JP2015059220A - Method of producing ship fuel of low sulfur content from hco produced by catalytic decomposition or slurry-type hydrocarbon-containing fraction using hydrogenation treatment stage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a ship fuel and a base for ship fuels which meet recommendation conditions of the MARPOL Convention, with respect to the equivalent sulfur content, and preferably meet conditions of Standard ISO8217.SOLUTION: A method of producing a ship fuel (47) starting from HCO produced by catalytic decomposition or a slurry-type hydrocarbon-containing fraction (10) comprises: a) a hydrogenation stage (a), (17), of producing a hydrogenated effluent; b) a step (b), (20), (24), (37), and (43), of separating the hydrogenated effluent hydrogenated in the stage (a) to obtain a gas fraction and a liquid hydrocarbon-containing fraction; and c) an optional stage (c), (46), of mixing the liquid hydrocarbon-containing fraction with a paraffin-rich hydrocarbon-containing fraction, in order to obtain the required ship fuel (47).

Description

  The present invention relates to the production of marine fuels from HCO or “slurry” type hydrocarbon containing fractions generated from catalytic crackers.

  The HCO fraction (abbreviation for “heavy cycle oil”) contains, inter alia, compounds containing sulfur-containing impurities, with an initial boiling point of at least 300 ° C. and a final boiling point of at least 450 ° C. Contains 80%. The so-called “slurry” fraction with a sulfur content above 0.5% by weight contains a minimum of 80% of a compound with a boiling point of at least 360 ° C. and a final boiling point of at least 520 ° C. The term “slurry” does not have a simple translation in French, so we will use the English term.

  In the following, whenever an HCO type fraction or "slurry" type fraction is mentioned, this will mean the above and will have the above characteristics.

  Catalytic cracking is known by the acronyms FCC (abbreviation for “Fluid Catalytic Cracking”) and RFCC (abbreviation for “Resid Fluid Catalytic Cracking”).

FCC and RFCC are methods for the conversion of vacuum distillates and / or distillation residues, in particular allowing the following products to be obtained:
-Liquefied petroleum gas-Gasoline fraction-Light distillate known as LCO ("Light Cycle Oil"): Initial boiling point is at least 200 ° C and final boiling point is at least 300 ° C, A typical distillation range contains at least 80% of a compound that is 220-350 ° C-a heavy distillate known as HCO ("Heavy Cycle Oil"): has an initial boiling point of at least 300 ° C and Contains a minimum of 80% of a compound with a final boiling point of at least 450 ° C. and a typical distillation range of 350-540 ° C.-optionally (especially in the case of RFCC) residue or "slurry": The catalyst particles are refined to obtain a clarified heavy oil (CLO) or decanted oil (DO); the initial boiling point of this residue is generally 5 It is 0 ℃ greater.

  Sometimes the HCO and “slurry” fractions are not separated.

  More specifically, the present invention is a method for producing marine fuel and a marine fuel base, the marine fuel and marine fuel base having good flammability and low sulfur content. Relates to a process starting from HCO-type or “slurry” fractions obtained from FCC or RFCC.

  The present invention has the object of producing marine fuels and marine fuel bases that comply with the recommendations of the Mar Paul Convention in terms of equivalent sulfur content, preferably also according to the standard ISO 8217.

  Annex VI of the Marpole Convention aims to progressively reduce the sulfur content of marine fuels. Ultimately, the maximum equivalent sulfur content will be 0.1% w / w in Sulfur Emission Control Areas (SECAs) and 0.5% w / w in the rest of the world.

  Among marine fuels, a distinction is made between distillate-type fuels and residue-type fuels in the standard ISO 8217. Within these two categories, there are multiple grades, and viscosity is one of the main distinguishing factors.

  For residue-type fuels, the characteristics reflecting the quality of combustion are measured by the Calculated Carbon Aromaticity Index (CCAI).

  The correlation between the aromatic character of the fuel and the ignition delay is known to those skilled in the art. The formula for calculating CCAI is described in the latest revision of standard ISO 8217. This formula specifically requires the density and viscosity of the fuel. For all marine fuel grades of residue type, ISO 8217 recommends a maximum CCAI of 870.

  The use of hydrocarbon fractions from catalytic cracking as a fuel base, especially as a base for marine fuels, has long been known, especially because of the low viscosity of the fraction from catalytic cracking Was known for degrading. However, such use is of a limited proportion in fuel pools, in particular marine fuel pools, due to the very aromatic character of the fraction resulting from catalytic cracking. If the predetermined content in the mixture is exceeded, the flammability deteriorates.

  In addition, the fractions resulting from catalytic cracking are generally sulfur-containing, and their incorporation into fuel pools, particularly marine fuel pools, is the International Maritime Organization (IMO) Marpole Convention. Increasingly problematic to meet the sulfur specification for the fuel recommended by Appendix VI.

The following documents in the related prior art may be mentioned:
Patent Document 1: A method for selective hydrogenation of heavy fractions of HCO type and its recycle to a catalytic cracker to improve the production of catalytic cracking middle distillates is described.
Patent Document 2: Describes a method for hydrogenating LCO, HCO with recycle of effluent to catalytic cracking to obtain a better grade of gasoline fraction.

French Patent Application Publication No. 2983208 European Patent Application No. 0432235

  Both of these documents describe fuel or fuel-based production with low sulfur content that meets the new recommendations of the International Maritime Organization and good flammability as required by the new version of the standard ISO 8217/2012. Not.

  The present invention relates to a hydrocarbon fraction from catalytic cracking containing at least 80% of a compound having a sulfur content of more than 0.5% by weight, a boiling point of at least 300 ° C. and a final boiling point of at least 450 ° C. The conditions for improving the quality of the so-called HCO fraction are described.

In order to solve the above problems, the present invention is intended to produce marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, a so-called HCO feedstock (abbreviation for Heavy Cycle Oil) or "slurry" feedstock. Wherein the HCO feedstock is a heavy fraction, a compound having a sulfur content of at least 0.5% by weight, a boiling point of at least 300 ° C. and a final boiling point of at least 450 ° C. At least 80% of the “slurry” feedstock having a sulfur content greater than 0.5% by weight, a boiling point of at least 360 ° C. and a final boiling point of at least 520 ° C. In the method, the sulfur content is 0.5% by weight or less and the CCAI is less than 870 (CCAI: “Calculated Carbon Aromaticity Index” according to the standard ISO 8217 (calculated carbon aromaticity). Number)) makes it possible to obtain at least one liquid hydrocarbon-containing fraction, this fraction constitutes a marine fuel, the method comprising the following successive stages:
^* ) Preliminary Filtration Stage (FILT): This is applied only to the “slurry” fraction to remove at least some of the fine particles it contains, resulting in a filtered term called CLO. And this CLO fraction is then treated in the same manner as the HCO fraction, i.e. it undergoes steps a); b); c).
a) hydroprocessing stage of an HCO or CLO feedstock (a), optionally co-processed with another hydrocarbon-containing feedstock to produce a hydrotreated effluent;
b) stage (b) of separation of the hydrotreated effluent resulting from stage (a), wherein at least one gas fraction and a liquid hydrocarbon-containing fraction are obtained,
c) optionally mixing the liquid hydrocarbon-containing fraction resulting from the separation step (b) with a paraffin-rich hydrocarbon-containing fraction (c)
Including a method.

The invention also relates to a method for producing marine fuel starting from a hydrocarbon-containing feedstock produced from catalytic cracking, wherein the hydrotreating stage a) when the starting feedstock is a so-called HCO feedstock. Is
-Temperature: 280-390 ° C, preferably 320-360 ° C,
-Absolute pressure: 5-15 MPa, preferably 6-10 MPa,
-Hydrocarbon feedstock space velocity: commonly referred to as LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst. 0.1 to 5 h ⁻¹ , preferably 0.2 to 2 h ⁻¹ , more preferably 0.3 to ¹ h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ ,
Performed under the operating conditions of
The step c) of mixing with the paraffinic fraction is unnecessary, since the liquid effluent from step b) results in a liquid effluent that complies with the specifications for marine fuels according to the standard.

The present invention is also a method for producing marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, where the starting feedstock is a so-called HCO feedstock, step a)
-Temperature: 280-390 ° C, preferably 320-360 ° C,
-Absolute pressure: less than 5 MPa,
-Hydrocarbon feedstock space velocity: commonly referred to as LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst. 0.1 to 5 h ⁻¹ , preferably 0.2 to 2 h ⁻¹ , more preferably 0.3 to ¹ h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ ,
Performed under the conditions of
-Mixing step c) with paraffinic fractions is necessary, said paraffinic fractions comprising the following fractions: fractions resulting from direct distillation (so-called "straight cut" fractions), for example atmospheric pressure or A process selected from vacuum distillates and / or atmospheric or vacuum residues.

The present invention is also a method for producing marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, wherein the starting feedstock is a “slurry” fraction and after filtration becomes a CLO fraction In some cases, the operating conditions of the hydrotreatment stage a) are:
-Temperature: 300-420 ° C, more preferably 340-390 ° C,
-Absolute pressure: 5-20 MPa, preferably 8-18 MPa,
-Space velocity of hydrocarbon feedstock (LHSV defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst): 0.1-2 .5 h ⁻¹ , preferably in the range of 0.3 to 0.8 h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³
The method is as follows.

  In the process for producing marine fuel starting from the above HCO or CLO type feedstock, preferably the paraffinic fraction used to carry out the mixing stage c) originated from direct distillation at atmospheric or vacuum Arising from a feed hydrotreating or hydrocracking process or conversion process.

In the method of producing marine fuel starting from the above HCO or CLO type feedstock, preferably in addition to the HCO or CLO feedstock, the hydrotreatment stage is used alone or in a mixture in co-processing. ,Less than:
-Gas oil from direct distillation at atmospheric pressure or vacuum,
-LCO from catalytic cracking,
-Gas oil from caulking,
-Gas oil from visbreaking,
-Up to 30% by weight of one of the gas oil feeds from the hydroconversion of the residue (hydrotreating and / or hydrocracking), based on the total feed (HCO + co-processed feed) Process with.

  In summary, the present invention is a method for producing marine fuel starting from HCO or “slurry” type hydrocarbon-containing fractions resulting from catalytic cracking, said method comprising: obtaining a required marine fuel A) a hydrotreating stage (a) producing a hydrotreated effluent, b) a stage (b) of separating the hydrotreated effluent resulting from stage (a), wherein the gas fraction And c) obtaining a liquid hydrocarbon-containing fraction, c) optionally comprising a step (c) of mixing said liquid hydrocarbon-containing fraction with a paraffin-rich hydrocarbon-containing fraction.

  According to the above method of the present invention, it is possible to produce marine fuels and marine fuel bases that comply with the recommendations of the Mar Paul Convention in terms of equivalent sulfur content, and preferably also comply with the standard ISO8217.

FIG. 1 presents a schematic diagram of the process according to the invention, with a) a hydrotreating zone, b) a zone for separating the effluent from the hydrotreating zone and c) an optional paraffin-rich fraction and The band for mixing is shown.

(Brief description of the invention)
The present invention is a method of producing marine fuel starting from a hydrocarbon-containing feedstock from catalytic cracking (so-called HCO (Heavy Cycle Oil) feedstock), which hydrocarbon-containing feedstock May be defined as a method containing at least 80% of a compound having a sulfur content of at least 0.5% by weight, an initial boiling point of at least 300 ° C. and a final boiling point of at least 450 ° C. Even if the initial feedstock is a “slurry” fraction containing at least 80% of a compound having a sulfur content greater than 0.5% by weight, a boiling point of at least 360 ° C. and a final boiling point of at least 520 ° C. Good. The process according to the invention obtains a liquid hydrocarbon fraction having a sulfur content of less than 0.5% by weight and a CCAI (abbreviation of Calculated Carbon Aromaticity Index according to Standard 8217) of less than 870. And the method comprises the following successive steps:
^* ) Preliminary Filtration Stage (FILT): This applies only to the “slurry” fraction, which removes at least some of the fine particles it contains, resulting in a filtered fraction called CLO And this filtered fraction is then treated in the same way as the HCO fraction, i.e. it undergoes steps a); b); c),
a) HCO feed hydrotreating stage (a); in some cases co-treatment with another hydrocarbon-containing feed to produce a hydrotreated effluent;
b) separating the hydrotreated effluent obtained from step (a) to obtain at least one gas fraction and one liquid hydrocarbon-containing fraction (b);
c) optionally mixing the liquid hydrocarbon-containing fraction resulting from the separation step (b) with a paraffin-rich hydrocarbon-containing fraction (c)
including.

According to a first variant of the method for producing marine fuel according to the invention, when the starting feed is an HCO fraction, the operating conditions of the hydrotreating stage are:
-Temperature: 250-450 ° C, preferably 280-390 ° C, more preferably 320-360 ° C,
-Absolute pressure: 5-15 MPa, preferably 6-10 MPa,
-Space velocity of hydrocarbon-containing feedstock: commonly referred to as LHSV, as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst Defined: in the range of 0.1-5 h ⁻¹ , preferably 0.2-2 h ⁻¹ , more preferably 0.3-1 h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³
And
-Since the liquid effluent from step b) results in a liquid effluent complying with the marine fuel specifications according to the standard, step c) mixing with the paraffinic fraction is not necessary.

According to a second variant of the method for producing marine fuel according to the invention, when the starting feedstock is an HCO fraction, the operating conditions of the hydrotreating stage are:
-Temperature: 250-450 ° C, preferably 280-390 ° C, more preferably 320-360 ° C,
-Absolute pressure: less than 6 MPa, preferably less than 5 MPa,
-Hydrocarbon feedstock space velocity: commonly referred to as LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst. 0.1 to 5 h ⁻¹ , preferably 0.2 to 2 h ⁻¹ , more preferably 0.3 to ¹ h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ ,
And
-Because step c) of mixing with paraffinic fractions is necessary, said paraffinic fractions are selected from the following fractions: fractions resulting from direct distillation, for example atmospheric or vacuum distillates and / Or residue at normal pressure or vacuum.

  Still in the context of the second variant, the paraffinic fraction used to carry out the mixing stage c) hydrotreats or hydrocrackes the feedstock resulting from direct distillation at atmospheric pressure or vacuum. May result from the process or the conversion process.

In the context of the two preceding variants, but more specifically from the first variant, the hydroprocessing stage a) is used alone or in a mixture in the co-treatment with the HCO feedstock: One of the feedstocks is processed at a rate of up to 30% by weight with respect to the total feedstock (HCO + coprocessed feedstock):
-Gas oil from direct distillation at atmospheric pressure or vacuum,
-LCO from catalytic cracking,
-Gas oil from caulking,
-Gas oil from visbreaking,
Gas oil from hydroconversion of the residue (hydrotreating and / or hydrocracking).

If the starting feed is a “slurry” fraction, the operating conditions for the hydrotreating stage are:
-Temperature: 300-420 ° C, more preferably 340-390 ° C,
-Absolute pressure: 5-20 MPa, preferably 8-18 MPa,
-Space velocity of hydrocarbon-containing feedstock (LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst): 0.1 2.5 h ^-1, preferably in the range of 0.3~0.8h ^-1,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ ,
And
-If the starting feed is still a "slurry" feed, it becomes a CLO feed after filtration, and this CLO feed is used alone or in a mixture with one of the following feeds: It may be processed at a rate of up to 30% by weight relative to the total feed (CLO + co-processed feed):
-Gas oil from direct distillation at atmospheric pressure or vacuum,
-LCO from catalytic cracking,
-Gas oil from caulking,
-Gas oil from visbreaking,
Gas oil from hydroconversion of the residue (hydrotreating and / or hydrocracking).

(Detailed description of the invention)
In general, “fuel” means a hydrocarbon-containing feedstock that can be used as marine fuel within the meaning of the standard ISO 8217 in the context of the present invention, and “fuel base” means a hydrocarbon-containing feedstock. It means what is mixed with other bases and constitutes marine fuel. The characteristics of these bases, in particular their sulfur content and their viscosity, vary greatly depending on the origin of said bases, in particular depending on the type of crude oil and the type of refining.

(Hydrocarbon-containing feedstock)
Hydrocarbon-containing type feedstocks are obtained from catalytic cracking and have a sulfur content of at least 0.5% by weight, a minimum boiling point of 300 ° C. and a final boiling point of at least 450 ° C. %contains. The feedstock therefore consists at least in part of the HCO fraction resulting from the catalytic cracking process. It may incorporate a “slurry” fraction resulting from the catalytic cracking process at a predetermined rate.

  The feed may be a mixture of multiple HCOs and / or slurry fractions originating from multiple FCC or RFCC type devices.

  Catalytic cracking processes that produce HCO feedstocks may be of the FCC or RFCC type and may process vacuum distillate or distillation residue type feedstocks originating from petroleum. If catalytic cracking is operated starting from feeds derived from coal, biomass, bituminous sand or its derivatives, bituminous shale or its derivatives, oil from its parent rock or its derivatives, used alone or in a mixture This will still be within the scope of the present invention.

  This feed may optionally be processed with at least one co-feed. This is called coprocessing.

  Among possible co-feeds, a gas oil type fraction (containing at least 80% of a compound with a boiling point of at least 200 ° C and a final boiling point of at least 300 ° C) or vacuum gas oil (boiling point of at least 300 ° C) And contains at least 80% of a compound with a final boiling point of at least 450 ° C.), and these fractions may be derived from direct distillation of crude oil or carbonized from petroleum, coal and / or biomass. Obtained at the end of the hydrogen feed conversion process (with hydrogen addition or carbon elimination).

They are therefore
-Direct distillation-catalytic cracking-coking-visbreaking-hydroconversion of residues (hydrotreating and / or hydrocracking)
The gas oil fraction obtained by

They are,
-Distillation-Coking-Visbreaking-Hydroconversion of residues (hydrotreatment and / or hydrocracking)
It may be a vacuum gas oil fraction obtained by

  The HCO hydrocarbon-containing feed may represent a minimum of 50 wt.%, Preferably a minimum of 70 wt.% Of the total hydrocarbon-containing feed processed by the process according to the present invention.

  Advantageously, the one or more co-feeds and the relative proportions of the feed and co-feeds (one or more) are hydrotreated to obtain one and the same quality marine fuel. The singular (s) is selected to operate under milder operating conditions than if the feed oil feed was processed alone (without co-feed).

(Hydroprocessing stage (a))
Throughout this specification, the hydroprocessing stage is generally in accordance with all embodiments known to those skilled in the art by at least one catalyst bed of fixed bed type and / or bubbling bed type and / or entrained flow type. It is understood that this may be done.

  Preferred embodiments include at least one fixed bed.

  “Hydrotreating” (commonly referred to as HDT) means catalytically purifying with a supply of hydrogen, ie sulfur and other impurities present in a hydrocarbon-containing feedstock. The ratio of hydrogen to carbon in the feedstock is increased, in particular by the hydrogenation of aromatic compounds, resulting in an improvement in the combustibility of fuels, in particular marine fuels, while greatly reducing the content of.

  Along with the hydrotreatment, a lighter fraction than the starting feed is formed. Hydroprocessing includes, inter alia, hydrodesulphurization (commonly referred to as HDS), hydrodenitrogenation (commonly referred to as HDN) reactions, which include hydrogenation, hydrogen Accompanied by hydrodeoxygenation, hydrodearomatic, hydroisomerization, hydrodealkylation, and hydrocracking reactions.

  In the case of very heavy feedstocks, especially “slurries” from catalytic cracking, this may contain metals and asphaltenes, reducing hydrodemetallation, hydrodeasphaltenes and Conradson carbon There may be a reaction.

  Preferably, the hydrotreating stage a) is carried out in a fixed bed by gas and liquid downflow. Nevertheless, any technique for performing the hydrotreating step is compatible with the present invention.

According to a first preferred embodiment, the method for treating an HCO-type hydrocarbon-containing feedstock resulting from catalytic cracking comprises a hydrotreatment stage (a) operated under the following conditions:
-Temperature: 250-450 ° C, preferably 280-390 ° C, more preferably 320-360 ° C,
-Absolute pressure: 5-15 MPa, preferably 6-10 MPa,
-Space velocity of hydrocarbon-containing feedstock: commonly referred to as LHSV, divided by the volumetric flow rate of the feedstock under standard conditions (1 atm and 25 ° C) divided by the total volume of the hydrotreating catalyst Defined: in the range of 0.1-5 h ⁻¹ , preferably 0.2-2 h ⁻¹ , more preferably 0.3-1 h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ .

  In this first embodiment, step c) of mixing with the paraffinic fraction is not necessary. This is because the hydroprocessing stage directly results in a liquid effluent that meets the specifications for marine fuels.

According to a second preferred embodiment, the process for treating HCO-type hydrocarbon-containing feedstock from catalytic cracking comprises a hydrotreatment stage (a) operated under the following conditions:
-Temperature: 250-450 ° C, preferably 280-390 ° C, more preferably 320-360 ° C,
-Absolute pressure: less than 6 MPa, preferably less than 5 MPa,
-Space velocity of hydrocarbon feedstock, commonly referred to as LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst. In the range of 0.1 to 5 h ⁻¹ , preferably 0.2 to 2 h ⁻¹ , more preferably 0.3 to ¹ h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ .

  According to this second preferred embodiment, step c) of mixing with paraffinic fractions is necessary, which paraffinic fractions, alone or in a mixture, are fractions well known to those skilled in the art, for example normal Selected from pressure or vacuum distillates or atmospheric or vacuum residue.

When the starting feed is a “slurry” fraction, the operating conditions for the LCO fraction are preferably as follows:
-Temperature: 300-420 ° C, more preferably 340-390 ° C,
-Absolute pressure: 5-20 MPa, preferably 8-18 MPa,
-Hydrocarbon feedstock space velocity (LHSV is defined as the feed volumetric flow rate under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst): 0.1 ˜2.5 h ⁻¹ , preferably in the range 0.3 to 0.8 h ⁻¹
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ .

  Among the possible co-feeds with LCO feed, gas oil type fractions (containing at least 80% of compounds with a boiling point of at least 200 ° C and a final boiling point of at least 300 ° C) or vacuum gas oil type Fractions (containing at least 80% of compounds with a boiling point of at least 300 ° C. and a final boiling point of at least 450 ° C.), these fractions resulting from direct distillation of crude oil, or Obtained at the end of the conversion process (by adding hydrogen or eliminating carbon) of hydrocarbon-containing feedstocks derived from petroleum, coal and / or biomass.

They are therefore
-Direct distillation-catalytic cracking-coking-visbreaking-hydroconversion of residues (hydrotreating and / or hydrocracking)
The gas oil fraction obtained by

They are,
-Distillation-Coking-Visbreaking-Hydroconversion of residues (hydrotreatment and / or hydrocracking)
It may be a vacuum gas oil fraction obtained by

  The hydrotreating catalyst used is generally a particulate catalyst containing at least one metal or metal compound having a hydrodehydrogenation function on a support. These catalysts are advantageously at least one Group VIII metal (generally selected from the group consisting of nickel and cobalt) and / or at least one Group VIB metal (preferably molybdenum). And / or tungsten).

For example, the catalyst that may be used is 0.5 to 10 wt% nickel, preferably 1 to 5 wt% nickel (expressed as nickel oxide NiO), and 1 to 30 wt% molybdenum, preferably 5 ˜20 wt% molybdenum (expressed as molybdenum oxide MoO ₃ ) is included on the mineral support.

  The carrier may be selected from the group consisting of, for example, alumina, silica, silica-alumina, magnesia, clay and a mixture of at least two of these minerals.

(Step b) Separation of effluent from hydrotreating)
The process according to the invention further comprises a separation stage (b) for obtaining at least one gas fraction and at least one liquid hydrocarbon-containing fraction. The effluent obtained at the end of the hydrotreatment step (a), a liquid fraction containing a hydrocarbon-containing compounds, gases, _{particularly, H 2, H 2 S,} NH 3, and _C 1 -C ₄ hydrocarbons And a gas fraction containing.

  This gas fraction can be separated from the hydrocarbon-containing effluent using separation equipment well known to those skilled in the art, in particular using one or more separation flasks, which are operated at different pressures and temperatures. Often combined with means for steam or hydrogen stripping in some cases.

  The effluent obtained at the end of the hydroprocessing stage (a) is advantageously separated into at least one gas fraction and at least one liquid fraction in at least one separation flask. These separators may be, for example, high-pressure and high-temperature (HPHT) separators and / or high-pressure, low-temperature (HPLT) separators.

  After optional cooling, this gas fraction is preferably treated in a means for the purification of hydrogen to recover the hydrogen not consumed during the hydrogenation reaction.

  The means for purifying the hydrogen may be an amine wash, a membrane separator, a PSA (Pressure Swing Adsorption) type system, or a plurality of these arranged in series.

  The purified hydrogen may then advantageously be recycled to the process according to the invention after optional recompression. Hydrogen may be introduced at the inlet of the hydroprocessing stage (a).

  Separation stage (b) may comprise atmospheric distillation and / or vacuum distillation. Advantageously, the separation stage (b) comprises atmospheric distillation, in which the liquid hydrocarbon-containing fraction (s) obtained after separation is separated by at least one species by atmospheric distillation. It is fractionated into an atmospheric distillate fraction and at least one atmospheric residue fraction.

  The atmospheric distillate fraction may contain fuel bases (naphtha, kerosene and / or diesel), which can be commercially up-cycled, for example, in refineries for producing automobile and flight fuel. Alternatively, it may be incorporated into a mixture in a fuel pool, in particular a marine fuel pool.

  Furthermore, the separation step (b) of the process according to the invention may advantageously comprise a vacuum distillation which produces at least one vacuum distillate fraction and a vacuum residue fraction.

  Preferably, the separation step (b) first comprises atmospheric distillation to produce at least one atmospheric distillate fraction and an atmospheric residue fraction, followed by at least one vacuum distillate fraction and vacuum. A residue fraction and a vacuum distillation of the atmospheric residue produced.

  The vacuum distillate fraction typically contains a vacuum gas oil type fraction (denoted VGO).

  This separation stage (b) may optionally be supplemented by a liquid-solid separation stage to remove the catalyst fines, especially in the “slurry” type in which the feedstock resulted from catalytic cracking. It is a case where the fraction is included.

  At the end of the separation stage (b), a liquid hydrocarbon-containing fraction is obtained, the sulfur content of this liquid hydrocarbon-containing fraction being not more than 0.5% by weight, preferably not more than 0.3% by weight, even more preferably 0.1% by weight or less.

  This liquid hydrocarbon-containing fraction may advantageously serve as a base for marine fuel or as marine fuel within the meaning of the invention.

  Advantageously, the total sulfur content of the liquid hydrocarbon-containing effluent obtained at the end of the separation stage (b) is not more than 0.5% by weight, preferably not more than 0.3% by weight.

(Optional mixing stage with paraffin-rich fraction c))
Depending on the pressure conditions of the hydrotreating stage a), optionally or necessarily, after the separation stage (b), the liquid hydrocarbon-containing fraction resulting from stage (b) contains at least one paraffin-rich hydrocarbon. Mixing with the fraction (c) may be performed. In diesel engines, paraffins have better flammability than naphthenes, and naphthenes have better flammability than aromatics in their turn.

  “Paraffin rich” means a fraction having a paraffin content higher than the paraffin content in the HCO feedstock entering the hydrotreating stage (a).

  When expanded, it is accepted that a feedstock having a higher hydrogen content than another feedstock is more paraffin rich. In fact, the H / C ratio of paraffin is higher than the H / C ratio of naphthene, and the H / C ratio of naphthene is higher than the H / C ratio of aromatic compounds.

  Paraffin-rich hydrocarbon-containing fractions are generally fractions obtained by direct distillation (called “straight run” cuts in English terminology), eg atmospheric pressure Or vacuum distillate and / or atmospheric or vacuum residue.

  The paraffin-rich hydrocarbon-containing fraction may result from a process for hydrotreating or hydrocracking a feedstock resulting from direct distillation or a conversion process. The hydroprocessing and hydrocracking methods operate under hydrogen pressure and make it possible to obtain an effluent having a higher hydrogen content than that of the feedstock.

  The fuel or fuel base, and in some cases the marine fuel or base for the marine fuel, is thus finally obtained from the liquid hydrocarbon-containing fraction resulting from the separation stage (b) and in some cases the hydroprocessing stage. Depending on the operating conditions, it is mixed with the paraffin-rich hydrocarbon-containing fraction during the mixing stage (c).

(Detailed description of the drawings)
An advantageous embodiment of the method according to the invention is shown in FIG.

  In FIG. 1, feedstock (10) is optionally mixed with co-feedstock (11), mixed with recycle hydrogen (31) and make-up hydrogen (50), and preheated in exchanger (13). , Heated to the reactor inlet temperature in a closed vessel (15), which is made via a common pipe (12) and (14) and introduced into the reactor (17) via the pipe (16). Recirculated hydrogen (32) may be used as the cooling gas and may be injected into the reactor (17) for thermal control of the reaction.

The effluent resulting from the hydroprocessing stage is routed along line (18), through the exchanger (13), and then along line (19) to the separation section. This separation section consists primarily of a high pressure high temperature (HPHT) separator (20), from which the gas fraction (21) and the liquid fraction (35) are recovered. The gas fraction (21) is generally sent to a high pressure low temperature (HPLT) separator (24) via an exchanger for cooling (not shown) or an air cooler (22) from which gas ( _{H 2, H 2 S, NH} 3, C 1 -C 4 gas fraction containing a hydrocarbon and the like) (25) and a liquid fraction (33) is recovered.

  The gas fraction (25) from the high pressure low temperature (HPLT) separator (24) is processed in an apparatus (26) for the purification of hydrogen from which hydrogen (28) is converted into the compressor (29) and line ( 30) and line (31) and / or recovered for recirculation via line (32) to the hydrotreating section.

  The apparatus for hydrogen purification may consist of an amine wash, a membrane, or a PSA type system. At least a portion of the gas containing at least light hydrocarbons and unwanted nitrogen- and sulfur-containing compounds is removed from the plant via stream (27) and / or via other streams not shown.

  The liquid fraction (33) from the high pressure low temperature (HPLT) separator (24) is expanded in the apparatus (34) and then sent to the fractionation system (37).

  The liquid fraction (35) resulting from the high pressure high temperature (HPHT) separation (20) is expanded in apparatus (36) and then sent to a fractionation system (37).

  Of course, fractions (35) and (33) may be sent together to system (37) after expansion. The fractionation system (37) comprises an atmospheric distillation system and contains at least gaseous effluent (38), at least one so-called light fraction (39) (in particular including naphtha), kerosene and / or diesel. One middle distillate fraction (40) and atmospheric residue fraction (41) are produced. A portion of the middle distillate fraction (40) may be sent to the fuel pool (47) via a pipe (51). Part of the atmospheric residue fraction (41) may be withdrawn via line (42) to constitute the required fuel base. Part or all of the atmospheric residue fraction (41) may be sent to a vacuum distillation column (43), where a fraction (45) containing vacuum residue and a vacuum distillate fraction (44) containing vacuum gas oil are present. Collected.

  The fuel (47) may be at least one middle distillate fuel base (51) and / or a vacuum distillate fuel base (44) and / or an atmospheric residue fuel base (42) and / or a vacuum residue fuel base (45). Composed of a mixture of

  In some cases, a paraffin-rich fraction (46) may be sent to the fuel pool (47).

  In some cases, the atmospheric residue fraction (42) and / or the vacuum residue fraction (45) may be subjected to a stage of catalyst residue separation (not shown). An alternative overview for separation and fractionation (not shown) may be performed by means of a steam stripping tower, which is a single species from a high pressure or intermediate pressure or low pressure separator or Process multiple types of heavy fractions. By this means, the bottom of the stripping tower is fed directly to the vacuum tower.

  The atmospheric distillation column will still process the distillate mixture, but not the (heaviest) unconverted fraction.

Other variations not shown are implemented, for example,
− Different thermal integration.
-Arrangement of different separation methods-different flow of hydrogen rich gas-alternative methods for thermal control of the reaction, in particular using liquid coolants based on feedstock and / or fractions obtained from the separation stage May be obtained.

(Example for comparison)
The following examples illustrate the invention but do not limit the scope of the invention.

(Example 1 (HCO feedstock))
An HCO-type fraction obtained from catalytic cracking is treated, this fraction contains 95% by weight of a compound boiling at a temperature above 300 ° C., and the density at 15 ° C. is 1.005 g / cm ³ . The viscosity at 50 ° C. is 34.5 cSt, and the sulfur content is 0.98% by weight.

  Without hydrotreating, this feedstock does not constitute marine fuel in the sense of standard ISO 8217.

  According to the revision 2012 of standard ISO 8217, this viscosity will require that this fuel be classified into a residual type marine fuel, for example RMD grade. However, the CCAI of 897 exceeds the CCAI standard at 860 (maximum of RMD grade).

Similarly, the density exceeds 975 kg / m ³ , which is the maximum value of the RMD grade.

  With respect to sulfur content, it is not a problem in 2012, but will be above the equivalent sulfur content recommended in Annex VI of the Mar Paul Convention.

  This poor flammability of the feedstock is due to the high content of aromatic compounds (greater than 60%). This high content of aromatic compounds leads to a low hydrogen content (9.5% w / w).

  The feedstock is subjected to a hydroprocessing stage (a).

  The operating conditions are given in Table 1 below.

Several experiments were performed:
Hydrotreating stage (a) treating the HCO feedstock at a pressure of 1-7 MPa,
Hydrotreating stage (a) treating the HCO feedstock at a pressure of 2-5 MPa,
Hydrotreating stage (a) treating the HCO feedstock and “straight-run” gas oil type co-feed at a pressure of 3-5 MPa.

  For each experiment, the effluent from the hydrotreating section (a) is then subjected to a separation stage (b) where gases and liquids are separated by a separator and an atmospheric distillation column. Compounds boiling in liquids at temperatures above 200 ° C. constitute a fuel base, for which analysis is performed (sulfur, viscosity and CCAI).

(Case 1)
Case 1 performs the hydrotreatment stage a) at a pressure of 7 MPa, producing a fuel base obtained with a CCAI of less than 860. Due to the low sulfur content, density and viscosity below the specifications of this CCAI, standard ISO 8217 RMD grade, the fuel base obtained by Experiment 1 may be directly up-cycled to RMD type marine fuels ( May eventually be used in SECAs due to the very low sulfur content of less than 0.1% w / w).

(Case 2)
Case 2 performs a hydrotreatment stage a) at a pressure of 5 MPa, which is not sufficient to accurately hydrogenate HCO and exceeds the 860 specification for the RME grade of ISO 8217, but RMG or RMK Characterized by CCAI that also exceeds the 870 specification for grades.

  The fuel base obtained in Experiment 2 therefore does not correspond to the specifications required for residual type marine fuel according to the revision 2012 of standard ISO 8217 (denoted NC).

(Case 3)
Case 3 is a case illustrating the co-processing of an HCO feedstock with “straight-run” gas oil and has good characteristics, in particular CCAI of less than 860 and is therefore up-cycled to RMD type marine fuel. (This may ultimately be used in SECAs due to the very low sulfur content of less than 0.1% w / w).

  An alternative to increasing the pressure of the hydrotreating stage is to perform the above stage of hydrotreating HCO under the same conditions (5 MPa) as in Experiment 2, but with a compound (fuel base and boiling) at a temperature above 200 ° C. Consisting of a part of the effluent containing (referred to) with a paraffin-rich fraction (experiments 4, 5, 6).

  To illustrate this production mode, three so-called “paraffinic” fractions are used to carry out the mixing stage c).

  (Case 4): “straight run” gas oil (GO) hydrotreated at 5 MPa and 340 ° C. on the hydrotreating catalyst bed.

  (Case 5): “straight-run” vacuum gas oil (VGO) hydrotreated at 350 ° C. and 9 MPa on the hydrotreating catalyst bed.

  (Case 6): A “straight-run” atmospheric residue (AR) hydrotreated at 15 MPa and 370 ° C. on a hydrotreated catalyst bed.

  During experiments 4, 5 and 6, the CCAI of the resulting mixture is less than 860 and the viscosity at 50 ° C. is less than 80 cSt. They may therefore be up-cycled to RMD type marine fuel. Furthermore, the sulfur content of mixtures 4 and 5 is less than 0.1% w / w, so it would be possible to use these fuels in SECAs after 2015. It would be possible to use this fuel outside SECAs after 2020-2025 because the sulfur content of mixture 6 is less than 0.5% w / w.

Example 2: "Slurry" feedstock leading to CLO feedstock
The fraction obtained from the LCO-type catalytic cracking is treated, this fraction contains 95% by weight of a compound boiling at a temperature above 360 ° C. and the density at 15 ° C. is 1.117 g / cm ³ . The viscosity at 70 ° C. is 32.0 cSt, and the sulfur content is 3.70% by weight.

  Without hydrotreating, this feedstock does not constitute marine fuel in the sense of standard ISO 8217.

  In examining the revision 2012 of standard ISO 8217, it can be seen that both the density of the feedstock and the sulfur content are too high.

  The feedstock is therefore subjected to a hydroprocessing stage (RDS), which will allow both the sulfur content and density of the feedstock to be reduced.

  The operating conditions are given in Table 4 below.

Several experiments were performed:
(Case 1a)-Hydroprocessing stage (RDS) in which the CLO feedstock is processed at a pressure of 18 MPa.

  (Case 2a)-Hydrotreatment stage (RDS) in which the CLO feedstock is treated at a pressure of 8 MPa.

  (Case 3a)-Hydroprocessing stage (RDS) treating CLO feed and co-feed of "straight-run" vacuum residue type at a level of 10 wt% at a pressure of 8 MPa.

  For each experiment, the effluent from the hydroprocessing section is then subjected to a separation stage where gases and liquids are separated by a separator and an atmospheric distillation column. Compounds that boil in liquids at temperatures above 200 ° C. constitute a fuel base and are analyzed for this fuel base (sulfur, viscosity and CCAI).

  The operating conditions for the various cases 1a, 2a, 3a are given in Table 5 below.

  Three cases are consistent with the present invention.

(Case 1a)
Case 1a hydrotreats at a pressure of 18 MPa, a temperature of 370 ° C., and a LHSV of 0.3 h ⁻¹ to produce a fuel base with a CCAI of less than 860.

  Due to the low sulfur content, density and viscosity below this CCAI, specification ISO 8217 RME grade specification, the fuel base obtained by Experiment 1 may be directly up-cycled to RME type marine fuel ( This may ultimately be used in SECAs due to the very low sulfur content of less than 0.1% w / w).

(Case 2a)
Case 2a performs the hydrotreatment stage at a pressure of 8 MPa, a temperature of 390 ° C., and a LHSV of 0.5 h ⁻¹ to produce a fuel base with a CCAI of less than 860.

  Due to the low sulfur content, density and viscosity below this CCAI, specification ISO 8217 RMK grade specification, the fuel base obtained by Experiment 2 may be directly up-cycled to RMK type marine fuel ( This may ultimately be used in SECAs due to the very low sulfur content of less than 0.1% w / w).

(Case 3a)
Case 3a is a case illustrating the co-processing of CLO feedstock and vacuum residue from direct distillation (referred to as “straight distillation”) and has good characteristics, in particular CCAI of less than 860, and therefore RMG A type of marine fuel may be up-cycled (which may ultimately be used in SECAs due to very low sulfur content of less than 0.1% w / w).

13 Exchanger 15 Sealed vessel 17 Reactor 20 High pressure high temperature (HPHT) separator 24 High pressure low temperature (HPLT) separator 26 Equipment for hydrogen purification 29 Compressor 37 Fractionation system 43 Vacuum distillation column

Claims (6)

A process for producing marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, a so-called HCO feedstock (abbreviation for Heavy Cycle Oil) or "slurry" feedstock, wherein the HCO feedstock is A heavy fraction, containing at least 80% of a compound having a sulfur content of at least 0.5% by weight, a boiling point of at least 300 ° C. and a final boiling point of at least 450 ° C., The “slurry” feedstock has a sulfur content of more than 0.5% by weight and contains at least 80% of a compound having a boiling point of at least 360 ° C. and a final boiling point of at least 520 ° C. At least one liquid hydrocarbon having a content of 0.5% by weight or less and a CCAI of less than 870 (CCAI: “Calculated Carbon Aromaticity Index” according to standard ISO 8217) It makes it possible to obtain fractions containing this fraction constitutes a marine fuel, the method comprising the following successive stages:
^* ) Preliminary Filtration Stage (FILT): This is applied only to the “slurry” fraction to remove at least some of the fine particles it contains, resulting in a filtered term called CLO. And this CLO fraction is then treated in the same manner as the HCO fraction, i.e. it undergoes steps a); b); c).
a) hydroprocessing stage of an HCO or CLO feedstock (a), optionally co-processed with another hydrocarbon-containing feedstock to produce a hydrotreated effluent;
b) stage (b) of separation of the hydrotreated effluent resulting from stage (a), wherein at least one gas fraction and a liquid hydrocarbon-containing fraction are obtained,
c) optionally mixing the liquid hydrocarbon-containing fraction resulting from the separation step (b) with a paraffin-rich hydrocarbon-containing fraction (c)
Including a method. A process for producing marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, where the starting feedstock is a so-called HCO feedstock, the hydrotreating stage a)
-Temperature: 280-390 ° C, preferably 320-360 ° C,
-Absolute pressure: 5-15 MPa, preferably 6-10 MPa,
-Hydrocarbon feedstock space velocity: commonly referred to as LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst. 0.1 to 5 h ⁻¹ , preferably 0.2 to 2 h ⁻¹ , more preferably 0.3 to ¹ h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ ,
Performed under the operating conditions of
The step c) of mixing with the paraffinic fraction is unnecessary, since the liquid effluent from step b) results in a liquid effluent complying with the specifications for marine fuels according to the standard. Stage a) is a process for producing marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, wherein the starting feedstock is a so-called HCO feedstock.
-Temperature: 280-390 ° C, preferably 320-360 ° C,
-Absolute pressure: less than 5 MPa,
-Hydrocarbon feedstock space velocity: commonly referred to as LHSV, defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst. 0.1 to 5 h ⁻¹ , preferably 0.2 to 2 h ⁻¹ , more preferably 0.3 to ¹ h ⁻¹ ,
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³ ,
Performed under the conditions of
-Mixing step c) with paraffinic fractions is necessary, said paraffinic fractions comprising the following fractions: fractions resulting from direct distillation (so-called "straight cut" fractions), for example atmospheric pressure or Process selected from vacuum distillate and / or atmospheric or vacuum residue. A process for producing marine fuel starting from a hydrocarbon-containing feedstock resulting from catalytic cracking, where the starting feedstock is a “slurry” fraction and a CLO fraction after filtration. The operating conditions of step a) are:
-Temperature: 300-420 ° C, more preferably 340-390 ° C,
-Absolute pressure: 5-20 MPa, preferably 8-18 MPa,
-Space velocity of hydrocarbon feedstock (LHSV defined as the volumetric flow rate of the feedstock under standard conditions (1 atm and 15 ° C) divided by the total volume of the hydrotreating catalyst): 0.1-2 0.5 h ⁻¹ , preferably in the range of 0.3 to 0.8 h ⁻¹
The amount of hydrogen mixed with the feedstock: 100-3000 standard cubic meters (Nm ³ ) / cubic meter (m ³ ) (liquid feedstock), preferably 200-2000 Nm ³ / m ³ , more preferably 300-1500 Nm ³ / m ³
The way that is.   The paraffinic fraction used to carry out the mixing stage c) results from a feed hydrotreating or hydrocracking process or conversion process resulting from direct distillation at atmospheric pressure or vacuum. A method of producing marine fuels starting from HCO or CLO type feedstock. In addition to the HCO or CLO feed, the hydroprocessing stage is used alone or in a mixture in co-processing, the following:
-Gas oil from direct distillation at atmospheric pressure or vacuum,
-LCO from catalytic cracking,
-Gas oil from caulking,
-Gas oil from visbreaking,
-Up to 30% by weight of one of the gas oil feeds from the hydroconversion of the residue (hydrotreating and / or hydrocracking), based on the total feed (HCO + co-processed feed) A process for producing marine fuel starting from an HCO or CLO type feedstock according to claim 1.

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