Methods and apparatus for measuring hydrogen sulfide in downhole fluids
US-10120097-B2 · Nov 6, 2018 · US
US9638682B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-9638682-B2 |
| Application number | US-201414548491-A |
| Country | US |
| Kind code | B2 |
| Filing date | Nov 20, 2014 |
| Priority date | Nov 20, 2013 |
| Publication date | May 2, 2017 |
| Grant date | May 2, 2017 |
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The present invention relates to a method of estimating, for a petroleum feedstock, values representative of the sulfur and carbon distributions in atmospheric and vacuum distillation residues, and a value representative of the sulfur content in coke. According to the method, the following stages are carried out: from a feedstock sample, measuring at least the Rock-Eval parameters S2b, Sulf S2b , RC, Sulf oxy using a Rock-Eval device comprising a sulfur measurement module, deducing from the measurements of these Rock-Eval parameters the values of the sulfur and carbon distributions (S PHF , S COKE , C PHF , C COKE ) in the distillation residues, and a sulfur content in relation to the carbon content in the coke.
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The invention claimed is: 1. A method of estimating, for crude oil, values representative of the distribution of sulfur and carbon in atmospheric and vacuum distillation residues, and a value representative of the sulfur in the coke, a method wherein the following stages are carried out: from a crude oil sample, measuring at least parameters S2b, Sulf S2b , RC, Sulf oxy using a device comprising at least one oven for pyrolysis in an inert atmosphere and at least one oxidation oven, said device comprising a sulfur measurement module, S2b being the mass proportion of heavy pyrolyzable compounds contained in said sample, Sulf S2b being the mass proportion of sulfur in the heavy pyrolyzable compounds contained in said sample, RC being the mass proportion of carbon of the pyrolysis residue of said sample, and Sulf oxy being the mass proportion of sulfur in the pyrolysis residue of said sample, deducing from said measurements of said parameters said values of the sulfur and carbon distributions in the distillation residues, and a sulfur content in relation to the carbon content in the coke. 2. A method as claimed in claim 1 , wherein said representative values are determined as follows: S PHF =Sulf S2b /[Sulf S2b +Sulf oxy ], where S PHF corresponds to the proportion of sulfur in the pyrolyzable heavy fraction, with said parameters Sulf S2b , Sulf S2b and Sulf oxy expressed in gram of sulfur per 100 grams of said sample, S COKE =Sulf oxy /[Sulf S2b +Sulf oxy ], where S COKE corresponds to the proportion of sulfur in the coke, with said parameters Sulf S2b , Sulf S2b and Sulf oxy expressed in gram of sulfur per 100 grams of said sample, with S PHF +S COKE =1, C PHF =S2b*0.083/[S2b*0.083+RC], where C PHF corresponds to the proportion of carbon in the pyrolyzable heavy fraction, with said parameters S2b expressed in gram of organic compounds per 1000 grams of said sample and RC expressed in gram of carbon per 100 grams of said sample, C COKE =RC/[S2b*0.083+RC], where C COKE corresponds to the proportion of carbon in the coke, with said parameters S2b expressed in gram of organic compounds per 1000 grams of said sample and RC expressed in gram of carbon per 100 grams of said sample, with C PHF +C COKE =1. 3. A method as claimed in claim 1 , wherein the value representative of the richness in sulfur in relation to the carbon content in the coke is determined as follows: Sulf oxy /RC, with said parameters Sulf oxy and RC expressed in gram of sulfur and carbon respectively per 100 grams of said sample. 4. A method of estimating, for crude oil, values representative of the distribution of sulfur and carbon in atmospheric and vacuum distillation residues, and a value representative of the sulfur in the coke, a method wherein the following stages are carried out: from a crude oil sample, measuring at least parameters S2b, Sulf S2b , RC, Sulf oxy using a device comprising at least one oven for pyrolysis in an inert atmosphere and at least one oxidation oven, said device comprising a sulfur measurement module, S2b being the mass proportion of heavy pyrolyzable compounds contained in said sample, Sulf S2b being the mass proportion of sulfur in the heavy pyrolyzable compounds contained in said sample, RC being the mass proportion of carbon of the pyrolysis residue of said sample, and Sulf oxy being the mass proportion of sulfur in the pyrolysis residue of said sample, deducing from said measurements of said parameters said values of the sulfur and carbon distributions in the distillation residues, and a sulfur content in relation to the carbon content in the coke, wherein said representative values of the sulfur and carbon distributions in the distillation residues are determined as follows: S PHF =Sulf S2b /[Sulf S2b +Sulf oxy ], where S PHF corresponds to the proportion of sulfur in the pyrolyzable heavy fraction, with said parameters Sulf S2b , Sulf S2b and Sulf oxy expressed in gram of sulfur per 100 grams of said sample, S COKE =Sulf oxy [Sulf s2b +Sulf oxy ], where S COKE corresponds to the proportion of sulfur in the coke, with said parameters Sulf S2b , Sulf S2b and Sulf oxy expressed in gram of sulfur per 100 grams of said sample, with S PHF +S COKE =1, C PHF =S2b*0.083/[S2b*0.083+RC], where C PHF corresponds to the proportion of carbon in the pyrolyzable heavy fraction, with said parameters S2b expressed in gram of organic compounds per 1000 grams of said sample and RC expressed in gram of carbon per 100 grams of said sample, C COKE =RC/[S2b*0.083+RC], where C COKE corresponds to the proportion of carbon in the coke, with said parameters S2b expressed in gram of organic compounds per 1000 grams of said sample and RC expressed in gram of carbon per 100 grams of said sample, with C PHF +C COKE =1, and wherein the value representative of the richness in sulfur in relation to the carbon content in the coke is determined as follows: Sulf oxy /RC, with said parameters Sulf oxy and RC expressed in gram of sulfur and carbon respectively per 100 grams of said sample.
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