# US 9,038,435 B2 · Measurement of carbon to hydrogen ratio in hydrocarbons

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- Number: US 9,038,435 B2
- Document ID: US9038435B2
- Status: Granted
- Kind: B2
- Application number: 13/669,813
- Filed: 2012-11-06
- Published: 2013-05-23
- Granted: 2015-05-26
- Earliest claimed: 2011-11-17
- Assignees: ExxonMobil Research and Engineering Company
- Applicants: ExxonMobil Research and Engiineering Company
- Inventors: Frank C Wang
- Web page: https://patentgrep.com/patent/US9038435B2

## CPC

- G01N 30/74: Optical detectors {(measurement of intensity, velocity, spectral content, polarisation, or phase of infrared, visible or ultraviolet light G01J)}
- G01N 2030/8854: {involving hydrocarbons}
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)

## Abstract

The ratio of carbon to hydrogen in hydrocarbon samples is determined using gas chromatography and atomic emission detection. Comparison of the carbon to hydrogen ratio from different samples allows for qualitative determination of relative hydrogen content. Establishing a carbon to hydrogen ratio for a reference sample allows a further quantitative determination of carbon to hydrogen ratio.

## Claims

### Claim 1

A method for characterizing the ratio of hydrogen to carbon in a sample, comprising:
separating a plurality of compounds in a first hydrocarbon sample using gas chromatography;
measuring atomic emissions from carbon atoms and hydrogen atoms for one or more compounds from the first hydrocarbon sample;
determining a first hydrogen to carbon peak area ratio based on the hydrogen peak area and carbon peak area for the one or more compounds from the first hydrocarbon sample;
separating a plurality of compounds in a second hydrocarbon sample using gas chromatography;
measuring atomic emissions from carbon atoms and hydrogen atoms for one or more compounds from the second hydrocarbon sample;
determining a second hydrogen to carbon peak area ratio based on the hydrogen peak area and carbon peak area for the one or more compounds from the second hydrocarbon sample; and
comparing the first hydrogen to carbon peak area ratio and the second hydrogen to carbon peak area ratio.

### Claim 2 (depends on 1)

The method of claim 1, wherein separating a plurality of compounds results in at least one grouping of two or more compounds that leaves the gas chromatography apparatus during a common retention time period.

### Claim 3 (depends on 1)

The method of claim 1 wherein the second hydrocarbon sample comprises a reference compound or a reference mixture of compounds.

### Claim 4 (depends on 1)

The method of claim 1, wherein the first hydrocarbon sample comprises a carrier or solvent.

### Claim 5 (depends on 4)

The method of claim 4, wherein the one or more compounds from the first hydrocarbon sample exclude the carrier or solvent.

### Claim 6 (depends on 1)

The method of claim 1, wherein the carbon atomic emissions are measured at 496 nm and the hydrogen atomic emissions are measured at 486 nm.

### Claim 7 (depends on 1)

The method of claim 1, wherein the one or more compounds from the first hydrocarbon sample comprise all of the compounds from the first sample.

### Claim 8 (depends on 1)

The method of claim 1, wherein the first hydrocarbon sample and the second hydrocarbon sample correspond to different feedstocks.

### Claim 9 (depends on 1)

The method of claim 1, wherein the first hydrocarbon sample and the second hydrocarbon sample correspond to a single feedstock, the first hydrocarbon sample and second hydrocarbon sample having different retention times along at least one dimension in the gas chromatography separation.

### Claim 10 (depends on 1)

The method of claim 1, further comprising selecting at least one distillation cut point for a feedstock corresponding to the first sample based on the comparing of the first hydrogen to carbon peak ratio and the second hydrogen to carbon peak ratio.

### Claim 11 (depends on 1)

The method of claim 1, wherein at least one of the first hydrocarbon sample and the second hydrocarbon sample corresponds to a refinery feed or product stream.

### Claim 12

A method for characterizing the ratio of hydrogen to carbon in sample, comprising:
separating a plurality of compounds in a hydrocarbon sample using gas chromatography;
measuring atomic emissions from carbon atoms and hydrogen atoms for one or more compounds from the hydrocarbon sample;
determining a hydrogen to carbon peak area ratio based on the hydrogen peak area and carbon peak area for the one or more compounds from the hydrocarbon sample; and
scaling the hydrogen to carbon peak area ratio to calculate a hydrogen to carbon ratio for the one or more compounds.

### Claim 13 (depends on 12)

The method of claim 12, wherein scaling the hydrogen to carbon peak ratio comprises:
measuring atomic emissions from carbon atoms and hydrogen atoms for a plurality of reference compounds;
determining a scaling factor based on hydrogen to carbon peak area ratios for the plurality of reference compounds; and
scaling the hydrogen to carbon peak area ratio for the one or more compounds using the determined scaling factor.

### Claim 14 (depends on 12)

The method of claim 12, wherein the hydrocarbon sample comprises a carrier or solvent.

### Claim 15 (depends on 14)

The method of claim 14, wherein the one or r more compounds from the hydrocarbon sample exclude the carrier or solvent.

### Claim 16 (depends on 12)

The method of claim 12, wherein the hydrocarbon sample corresponds to a refinery feed or product stream.

### Claim 17

A method for characterizing the ratio of hydrogen to carbon in a sample, comprising:
separating a plurality of compounds in a first hydrocarbon sample using gas chromatography;
measuring atomic emissions from carbon atoms and hydrogen atoms for one or more compounds from the first hydrocarbon sample, the measured atomic emissions corresponding to a first carbon peak area and a first hydrogen peak area;
separating a plurality of compounds in a second hydrocarbon sample using gas chromatography;
measuring atomic emissions from carbon atoms and hydrogen atoms for one or more compounds from the second hydrocarbon sample, the measured atomic emissions corresponding to a second carbon peak area and a second hydrogen peak area;
calculating a normalizing factor for the first carbon peak area, the first carbon peak area multiplied by the normalizing factor corresponding to the second carbon peak area;
normalizing the first hydrogen peak area based on the normalizing factor; and
comparing the normalized first hydrogen peak area and the second hydrogen peak area.

### Claim 18 (depends on 17)

The method of claim 17, wherein the second hydrocarbon sample comprises a reference compound or a reference mixture of compounds.

### Claim 19 (depends on 17)

The method of claim 17, wherein the first hydrocarbon sample comprises a carrier or solvent.

### Claim 20 (depends on 19)

The method of claim 19, wherein the one or more compounds from the first hydrocarbon sample exclude the carrier or solvent.
