The field of the invention relates to a method using a Rock-Eval™ apparatus (IFPEN) comprising a device for quantitative sulfur characterization (Rock-Eval Sulfur). From the analysis of a sample of some milligrams of raw sulfur-containing petroleum products, this method allows to estimate the values of:—the sulfur and carbon distribution in the atmospheric residue and the vacuum residue, and—the richness in sulfur of the coke in relation to the carbon content in coke, after distillation of this raw petroleum product.
This method is particularly intended for the sphere of petroleum product refining, but it can also apply to any technical field where the quantification of sulfur and/or of carbon and of their thermal reactivity in a solid or liquid product is required.
Document WO-2010/049,609 notably describes the Rock-Eval method and process for sulfur analysis. The Rock-Eval is a device comprising at least one oven for pyrolysis in an inert atmosphere and at least one oxidation oven. A sulfur measurement module is in particular added to this device for sulfur analysis.
The prior art relative to refining for estimating the sulfur and carbon content of distillation residues can notably be:
Coke as such is not present in crude oil before it is processed by thermal cracking and it is therefore not measured in the crude. However, the potential coke to be generated varies from one crude to the next and it can be measured according to conventional methods that are relatively long and complex. The present invention allows these drawbacks to be overcome.
The 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, wherein the following stages are carried out:
According to the method, said representative values can be determined as follows (in g/g):
The value representative of the richness in sulfur in relation to the carbon content in the coke can be determined with:
Thus, by means of simple Rock-Eval type measurements, refiners can rapidly obtain useful information on the distribution of the sulfur among the pyrolyzable products and the coke from different types of petroleum products.
Other features and advantages of the invention will be clear from reading the description hereafter, given by way of non limitative example, with reference to the accompanying figures wherein:
a and 1b give the measurements of the compounds released during the pyrolysis of a sulfur-containing petroleum product, with the Rock-Eval provided with a device for analyzing sulfur (as described in document WO-2010/049,609), as a function of the temperature of the sample (vertical axis to the right) and of the heating time (horizontal axis):
a, 2b, 2c give the measurements of the compounds released during the oxidation of the pyrolysis residue of a sulfur-containing petroleum product, with the Rock-Eval Sulfur device (as described in document WO-2010/049,609), as a function of the temperature of the sample (vertical axis to the right) and of the heating time (horizontal axis):
In this method, a petroleum product sample is analyzed using the Rock-Eval apparatus provided with a device for measuring sulfur. The whole device is described in detail in patent WO-2010/049,609.
In this method, depending on the type of product analyzed, between 3 mg and 15 mg of feedstock are required per analysis. The sample is placed in a boat of the Rock-Eval apparatus between two finely crushed silica layers. The analysis is carried out in two automated stages. The first stage, referred to as pyrolysis, consists in heating the petroleum product sample in a continuous inert gas stream, which can be nitrogen. The temperature of the sample rises from an initial temperature ranging between 100° C. and 180° C. to a final temperature ranging between 650° C. and 800° C., while following a predetermined temperature program. During this first stage, the petroleum product sample releases carbon-containing and sulfur-containing effluents that are carried along by the inert gas stream towards specific analyzers where they are subjected to continuous measurement.
At the same time, a fraction of the pyrolysis effluents enters an oxidation oven. The sulfur contained in these effluents is then oxidized to SO2 and it is sent to the specific analyzer to be subjected to continuous measurement. An example of the result of this measurement is shown in
At the end of the pyrolysis process, a petroleum product residue referred to as pyrolysis residue remains in the bottom of the boat. This residue is transferred in its boat to an oxidation oven. The second stage of the analysis is referred to as oxidation and it consists in heating the pyrolysis residue in a continuous air stream according to a predetermined temperature program. The initial temperature ranges between 300° C. and 400° C., and the final temperature ranges between 700° C. and 1200° C. depending on the type of product analyzed.
During this second stage, the pyrolysis residue of the sample is oxidized and it releases carbon-containing and sulfur-containing gases that are carried along by the air stream towards the specific analyzers where they are subjected to continuous measurement. An example of the result of these measurements is shown in
Among the base parameters provided by the Rock-Eval Sulfur device, four parameters are used in this method:
It is the mass of organic compounds released by the sample through thermal cracking during the pyrolysis stage between approximately 400° C. and the final pyrolysis temperature (
S2b is generally given in the following unit: g (organic compounds)/1000 g (sample).
It is the mass of sulfur released by the sample during thermal cracking in the pyrolysis stage that is conducted between approximately 400° C. and the final pyrolysis temperature (
SulfS2b is generally given in the following unit: g (Sulfur)/100 g (sample).
It is the mass of carbon in the residual sample after pyrolysis, in relation to the initial mass of the petroleum product sample; this carbon is released during the stage of oxidation of the pyrolysis residue, between 350° C. and the maximum oxidation temperature that can range between 700° C. and 1200° C. depending on the temperature program selected (
RC=S4CO2×12/440+S4CO×12/280, where:
RC is generally given in the following unit: g (C)/100 g (sample).
It is the mass of residual sulfur after pyrolysis in relation to the initial sample mass; this sulfur is released during the oxidation of the pyrolysis residue, between 350° C. and the maximum oxidation temperature (
Sulfoxy is generally given in the following unit: g (Sulfur)/100 g (sample).
The organic compounds that are released during the pyrolysis between approximately 400° C. and the final pyrolysis temperature, which are characterized by parameters S2b (for carbon) and SulfS2b (for sulfur), come from the pyrolyzable heavy fraction of the petroleum product analyzed that is thermally crackable.
The organic compounds that are released during the oxidation of the pyrolysis residue, which are characterized by parameters RC (for carbon) and Sulfoxy (for sulfur), come from the non-pyrolyzable heavy fraction of the petroleum product analyzed.
It has been noted that this non-pyrolyzable heavy fraction defined by the Rock-Eval analysis appears to be representative of the coke obtained after refining a petroleum feedstock. This is supported by the correlation observed between Rock-Eval parameter RC (residual carbon) and the carbon content of the residue obtained through ASTM D189 (CCR) and ASTM D4530 (MCR), this residue being itself representative of the coke obtained by refining a petroleum product (
From this conception of the origin of the Rock-Eval pyrolysis and oxidation effluents, four indicators describing the proportion of sulfur and carbon in the pyrolyzable heavy fraction (PHF) and in the coke can be defined.
Two indicators describe the proportion of sulfur in the pyrolyzable heavy fraction (PHF) and in the coke:
SPHF=SulfS2b/[SulfS2b+Sulfoxy] expressed in g/g a.
SCOKE=Sulfoxy/[SulfS2b+Sulfoxy] expressed in g/g. b.
They satisfy the equality as follows:
SPHF+SCOKE=1.
Two indicators describe the proportion of carbon in the pyrolyzable heavy fraction (PHF) and in the coke:
CPHF=S2b*0.083/[S2b*0.083+RC] expressed in g/g c.
CCOKE=RC/[S2b*0.083+RC] expressed in g/g. d.
They satisfy the equality as follows:
CPHF+CCOKE=1.
A fifth indicator describes the richness in sulfur of the coke in relation to carbon, carbon being the main element in coke:
Sulfoxy/RC expressed in g/g. e.
These five indicators are used within the context of the present invention.
The interests and advantages of the five indicators of the method according to the invention, compared to existing methods of evaluation, are as follows:
a. There is no known method allowing, in a single analysis, to distinguish thermally extractable sulfur compounds from those thermally crackable and those thermally refractory.
b. To our knowledge, neither is there a method for simultaneously separating extractable carbon-containing species from those thermally crackable and those thermally refractory.
Eight petroleum product samples were analyzed with the Rock-Eval Sulfur device and their indicators SPHF, SCOKE, CPHF, CCOKE, Sulfoxy/RC were quantified.
These samples were:
a heavy oil A and a conventional oil B,
their respective atmospheric residues, after atmospheric distillation,
their respective vacuum residues, after vacuum distillation of the atmospheric residue,
their respective asphaltenes fractions.
The results obtained are given in Tables 1 and 2 and in
If we compare the five indicators SPHF, SCOKE, CPHF, CCOKE, Sulfoxy/RC in Tables 1 and 2, for the crude oils, their atmospheric distillation residues and their vacuum distillation residues, we observe very close results. By comparison, these five indicators applied to the asphaltenes show very different results from those obtained for the crude oils and the distillation residues.
This clearly shows that the values of the indicators according to the invention (SPHF, SCOKE, CPHF, CCOKE, Sulfoxy/RC), obtained on the crude oil by means of a Rock-Eval analysis (S2b, SulfS2b. Sulfoxy, RC), allow to estimate those of the distillation residues. These fast and therefore inexpensive estimations are very advantageous for evaluating the thermal reactivity of the sulfur and the carbon of the residues of a feedstock to be refined.
Number | Date | Country | Kind |
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13/61.389 | Nov 2013 | FR | national |