Petroleum source rock identification

• US 4,463,096 A
• Filed: 11/16/1981
• Issued: 07/31/1984
• Est. Priority Date: 11/16/1981
• Status: Expired due to Fees

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Hughes, William B.
• Primary Examiner(s): Marcus, Michael S.
• Application Number:
  US06/321,507
• Time in Patent Office: 988 Days
• Field of Search: 436/29-31, 436/91, 436/120, 436/171, 436/140, 436/161, 73/23.1
• US Class Current: 436/29
• CPC Class Codes: G01N 33/241 for hydrocarbon content
• CPC Class Codes: G01N 33/287 Sulfur content
• CPC Class Codes: Y10T 436/14 Heterocyclic carbon compound [i.e. , O, S, N, Se, Te, as only ring hetero atom]
• CPC Class Codes: Y10T 436/182 Organic or sulfhydryl containing [e.g., mercaptan, hydrogen, sulfide, etc.]
• CPC Class Codes: Y10T 436/212 Aromatic

Abstract

The geochemical oil prospecting method is disclosed in which a crude oil sample is analyzed for the presence of distinctive patterns of aromatic sulfur compounds which are indicative of the petroleum source rock type. Using relative proportions of benzothiophenes, dibenzothiophene, isomeric methyl dibenzothiophenes, dimethyl- and trimethydibenzothiophenes a crude oil can be identified as having a carbonate or siliciclastic source. The information obtained can be used in combination with geological and seismic studies to determine potential oil locations.

Claims

1. A method for determining the source rock type of a crude oil sample comprising:

(a) determining the relative amounts of benzothiophenes and dibenzothiophenes in the sample of crude oil;

(b) determining the relative amounts of the isomeric methyldibenzothiophenes present in the sample of crude oil;

(c) determining the relative amounts of dimethyl- and trimethyldibenzothiophenes present in the sample of crude oil; and

(d) identifying, on the basis of the results of steps a, b, and c, the source rock type of the crude oil sample.

2. The method of claim 1 which comprises performing steps a, b and c by gas chromatography using a chromatographic column.

3. The method of claim 2 which further comprises fractionating the crude oil into components including an aromatic fraction and performing steps a, b, and c and d with the aromatic fraction.

4. The method of claim 3 which comprises

detecting the benzothiophenes and dibenzothiophenes which elute from the chromatographic column with a flame photometric detector and producing respective first and second sets of output signals representative of the amount of benzothiophenes and dibenzothiophenes detected,

detecting first, second and third major isomers of methyldibenzothiophene which elute from the chromatographic column with a flame photometric detector and producing third, fourth and fifth output signals representative of the respective amounts detected, and

detecting the dimethyl- and trimethyldibenzothiophenes which elute from the chromatographic column with a flame photometric detector and producing respective sixth and seventh sets of output signals proportional to the amount of dimethyl- and trimethyldibenzothiophenes detected.

5. The method of claim 4 which further comprises comparing the third, fourth and fifth output signals.

6. The method of claim 5 additionally comprising comparing the third, fourth and fifth signals and determining that the crude oil sample is from a carbonate source rock in response to the third signal being representative of an amount of first isomer at least equal to the amount of third isomer represented by the fifth signal and the fifth signal being representative of an amount of third isomer greater than the amount of second isomer represented by the fourth signal.

7. The method of claim 4 which further comprises comparing the first and second sets of output signals, comparing the third, fourth and fifth output signals, and comparing the combined second, third, fourth and fifth output signals with the combined sixth and seventh output signals.

8. The method of claim 7 additionally comprising determining that the crude oil sample is from a siliciclastic type source rock in response to the amount of first isomer represented by the third signal being at least equal to the amount of second isomer represented by the fourth signal, the amount of second isomer represented by the fourth signal being greater than the amount of third isomer represented by the fifth signal, and the combined amount of dibenzothiophene and methyldibenzothiophenes represented by the second set of output signals and the third, fourth and fifth output signals being greater than the combined amount of dimethyl- and trimethyldibenzothiophenes represented by the combined sixth and seventh sets of output signals.

9. The method of claim 7 which further comprises drilling a borehole proximate to a formation which corresponds in type to the identity of the source rock determined.

10. A method of geochemical oil prospecting which involves identifying a crude oil sample as having a carbonate source, the method comprising:

(a) extracting an organosulfur-containing aromatic fraction from the crude oil;

(b) injecting the aromatic fraction into a gas chromatograph column and separating on the column constituents comprising benzothiophenes, dibenzothiophenes, three major isomers of methyldibenzothiophenes, dimethyldibenzothiophenes and trimethyldibenzothiophenes;

(c) detecting each constituent as it elutes from the column and producing an output signal for each which is proportional to the amount of each constituent present;

(d) obtaining an output signal for benzothiophenes which is at least approximately equal to the output signal for dibenzothiophenes;

(e) obtaining an output signal for the first major isomer which is greater than or equal to the output signal for the third major isomer of methyldibenzothiophene which in turn is greater than the output signal for the second major isomer of methyldibenzothiophene the first, second and third major isomer being numbered in terms of their order of elution from the column; and

(f) obtaining output signals for methyl-, dimethyl- and trimethyldibenzothiophenes, none of which is more than twice the magnitude of any other of the three.

11. The method of claim 10 in which the constituents are detected by means of a flame photometric detector, the output signals are recorded as peaks on a gas chromatogram, and the areas under the peaks are automatically calculated.

12. The method of claim 10 in which the oil came from an underground reservoir and which further comprises performing a geologic and seismic study to locate oil reservoirs having carbonate source.

13. A method of geochemical oil prospecting which involves identifying a crude oil sample as having a siliciclastic source, the method comprising:

(a) extracting an organosulfur-containing aromatic fraction from the crude oil;

(b) injecting the aromatic fraction into a gas chromatograph column and separating on the column constituents comprising benzothiophenes, dibenzothiophenes, three major isomers of methyldibenzothiophene, dimethyldibenzothiophenes and trimethyldibenzothiophenes;

(c) detecting each constituent as it elutes from the column and producing an output signal for each which is representative of the amount of each constituent present;

(d) obtaining an output signal for benzothiophenes which is small in comparison with the output signal for dibenzothiophenes;

(e) obtaining an output signal for the first isomer of methyldibenzothiophene which is greater than or equal to the output signal for the second isomer, which in turn is greater than the output signal for the third isomer, the first, second and third isomers being numbered according to their order of elution from the column;

(f) obtaining combined output signals for dibenzothiophenes and methyldibenzothiophenes which are greater than the combined output signals for dimethyl- and trimethyldibenzothiophenes.

14. The method of claim 13 in which the constituents are detected by means of a flame photometric detector, the output signals are recorded as peaks on a gas chromatogram, and the areas under the peaks are automatically calculated.

15. The method of claim 13 in which the crude oil was obtained from an underground reservoir and which further comprises performing a seismic study to locate other oil reservoirs having a siliciclastic source.

16. A method of geochemical oil prospecting which involves identifying a mature crude oil sample as having a carbonate source, the method comprising:

(a) extracting an aromatic fraction from the crude oil;

(b) injecting the aromatic fraction into a gas chromatograph column and separating on the column constituents comprising benzothiophenes, dibenzothiophenes, three major isomers of methyldibenzothiophene, dimethyldibenzothiophenes and trimethyldibenzothiophenes;

(c) detecting each constituent as it elutes from the column and producing an output signal for each which is proportional to the amount of each constituent present;

(d) obtaining an output signal for benzothiophenes which is no greater than the output signal for dibenzothiophenes;

(e) obtaining an output signal for the first isomer of methyldibenzothiophene which is greater than the output signal for the second isomer which in turn is greater than or equal to the output signal for the third isomer, the first, second and third isomers being numbered according to their order of elution from the column; and

(f) obtaining combined output signals for dibenzothiophene and methyldibenzothiophenes which are no greater than the combined output signals for dimethylbenzothiophenes and trimethyldibenzothiophenes.