi-channel data logger to record real-time signals from the sulfur dioxide chemiluminescent detector and real-time sample temperature;
displaying peak information within a thermogram indicating the presence of the sulfur species within the crude oil sample; and
continuously scanning the crude oil sample using the multi-channel data logger in a temperature range from ambient to about 700° C., where the thermograms obtained contains all possible distillation range information,
whereby multi-elements scanning thermal analysis simultaneously determines sulfur impurities and distillation ranges within the crude oil sample.

2. The method of claim 1 , wherein the sulfur impurities in the crude oil sample includes organic sulfur and reduced inorganic sulfur.

3. The method of claim 1 , wherein nitrogen impurities in the sample are determined simultaneous with the distillation ranges and the sulfur impurities in the sample by performing the multi-element scanning thermal analysis on the sample.

4. The method of claim 1 , wherein the one or more elements further includes a carbon species, a nitrogen species, and a hydrogen species, wherein the sulfur species, the carbon species, the nitrogen species, and the hydrogen species correspond to distillation properties of sulfur compounds, hydrocarbon compounds, and nitrogen compounds in the crude oil sample.

5. The method of claim 4 , wherein differences in ratios of the carbon species, the nitrogen species, the sulfur species, and the hydrogen species within the sample are determined based on the thermogram.

6. The method of claim 1 , wherein the thermogram generated through the multi-element scanning thermal analysis is sensitive to less than about 0.01 μg of the sulfur species within the sample.

7. The method of claim 1 , wherein the multi-element scanning thermal analysis includes continuous scanning in a temperature range from about 40° C. to about 800° C. within a programmed sample compartment furnace.

8. The method of claim 1 , wherein the multi-element scanning thermal analysis includes a constant heating rate with flow of a carrier gas.

9. The method of claim 8 , wherein the constant heating rate is about 50° C./min.

10. The method of claim 8 , wherein the carrier gas is an approximate 40/60 volume mixture of oxygen and helium, whereby the mixture minimizes an artifact of charring organic carbon into black carbon during the multi-element scanning thermal analysis.

11. The method of claim 8 , wherein the flowrate of the carrier gas in a sample compartment furnace and in a combustion furnace is about 80 mL/min and about 350 mL/min, respectively.

12. The method of claim 11 , wherein
the one or more elements further includes a carbon species, a nitrogen species, and a hydrogen species,
the carrier gas carries volatile from the sample during heating into the combustion furnace that is fed by oxygen, thereby oxidizing the carbon species into carbon dioxide, the nitrogen species into nitrogen dioxide, the sulfur species into sulfur dioxide, and the hydrogen species into water.

13. The method of claim 12 , wherein the carbon dioxide is quantified by a carbon dioxide infrared analyzer, the nitrogen dioxide is quantified by a nitrogen dioxide detector, and the water is quantified by an infrared analyzer.

14. The method of claim 13 , further comprising utilizing the multi-channel data logger to record real-time signals from the carbon dioxide, signals from the nitrogen dioxide, and signals from the water.

15. The method of claim 14 , further comprising generating calibration curves of the carbon species, the nitrogen species, and the sulfur species based on known standards of mixtures of pure cystine and glucose.

16. The method of claim 15 , further comprising distinguishing between compounds having overlapping decomposition temperatures by normalizing the area under the peaks in the calibration curves, thus quantifying the carbon species, the nitrogen species, the hydrogen species, and the sulfur species.

17. The method of claim 1 , further comprising calibrating a temperature of the sample using elemental sulfur and silver sulfide internal standards to ensure proper temperature readings during the multi-element scanning thermal analysis.

18. The method of claim 1 , further comprising washing the sample substantially free of sulfuric acid prior to performing the multi-element scanning thermal analysis to ensure that no organosulfur is created during the multi-element scanning thermal analysis.

19. A method of analyzing a crude oil sample directly using multi-element scanning thermal analysis, the method comprising the steps of:
washing the sample substantially free of sulfuric acid using a solvent to ensure that no organosulfur is created in the sample;
heating the crude oil sample within a sample compartment furnace fed by oxygen;
disposing a carrier gas through the sample compartment furnace to a combustion furnace, thereby carrying volatile from the sample compartment furnace heating of the crude oil sample to the combustion furnace, such that one or more elements within the crude oil sample are oxidized, wherein the one or more elements includes
a sulfur species, a nitrogen species, a carbon species, and a hydrogen species;
wherein the sulfur species, the carbon species, the nitrogen species, and the hydrogen species correspond to distillation properties of sulfur compounds, hydrocarbon compounds, and nitrogen compounds in the crude oil sample;
determining the differences in the ratios of the carbon species, the nitrogen species, the sulfur species, and the hydrogen species based on the thermogram;
continuously scanning the crude oil sample using a multi-channel data logger in a temperature range from about 40° C. to about 800° C. within a programmed sample compartment furnace, where the thermogram obtained contains all possible distillation range information,
wherein the multi-element scanning thermal analysis includes a constant approximately 50° C./min heating rate with flow of a carrier gas, wherein the carrier gas is an approximate 40/60 volume mixture of purified oxygen and helium, whereby the mixture minimizes an artifact of charring organic carbon into black carbon during the multi-element scanning thermal analysis;
determining using a flow meter the flowrate of the carrier gas in a sample compartment furnace and in a combustion furnace, wherein the flowrate is about 80 mL/min and about 350 mL/min, respectively;
quantifying the carbon dioxide using a carbon dioxide infrared analyzer, quantifying the nitrogen dioxide using a nitrogen dioxide chemiluminescent detector, quantifying the sulfur dioxide a sulfur dioxide chemiluminescent detector; and quantifying the water using an infrared analyzer;
calibrating a temperature of the sample using elemental sul

Assignees

• Florida A&M Univ

Inventors

• Hsieh Yuch Ping

Classifications

• G01J5/00

  Radiation pyrometry, e.g. infrared or optical thermometry · CPC title

• G01N33/2823

  Raw oil, drilling fluid or polyphasic mixtures · CPC title

• G01N25/08 Primary

  of boiling point · CPC title

• G01N33/287

  Sulfur content · CPC title

• F23G2202/60

  in a catalytic combustion chamber · CPC title