TW201516138A - Process for producing marine fuels with low sulphur content from a hydrocarbon-containing cut originating from catalytic cracking of the HCO or slurry type, and employing a hydrotreating stage - Google Patents

Abstract

The present invention describes a process for producing marine fuels starting from hydrocarbon-containing cuts originating from catalytic cracking, of the HCO or "slurry" type, said process comprising: (a) a hydrotreating stage (a) producing a hydrotreated effluent, (b) a stage (b) of separation of the hydrotreated effluent originating from stage (a) in order to obtain a gas fraction and a liquid hydrocarbon-containing fraction, (c) an optional stage (c) of mixing said liquid hydrocarbon-containing fraction with a paraffin-rich hydrocarbon-containing cut with a view to obtaining the required marine fuel.

Description

Method for producing marine fuel having low sulfur content from hydrocarbon-containing fraction produced by HCO or slurry-based catalytic cracking and method using hydrogenation treatment stage

The present invention relates to the manufacture of marine fuels from hydrocarbon-containing fractions produced from HCO or "slurry" type catalytic cracking units.

The HCO fraction (abbreviation of "heavy cycle oil") in particular contains sulfur-containing impurities and contains at least 80% of compounds having an initial boiling point of at least 300 ° C and a final boiling point of at least 450 ° C. The so-called "slurry" fraction having a sulfur content of more than 0.5% by weight 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. Since the term "slurry" does not have a simple translation in French, we should use English terminology.

In the following, whenever an HCO-like fraction or "slurry" fraction is mentioned, this will be of interest and has the features defined above.

Catalytic cracking is known from the initial FCC (short for "fluid catalytic cracking") and RFCC (short for "residual fluid catalytic cracking").

FCC and RFCC are processes for the conversion of vacuum distillates and/or distillation residues, which in particular allow to obtain the following products:

-liquefied petroleum gas

- gasoline fraction

a light distillate called LCO ("light cycle oil") containing at least 80% of a compound having an initial boiling point of at least 200 ° C and a final boiling point of at least 300 ° C, which is a typical distillation in the range of 220 ° C to 350 ° C

a heavy distillate called HCO ("heavy cycle oil") containing at least 80% of compounds having an initial boiling point of at least 300 ° C and a final boiling point of at least 450 ° C, which is a typical distillation in the range of 350 ° C to 540 ° C

- Residues or "slurry", as the case may be (especially RFCC), which are generally purified from the catalyst particles contained in order to obtain a decant oil (CLO) or decant oil (DO). This residue generally has an initial boiling point in excess of 500 °C.

Sometimes the HCO and "slurry" fractions are not separated.

More specifically, the present invention relates to a method for producing marine fuels and marine fuel matrices having good combustion characteristics and low sulfur content using HCO-based fractions or "slurry" fractions obtained from FCC or RFCC as starting materials. .

The present invention has the objective of complying with the MARPOL Convention on the equivalent sulfur content and preferably also complying with the standard ISO 8217 for the manufacture of marine fuels and marine fuel matrices.

Appendix VI of the MARPOL Convention aims to gradually reduce the sulfur content of marine fuels. Ultimately, the maximum equivalent sulfur content will be 0.1% by weight in the sulfur emission control zone (SECA) and 0.5% by weight in the rest of the world.

In marine fuels, the standard ISO8217 distinguishes between distillate fuels and residual fuels. There are several levels in these two categories, with viscosity being one of the main distinguishing elements.

For residual fuels, the characteristics that reflect the quality of combustion are measured by calculating the carbon aromaticity index (CCAI).

The correlation between fuel aromatic characteristics and ignition delay is known to those skilled in the art. The formula for calculating CCAI is described in the latest revision of the standard ISO8217. This formula is especially It involves the density and viscosity of the fuel. For all marine grade residual fuels, ISO 8217 recommends a maximum CCAI of 870.

It has long been known to use hydrocarbon fractions from catalytic cracking as a fuel matrix, especially as a marine fuel matrix, which is especially useful for reducing the viscosity of fuel oil due to the low viscosity of the fraction from catalytic cracking. However, since the fractions produced by catalytic cracking are extremely aromatic, this use has a limited proportion in fuel pools, and especially in marine fuel pools. When the mixture exceeds a certain amount, the combustion characteristics deteriorate.

In addition, the fractions produced by catalytic cracking generally contain sulfur and are incorporated into the fuel pool, especially in marine fuel pools for sulfur specifications that are recommended for the fuels in accordance with Annex VI of the MARPOL Convention of the International Maritime Organization (IMO). There are more and more problems. Possible references to the following documents in the related prior art:

- FR 2 983 208 describes a process for the selective hydrogenation of HCO-based heavy fractions and recycling them to a catalytic cracking unit in order to improve the manufacture of catalytic cracking middle distillates.

- EP0432235 describes a process for hydrogenating LCO, HCO, with recycle of the effluent from catalytic cracking in order to obtain a better grade of gasoline fraction.

Neither of these documents describes the manufacture of a fuel or fuel matrix having a low sulfur content that meets the new recommendations of the International Maritime Organization and has good combustion characteristics as required by the new standard ISO 8217/2012.

The present invention describes conditions for upgrading a hydrocarbon fraction (so-called HCO fraction) of a compound having a sulfur content of more than 0.5% by weight and containing at least 80% of a boiling point of at least 300 ° C and a final boiling point of at least 450 ° C.

The invention may be defined as a hydrocarbon-containing feedstock having a compound having at least 0.5% sulfur content from catalytic cracking and containing at least 80% of an initial boiling point of at least 300 ° C and a final boiling point of at least 450 ° C (so-called HCO (recycled oil feed) Materials)) A method of producing marine fuels for starting materials. The initial feed may also be a "slurry" fraction of a compound having a sulfur content of more than 0.5% by weight and containing 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. The process according to the invention makes it possible to obtain a liquid hydrocarbon fraction having a sulfur content of less than or equal to 0.5% by weight and a CCAI (abbreviation of the calculated carbon aromaticity index according to standard 8217) of less than 870, the process comprising the following successive stages:

*) Pre-filtration (FILT) stage, which is only applicable to the "slurry" fraction in order to remove at least a certain proportion of the fine particles contained, resulting in a filtered fraction called CLO, which is subsequently filtered. Treated as HCO fraction, ie it is subjected to stage a); b); c).

a) the HCO feed is treated in combination with another hydrocarbon-containing feed to produce a hydrotreating stage (a) of the hydrotreated effluent, b) separating the hydrotreated effluent from stage (a) to obtain at least one gas stream And phase (b) of a liquid hydrocarbon-containing fraction, c) optionally stage (c) of mixing the liquid hydrocarbon-containing fraction produced in the separation stage (b) with the paraffin-rich hydrocarbon-containing fraction.

According to a first variant of the process for producing a marine fuel of the invention, when the starting feed is an HCO fraction, the operating conditions of the hydrotreating stage are as follows: - comprising between 250 ° C and 450 ° C, preferably 280 ° C and 390 between ℃, and more preferably a temperature between 320 ℃ and 360 ℃, - comprising an absolute pressure, preferably between 6MPa 5MPa and between 10MPa and 15MPa, - comprising 0.1h ^-1 to 5h ^-1, preferably 0.2 The space velocity of the hydrocarbon-containing feedstock in the range of h ^-1 to 2h ^-1 , and more preferably in the range of 0.3h ^-1 to 1h ^-1 , is commonly referred to as LHSV, which is defined under standard conditions (1 atmosphere and 15 ° C) The volumetric flow rate of the feed divided by the total volume of the hydrotreating catalyst, and comprises between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably 200 Nm ³ /m ³ and 2000 Nm ³ between / m ^3, and more preferably 300Nm ³ / m ³ was mixed with a quantity of ³ / liquid feed material between the feed was ³ 1500Nm m hydrogen, - mixed paraffinic fraction of stage c), is not necessarily followed by Because the liquid effluent from stage b) produces a liquid effluent that complies with the standard marine fuel specification.

According to a second variant of the process for producing a marine fuel according to the invention, when the starting feed is an HCO fraction, the operating conditions of the hydrotreating stage are as follows: - comprising between 250 ° C and 450 ° C, preferably 280 ° C and 390 between ℃, and more preferably a temperature between 360 and 320 ℃ ℃, - less than 6MPa 5MPa and preferably less than the absolute pressure, - comprising at 0.1h ^-1 to 5h ^-1, 2H preferred 0.2h ^-1 to ^{- 1} and more preferably the space velocity of the hydrocarbon feed in the range 0.3h ^-1 to 1h ^-1 , commonly referred to as LHSV, which is defined as the volumetric flow rate of the bulk material under standard conditions (1 atmosphere and 15 ° C) divided by The total volume of the hydrotreating catalyst, and comprises between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably between 200 Nm ³ /m ³ and 2000 Nm ³ /m ³ , and more a quantity of hydrogen mixed with a feed of liquid feed between 300 Nm ³ /m ³ and 1500 Nm ³ /m ³ - when stage c) which is subsequently necessary to be mixed with the paraffin fraction, the paraffin fraction is selected from the following Fraction: A fraction produced by direct distillation, such as atmospheric or vacuum distillate and/or atmospheric or vacuum residue.

Still in the case of the second variant, the paraffin fraction used to carry out the mixing stage c) may also be derived from a hydrotreating or hydrocracking process of a feed produced by atmospheric or vacuum direct distillation, or from a conversion process.

In the case of the two variants described above, but more specifically the first variant, the hydrotreating stage a) treatment is used alone or in combination with the total feed (HCO+) when co-processing with the HCO feed One of the following feeds used in a mixture of up to 30% by weight of the feed): - Gasoline from atmospheric or vacuum direct distillation, - LCO from catalytic cracking, - gasoline from coking, - gasoline from visbreaking, - gasoline from hydroconversion (hydrogenation and/or hydrocracking residue).

When the starting feed is a "slurry" fraction, the operating conditions of the hydrotreating stage are as follows: - including between 300 ° C and 420 ° C, and more preferably between 340 ° C and 390 ° C, - including 5 MPa and 20 MPa between 8MPa preferred absolute pressure of between 18MPa, - comprising at 0.1h ^-1 to 2.5h ^-1, preferably within the range of 0.3h ^-1 to 0.8h ^-1 of the hydrocarbon-containing feed material (LHSV is defined as The space velocity of the feed volume flow rate under standard conditions (1 atm and 15 °C divided by the total volume of the hydrotreating catalyst), and contains 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m between ^3), preferably 200Nm ³ / m ³ between 2000Nm ³ / m ³ and, more preferably and 300Nm ³ / m ³ was mixed with a quantity of ³ / liquid feed material between the feed was ³ 1500Nm m hydrogen - When the starting feed is still a "slurry" feed (which becomes a CLO feed after filtration), this CLO feed can be used separately or in combination with the total feed (CLO+ co-processed feed) a mixture of up to 30% by weight of the mixture used in one of the following feeds: - gasoline from atmospheric or vacuum direct distillation, - LCO from catalytic cracking, - gasoline from coking , - from visbroken gasoline, - gasoline from hydroconversion (hydrogenation and / or hydrocracking residues).

10‧‧‧ Feeds

11‧‧‧Common feed

12‧‧‧Common management

13‧‧‧Switch

14‧‧‧Common management

15‧‧‧Shell

16‧‧‧ tube

17‧‧‧Reactor

18‧‧‧ pipeline

19‧‧‧ pipeline

20‧‧‧High pressure, high temperature (HPHT) separator

21‧‧‧ gas fraction

22‧‧‧Air cooler

24‧‧‧High pressure, low temperature (HPLT) separator

25‧‧‧ gas fraction

26‧‧‧Unit for purifying hydrogen

27‧‧‧ Logistics

28‧‧‧ Hydrogen

29‧‧‧Compressor

30‧‧‧ pipeline

31‧‧‧Line/recycle hydrogen

32‧‧‧ pipeline

33‧‧‧ liquid fraction

34‧‧‧ devices

35‧‧‧ liquid fraction

36‧‧‧ devices

37‧‧‧System

38‧‧‧Gaseous effluent

39‧‧‧Light fractions

40‧‧‧Middle distillate fraction

41‧‧‧Atmospheric residue fraction

42‧‧‧ pipeline

43‧‧‧vacuum distillation tower

44‧‧‧vacuum distillate fraction

45‧‧‧vacuum residue

46‧‧‧rich in paraffin fractions

47‧‧‧fuel pool

50‧‧‧Supply hydrogen

51‧‧‧Tube/Middle Distillate Fuel Substrate

Figure 1 presents a schematic representation of a process according to the invention showing a) a hydrotreated zone, b) separating the zone of effluent from the hydrotreating zone, and c) optionally mixed zones with the paraffin-rich fraction.

In general, in the context of the present invention, "fuel" means a hydrocarbon-containing feedstock that can be used as a marine fuel within the meaning of ISO8217, and "fuel matrix" means mixed with other substrates to constitute a hydrocarbon fuel for marine fuels. Feeding. The properties of such matrices, especially their sulfur content and their viscosity, vary greatly depending on the source of the matrices, particularly depending on the type of crude oil and the type of refining.

Hydrocarbon-containing feed

The hydrocarbon-containing feed is obtained from catalytic cracking having a sulfur content of at least 0.5% by weight and containing at least 80% of a compound having a boiling point of at least 300 ° C and a final boiling point of at least 450 ° C. The feed therefore consists of at least a certain proportion of the HCO fraction produced by the catalytic cracking process. It can also incorporate a proportion of the "slurry" fraction produced in the catalytic cracking process.

The feedstock may also be a mixture of several HCO and/or slurry fractions produced in several units of the FCC or RFCC class.

The catalytic cracking process for making the HCO feed can be of the FCC or RFCC type and can process feeds of petroleum-derived vacuum distillates or distillation residues. If the catalytic cracking is operated as a starting material, either alone or in a mixture of coal, biomass, bituminous coal or its derivatives, bituminous rock or its derivatives, oil from a parent rock or a derivative thereof, This will remain within the field of the invention.

This feed can optionally be treated with at least one common feed. This is also called co-processing.

Among possible co-feeds, mention may be made of gasoline-based fractions (comprising at least 80% of compounds having a boiling point of at least 200 ° C and a final boiling point of at least 300 ° C) or vacuum gasoline fractions (containing at least 80% boiling point of at least 300 ° C and a final boiling point) a compound of at least 450 ° C), these fractions are produced in the original Direct distillation of the oil or at the end of the conversion process (addition of hydrogen or carbon inhibition) of hydrocarbon feeds produced from petroleum, coal and/or biomass.

Therefore, it can be a gasoline fraction obtained by:

- direct distillation

- catalytic cracking

- coking

- visbreaking

- Hydrogenation conversion (hydrogenation and / or hydrocracking) residues

It can also be a vacuum gasoline fraction obtained by:

- distillation

- coking

- visbreaking

- Hydrogenation conversion (hydrogenation and / or hydrocracking) residues

The HCO hydrocarbon-containing feed may represent at least 50% by weight, and preferably 70% by weight, of the total hydrocarbon-containing feedstock treated by the process according to the invention.

Advantageously, the common feed and the relative proportion of feed to co-feed are selected such that the hydrotreating stage (a) operates at a lighter operating condition than processing the feed separately (without co-feeding) so that Get the same quality marine fuel.

Hydrogenation stage (a)

Throughout this document, it is understood that the hydrotreating stage can be carried out according to all of the examples known to those skilled in the art, which typically employ at least one catalyst bed of fixed bed and/or bubble bed and/or carrier flow. .

The preferred embodiment comprises at least one fixed bed.

"Hydrogenation", commonly referred to as HDT, means the use of a catalytic treatment of a hydrogen supply for refining, that is, greatly reducing the amount of sulfur and other impurities present in the hydrocarbon-containing feed, especially by the aromatic compound. Hydrogenation increases the ratio of hydrogen to carbon in the feed, The combustion characteristics of good fuels (especially marine fuels).

The hydrotreating process is accompanied by the formation of a fraction that is lighter than the starting feed. Hydrotreating includes, inter alia, hydrodesulfurization (commonly referred to as HDS) reactions followed by hydrogenation, hydrodeoxygenation, hydrogenation dearomatization, hydroisomerization, hydrodealkylation and hydrocracking reactions, hydrodenitrogenation (commonly referred to as HDN) reactions. .

In the case of extremely heavy feeds, especially from catalytic cracking, which may contain "slurry" of metals and asphaltenes, there may also be reactions of hydrodemetallization, hydrodeasphalting, and reduction of Conradson carbon.

Preferably, the hydrotreating stage a) is carried out in a fixed bed having a decreasing gas and liquid flow. However, any technique used to carry out the hydrogenation stage is compatible with the present invention.

According to a first preferred embodiment, the method for treating a hydrocarbon-containing feed produced by HCO-based catalytic cracking comprises a hydrotreating stage (a) operated under the following conditions: - comprising between 250 ° C and 450 ° C, preferably deg.] C between 280 and 390 deg.] C, and more preferably a temperature between 320 ℃ and 360 ℃, - comprising an absolute pressure, preferably between 6MPa 5MPa and between 10MPa and 15MPa, - comprising 0.1h ^-1 to 5h ^-1 Preferably, the space velocity of the hydrocarbon-containing feedstock in the range of 0.2 h ^-1 to 2 h ^-1 , and more preferably 0.3 h ^-1 to 1 h ^-1 , is commonly referred to as LHSV, which is defined as under standard conditions (1 atmosphere and The volumetric flow rate of the feed at 25 ° C is divided by the total volume of the hydrotreating catalyst, and comprises between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably 200 Nm ³ / m ³ and between 2000Nm ³ / m ^3, and more preferably 300Nm ³ / m ³ was mixed with a quantity of 1500Nm ³ / feed liquid feed was fed between the hydrogen of ³ m.

In this first embodiment, stage c) of mixing with the paraffin fraction is not necessary because the hydrotreating stage directly produces a liquid effluent that meets the marine fuel specification.

According to a second preferred embodiment, the method for treating a hydrocarbon-containing feedstock from catalytically cracked HCOs comprises a hydrotreating stage (a) operated under the following conditions: - comprising between 250 ° C and 450 ° C, preferably deg.] C between 280 and 390 deg.] C, and more preferably a temperature between 360 and 320 ℃ deg.] C, - less than 6MPa 5MPa and preferably less than the absolute pressure, - comprising at 0.1h ^-1 to 5h ^-1, preferably 0.2H ^- The space velocity of the hydrocarbon feed in the range of ¹ to 2 h ^-1 , and more preferably 0.3 h ^-1 to 1 h ^-1 , is commonly referred to as LHSV, which is defined as feeding under standard conditions (1 atm and 15 ° C). The volumetric flow rate is divided by the total volume of the hydrotreating catalyst, and comprises between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably 200 Nm ³ /m ³ and 2000 Nm ³ /m ³ A certain amount of hydrogen is mixed between the feed of the liquid feed between 300 Nm ³ /m ³ and 1500 Nm ³ /m ³ .

According to this second preferred embodiment, stage c) in admixture with the paraffin fraction is necessary, and the paraffin fraction, such as atmospheric or vacuum distillate, is selected either alone or in a mixture, as is well known to those skilled in the art. Or atmospheric or vacuum residue.

When the starting feed is a "slurry" fraction, the operating conditions for the LCO fraction are preferably as follows: - comprising between 300 ° C and 420 ° C, and more preferably between 340 ° C and 390 ° C, - comprising between 5MPa and 20MPa, preferably 8MPa absolute pressure between 18MPa, - comprising at 0.1h ^-1 to 2.5h ^-1, preferably in the range of 0.3h ^-1 to hydrocarbon feed material of 0.8h ^-1 Space velocity (LHSV is defined as the feed volume flow rate under standard conditions (1 atm and 15 °C) divided by the total volume of the hydrotreating catalyst), and contains 100 and 3000 standard cubic meters (Nm ³ ) / cubic between meters (m ^3), preferably 200Nm ³ / m ³ between 2000Nm ³ / m ³ and, more preferably and 300Nm ³ / m ³ feed was mixed with the liquid feed was between ³ / m ³ 1500Nm of A certain amount of hydrogen.

Among the possible common feeds with LCO feeds, mention may be made of gasoline fractions (including a compound having at least 80% boiling point of at least 200 ° C and a final boiling point of at least 300 ° C) or a vacuum gasoline fraction (comprising at least 80% of a compound having a boiling point of at least 300 ° C and a final boiling point of at least 450 ° C), such fractions Obtained at the end of direct distillation of crude oil or at the end of the conversion process (addition of hydrogen or carbon inhibition) of hydrocarbon feeds produced from petroleum, coal and/or biomass.

Therefore, it can be a gasoline fraction obtained by:

- direct distillation

- catalytic cracking

- coking

- visbreaking

- Hydrogenation conversion (hydrogenation and / or hydrocracking) residues

It can also be a vacuum gasoline fraction obtained by:

- distillation

- coking

- visbreaking

- Hydrogenation conversion (hydrogenation and / or hydrocracking) residues

The hydrotreating catalyst used is generally a particulate catalyst comprising at least one metal or metal compound having a hydrodehydrogenation function on a support. These catalysts are preferably catalysts comprising 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, 0.5% by weight to 10% by weight of nickel, preferably 1% by weight to 5% by weight of nickel (expressed as nickel oxide NiO), and 1% by weight to 30% by weight of molybdenum, preferably from 0.5% by weight to 10% by weight, based on the mineral carrier, may be used. A catalyst of 5 to 20% by weight of molybdenum (expressed as molybdenum oxide MoO ₃ ).

The support may, for example, be selected from the group consisting of alumina, ceria, ceria-alumina, magnesia, clay, and mixtures of at least two such minerals.

Separating stage b) from the hydrotreated effluent

The process according to the invention further comprises a separation stage (b) of obtaining at least one gas fraction and at least one liquid hydrocarbon-containing fraction. The effluent obtained at the end of the hydrotreating stage (a) comprises a liquid fraction comprising a hydrocarbon-containing compound and a gas fraction comprising a gas, in particular H ₂ , H ₂ S, NH ₃ and C ₁ -C ₄ hydrocarbons.

Separating devices well known to those skilled in the art, in particular using one or more separation bottles (which can be operated at different pressures and temperatures, optionally in combination with equipment for steam or hydrogen stripping), this gas fraction can be self-contained The hydrocarbon-containing effluent is separated.

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

After cooling optionally as appropriate, the gas fraction is preferably treated in a component for hydrogen purification to recover hydrogen that was not consumed during the hydrotreating reaction.

The means for hydrogen purification may be an amine wash, a membrane separation unit, a PSA (pressure swing adsorption) type system or a number of such equipment arranged in series.

The purified hydrogen can then be advantageously recycled to the process of the invention after recompression, as appropriate. Hydrogen can be introduced to the inlet of the hydrotreating stage (a).

The separation stage (b) may also comprise atmospheric distillation and/or vacuum distillation. Advantageously, the separation stage (b) comprises atmospheric distillation, wherein the liquid hydrocarbon-containing fraction obtained after separation is fractionated by atmospheric distillation into at least one atmospheric distillate fraction and at least one atmospheric residue fraction.

The atmospheric distillate fraction may contain a fuel matrix (naphtha, kerosene, and/or diesel) that may be commercially upgraded, such as in a refinery for the manufacture of automobiles and aviation fuels, or may be incorporated into a fuel. Pool, especially in a mixture of marine fuel pools.

Additionally, the separation stage (b) of the process of the invention preferably comprises vacuum distillation to produce at least one vacuum distillate fraction and a vacuum residue fraction.

Preferably, the separation stage (b) first comprises atmospheric distillation to produce at least one atmospheric distillate fraction and atmospheric residue fraction, followed by at least one vacuum distillate fraction and vacuum residue fraction. Vacuum distillation of atmospheric residue.

The vacuum distillate fraction typically contains a vacuum gasoline fraction designated VGO.

This separation stage (b) may optionally be supplemented with a stage of liquid solids separation to remove catalyst fines, especially if the feed comprises a "slurry" fraction produced by catalytic cracking.

At the end of the separation stage (b), a liquid hydrocarbon-containing fraction having a sulfur content of less than or equal to 0.5% by weight, preferably less than or equal to 0.3% by weight, and even more preferably less than or equal to 0.1% by weight, is obtained.

Within the meaning of the invention, the liquid hydrocarbon-containing fraction preferably serves as a substrate for marine fuels or as a marine fuel.

Advantageously, all of the liquid hydrocarbon-containing effluent obtained at the end of the separation stage (b) has a sulfur content of less than or equal to 0.5% by weight, and preferably less than or equal to 0.3% by weight.

Stages selected as appropriate for mixing with paraffin-rich fractions c)

Depending on the circumstances or depending on the pressure conditions of the hydrotreating stage a), the separation stage (b) may be followed by the liquid hydrocarbon-containing fraction produced in stage (b) and at least one paraffin-rich hydrocarbon-containing fraction. Mixed stage (c). For diesel engines, paraffin wax has better combustion characteristics than naphthenics, and cyclohexane has better combustion characteristics than aromatics.

"Paraffin-rich" means that the paraffin content of the fraction is higher than the paraffin content of the HCO feed entering the hydrotreating stage (a).

Relatedly, feeds that have received a higher hydrogen content than another feed are more enriched with paraffin. In fact, the H/C ratio of paraffin is greater than the H/C ratio of naphthenic, and the H/C ratio of naphthenic is greater than the H/C ratio of aromatics.

The paraffin-rich hydrocarbon-containing fraction is a fraction generally obtained by direct distillation (referred to as "straight-run" fraction in English terminology), such as atmospheric or vacuum distillate and/or atmospheric or vacuum residue. .

The paraffin-rich hydrocarbon-containing fraction may also be derived from a hydrotreating or hydrocracking process produced from a direct distillation feed or from a conversion process. Hydrogenation and hydrocracking processes in hydrogen Operating under gas pressure and making it possible to obtain an effluent having a higher hydrogen content than the feed.

Thus, the fuel or fuel matrix, if appropriate, the marine fuel or marine fuel matrix is ultimately produced in the separation stage (b), during the mixing phase (c) depending on the operating conditions of the hydrotreating stage, optionally with paraffin-rich The liquid containing hydrocarbon fraction is a hydrocarbon-containing fraction.

Detailed description of the schema

An advantageous embodiment of the method of the invention is shown in Figure 1.

In Figure 1, mixing with the common feed (11) as appropriate, mixing with the recycle hydrogen (31) and make-up hydrogen (50), preheating in the exchanger (13) and heating in the housing (15) to The feed (10) of the inlet temperature of the reactor is introduced into the reactor (17) via a common tube (12) and (14) via a tube (16). The recycled hydrogen (32) can be used as a cooling gas and can be injected into the reactor (17) for reaction heat control.

The effluent produced in the hydrotreating stage is passed along line (18), through exchanger (13), and then along line (19) to a separation section, first by a high pressure, high temperature (HPHT) separator. (20) A composition in which a gas fraction (21) and a liquid fraction (35) are recovered from the separation section. The gas fraction (21) is typically passed through an exchanger (not shown) or an air cooler (22) for cooling to a high pressure, low temperature (HPLT) separator (24) from which the contained gas is recovered (H) ₂ , gas fraction (25) of H ₂ S, NH ₃ , C ₁ -C ₄ hydrocarbon, etc., and liquid fraction (33).

A gas fraction (25) from a high pressure, low temperature (HPLT) separator (24) is treated in a unit (26) for purifying hydrogen from which hydrogen (28) is recovered for use in a compressor (29) and pipeline (30) and line (31) and/or line (32) are recycled to the hydrotreating section.

The unit for purifying hydrogen may consist of an amine washing, membrane or PSA type system. At least a proportion of the gas containing at least the light hydrocarbons and the undesired nitrogen and sulfur containing compounds are removed from the apparatus via stream (27) and/or via other unillustrated streams.

The liquid fraction (33) from the high pressure, low temperature (HPLT) separator (24) is expanded in unit (34) and subsequently passed to a fractionation system (37).

A liquid fraction (35) produced in a high pressure, high temperature (HPHT) separator (20) is in the apparatus (36) Expanded and subsequently transferred to the fractionation system (37).

Of course, after expansion, fractions (35) and (33) can be co-delivered to system (37). The fractionation system (37) comprises a middle distillate fraction for producing a gaseous effluent (38), at least one so-called light fraction (39) (especially containing naphtha), at least one containing kerosene and/or diesel ( 40), and an atmospheric distillation system of atmospheric residue (41). A proportion of the middle distillate fraction (40) can be passed to the fuel pool (47) via line (51). A certain proportion of atmospheric residue fraction (41) can be withdrawn via line (42) to form the matrix of the desired fuel. Some or all of the atmospheric residue fraction (41) may be passed to a vacuum distillation column (43) for recovery of a fraction containing vacuum residue (45) and a vacuum distillate fraction containing vacuum gasoline (44) .

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

Optionally, the paraffin-rich fraction (46) can be delivered to the fuel pool (47).

As the case may be, the atmospheric residue fraction (42) and/or the vacuum residue fraction (45) may be subjected to the stage of catalyst residue separation (not shown). An alternative (not shown) for separation and fractionation can be carried out by means of a steam stripper which processes heavy fractions or fractions from a high pressure or medium or low pressure separator. By this method, the vacuum tower is directly supplied to the bottom of the stripper.

The atmospheric distillation column still processes the distillate mixture but does not treat the (most heavier) unconverted fraction.

Other variants not shown may be implemented to obtain, for example:

- Different heat integration

- Arrangement of different separation methods

- different hydrogen-rich gas circulation

- an alternative method for heat control of the reaction, in particular using a liquid coolant based on feeds and/or fractions obtained from the separation stage

Comparative example

The following examples illustrate the invention without limiting its scope.

Example 1 (HCO feed)

Treatment of a compound obtained from HCO-based catalytic cracking containing 95% by weight of a compound boiling at a temperature exceeding 300 ° C, having a density of 1.005 g/cm ³ at 15 ° C, a viscosity of 34.5 cSt at 50 ° C and a sulfur content of 0.98% by weight Share.

In the absence of hydrotreating, this feed does not constitute a marine fuel in the sense of standard ISO 8217.

According to the 2012 revision of the standard ISO 8217, this viscosity will require the classification of this fuel in residual class marine fuels, such as the RMD level. However, the CCAI of 897 exceeds the CCAI specification 860, the maximum of the RMD level.

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

Regarding the sulphur content, it is not a problem in 2012, but will exceed the equivalent sulphur content recommended in Annex VI of the MARPOL Convention.

The poor combustion characteristics of this feed are attributed to high levels of aromatics (over 60%). This high content of aromatics results in a low hydrogen content (9.5 wt%).

The feed is subjected to a hydrotreating stage (a).

Operating conditions are given in Table 1 below.

Conduct several experiments:

1- Hydrogenation treatment stage of processing HCO feed at 7MPa pressure (a)

2- Hydrogenation treatment stage for treating HCO feed at 5MPa pressure (a)

3- Treatment of the hydrogenation treatment stage (a) of the HCO feed and the "straight-run" gasoline-based feedstock at a pressure of 5 MPa.

For each experiment, the effluent from the hydrotreating section (a) was subsequently subjected to The separator and the atmospheric distillation column separate the separation phase of the gas and the liquid (b). In a liquid, a compound boiling at a temperature exceeding 200 ° C constitutes a fuel matrix, which is analyzed (sulfur, viscosity, and CCAI).

Case 1 Hydrogenation stage a) was carried out at a pressure of 7 MPa, and a fuel matrix obtained at a CCAI of less than 860 was produced. Due to this CCAI, the low sulfur content, density and viscosity are less than the RMD grade specification of the standard ISO8217. The fuel matrix obtained according to the experiment 1 can be directly upgraded into the RMD class marine fuel (due to the extremely low sulfur content of less than 0.1% by weight, it can be Ultimately used for SECA).

Case 2 Hydrogenation stage a) was carried out at a pressure of 5 MPa, which was insufficient to properly hydrogenate the HCO, which was characterized by exceeding the RME grade specification 860 and also exceeding the ISO 8217 RMG or RMK grade specification 870 CCAI.

Therefore, the fuel matrix obtained in Experiment 2 did not meet the specifications (labeled NC) required for the residual marine fuel according to the 2012 revision of the standard ISO8217.

Case 3 illustrates the HCO feedstock co-processing with "straight-run" gasoline with good characteristics, especially CCAI less than 860, and therefore upgradeable to RMD-type marine fuel (due to an extremely low sulfur content of less than 0.1% by weight) Can be used for SECA).

An alternative to increasing the pressure in the hydrotreating stage consists of the hydrotreating stage in which HCO is carried out under the same conditions as in Experiment 2 (5 MPa), but a certain proportion of the effluent of the compound boiling at a temperature exceeding 200 ° C is called (referred to as The fuel matrix) was mixed with the paraffin-rich fraction (Experiments 4, 5, 6).

To illustrate this mode of manufacture, three so-called "paraffin" fractions were used for the mixing stage c).

- Case 4 : Hydrogenation of "straight-run" gasoline (GO) was carried out on a hydrotreating catalyst bed at 5 MPa and 340 °C.

- Case 5 : Hydrogenation of "straight-run" vacuum gasoline (VGO) was carried out on a hydrotreating catalyst bed at 9 MPa and 350 °C.

- Case 6 : The "straight-run" atmospheric residue (AR) was subjected to hydrogenation treatment on a hydrotreating catalyst bed at 15 MPa and 370 °C.

During the experiments 4, 5 and 6, the obtained mixture had a CCAI of less than 860 at 50 ° C and a viscosity of less than 80 cSt. Therefore, it can be upgraded into RMD class marine fuel. Additionally, Mix 4 and Mix 5 have a sulfur content of less than 0.1% by weight, so it will be possible to use such fuels in SECA after 2015. Since the sulfur content of the mixture 6 is less than 0.5 %, so it will be possible to use this fuel outside the SECA after 2020-25.

Example 2 ("Slurry" feed that produces CLO feeds)

Treating a compound obtained by CLO-based catalytic cracking containing 95% by weight of boiling at a temperature exceeding 360 ° C, having a density of 1.117 g/cm ³ at 15 ° C, a viscosity of 32.0 cSt at 70 ° C and a sulfur content of 3.70% by weight Distillate. In the absence of hydrotreating, this feed does not constitute a marine fuel in the sense of standard ISO 8217.

When checking the 2012 revision of the standard ISO8217, it can be seen that the density and sulfur content of the feed are too high.

Therefore, the feed is subjected to a hydrotreating stage (RDS) which will reduce the sulfur content and density of the feed.

The operating conditions are given in Table 4 below.

Conduct several experiments:

Case 1a - Treatment of the hydrogenation stage (RDS) of the CLO feed at a pressure of 18 MPa.

Case 2a - Hydrogenation stage (RDS) of the CLO feed at a pressure of 8 MPa.

Case 3a - Hydrogenation stage (RDS) of a CLO feed and a 10% by weight "straight-run" vacuum residue co-feed at 8 MPa.

For each experiment, the effluent from the hydrotreating section was subsequently subjected to a separation stage in which the gas and liquid were separated by means of a separator and an atmospheric distillation column. In a liquid, a compound boiling at a temperature exceeding 200 ° C constitutes a fuel matrix, which is analyzed (sulfur, viscosity, and CCAI).

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

The following three cases are in accordance with the present invention.

- Case 1a was subjected to a hydrotreating stage at a pressure of 18 MPa, a temperature of 370 ° C and a temperature of 0.3 h ^-1 LHSV and a fuel matrix having a mass of less than 860 CCAI was produced.

Due to this CCAI, the low sulfur content, density and viscosity are lower than the RME grade specification of the standard ISO8217. The fuel matrix obtained according to Experiment 1 can be directly upgraded into RME type marine fuel (due to the extremely low sulfur content of less than 0.1% by weight, it can be Ultimately used for SECA).

- Case 2a The hydrogenation stage was carried out at a pressure of 8 MPa, a temperature of 390 ° C and a temperature of 0.5 h ^-1 LHSV and a fuel matrix having a mass of less than 860 CCAI was produced.

Due to this CCAI, the low sulfur content, density and viscosity are less than the RMK grade specification of the standard ISO8217. The fuel matrix obtained according to Experiment 2 can be directly upgraded into RMK marine fuel (because of the extremely low sulfur content of less than 0.1% by weight, it can be Ultimately used for SECA).

- Case 3a is a description of the co-processing of CLO feeds with vacuum residues from direct distillation (called "straight run"), with good characteristics, especially less than 860 CCAI, and therefore upgradeable to RMG-type marine fuels ( Due to the very low sulfur content of less than 0.1% by weight, it can ultimately be used in SECA).

10‧‧‧ Feeds

11‧‧‧Common feed

12‧‧‧Common management

13‧‧‧Switch

14‧‧‧Common management

15‧‧‧Shell

16‧‧‧ tube

17‧‧‧Reactor

18‧‧‧ pipeline

19‧‧‧ pipeline

20‧‧‧High pressure, high temperature (HPHT) separator

21‧‧‧ gas fraction

22‧‧‧Air cooler

24‧‧‧High pressure, low temperature (HPLT) separator

25‧‧‧ gas fraction

26‧‧‧Unit for purifying hydrogen

27‧‧‧ Logistics

28‧‧‧ Hydrogen

29‧‧‧Compressor

30‧‧‧ pipeline

31‧‧‧Line/recycle hydrogen

32‧‧‧ pipeline

33‧‧‧ liquid fraction

34‧‧‧ devices

35‧‧‧ liquid fraction

36‧‧‧ devices

37‧‧‧System

38‧‧‧Gaseous effluent

39‧‧‧Light fractions

40‧‧‧Middle distillate fraction

41‧‧‧Atmospheric residue fraction

42‧‧‧ pipeline

43‧‧‧vacuum distillation tower

44‧‧‧vacuum distillate fraction

45‧‧‧vacuum residue

46‧‧‧rich in paraffin fractions

47‧‧‧fuel pool

50‧‧‧Supply hydrogen

51‧‧‧Tube/Middle Distillate Fuel Substrate

Claims (6)

A method for producing a marine fuel starting from a hydrocarbon-containing feedstock produced by so-called HCO feed (abbreviation of heavy cycle oil) or "slurry" feedstock, the HCO feed being a heavy fraction having at least 0.5 a compound having a sulfur content of at least 80% and a boiling point of at least 300 ° C and a final boiling point of at least 450 ° C, the "slurry" feed having a sulfur content of more than 0.5% by weight and containing at least 80% boiling point of at least 360 ° C and a final boiling point a compound having a sulfur content of at least 520 ° C, such that at least one sulfur content of less than or equal to 0.5% by weight and a CCAI of less than 870 (CCAI: "calculated carbon aromaticity index" according to standard ISO 8217), a liquid hydrocarbon-containing distillation constituting the marine fuel Fractions are possible, the process comprises the following successive stages: *) Pre-filtration (FILT) stage, which is only applicable to the "slurry" fraction, in order to remove at least a certain proportion of the fine particles contained, resulting in a filtered distillation called CLO And the filtered fraction is subsequently treated as a HCO fraction, ie it is subjected to stage a); b); c), a) the HCO or CLO feed is treated jointly with another hydrocarbon-containing feed as appropriate Hydrogenation of hydrogenation effluent Stage (a), b) separating the hydrogenation treatment effluent produced in stage (a) to obtain at least one gas fraction and liquid hydrocarbon fraction (b), c) will be produced in the separation stage (b) The liquid phase (c) is optionally selected by mixing the liquid hydrocarbon-containing fraction with the paraffin-rich hydrocarbon-containing fraction. A method for producing marine fuels from a hydrocarbon-containing feedstock produced by catalytic cracking, wherein when the initial feed is a so-called HCO feed, stage a) of the hydrotreatment is carried out under the following operating conditions: comprising 280 ° C deg.] C and between 390, and preferably a temperature of between 360 ℃ 320 ℃, between 5MPa to 15MPa comprising, between absolute pressure and 10 MPa or preferably 6MPa, in 0.1h ^-1 to 5h ^-1, preferably 0.2 The space velocity of the hydrocarbon feed in the range from h ^-1 to 2h ^-1 , and more preferably from 0.3 h ^-1 to 1 h ^-1 , is commonly referred to as LHSV, which is defined under standard conditions (1 atm and 15 ° C) The volumetric flow rate of the feed divided by the total volume of the hydrotreating catalyst, and between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably 200 Nm ³ /m ³ and 2000 Nm ³ between / m ^3, and more preferably 300Nm ³ / m ³ was mixed with a quantity of ³ / the feed liquid feed material is fed between the ³ 1500Nm m hydrogen, mixed with the fraction of paraffin stage c) is not necessary, Because the liquid effluent from stage b) produces a liquid effluent that complies with the standard marine fuel specifications. A method for producing a marine fuel starting from a hydrocarbon-containing feedstock produced by catalytic cracking, wherein when the starting feed is a so-called HCO feed, stage a) is carried out under the following conditions: comprising 280 ° C and 390 ° C room, and preferably an absolute pressure and a temperature between 360 deg.] C, of less than 5MPa 320. deg.] C, contained in 0.1h ^-1 to 5h ^-1, preferably 0.2h ^-1 to 2h ^-1, and more preferably 0.3h ^-1 The space velocity of the hydrocarbon feedstock in the range of 1 h ^-1 , commonly referred to as LHSV, is defined as the volumetric flow rate of the bulk material divided by the total volume of the hydrotreating catalyst under standard conditions (1 atm and 15 ° C). And between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably between 200 Nm ³ /m ³ and 2000 Nm ³ /m ³ , and more preferably 300 Nm ³ /m ³ A certain amount of hydrogen mixed with the feed of the liquid feed between 1500 Nm ³ /m ³ is necessary for the stage c) of mixing with the paraffin fraction, the paraffin fraction being selected from the following fractions: produced by direct distillation Fractions (so-called "straight-run" fractions) such as atmospheric or vacuum distillates and/or atmospheric or vacuum residues. A method for producing a marine fuel using a hydrocarbon-containing feedstock produced by catalytic cracking, wherein when the initial feed is a "slurry" fraction and becomes a CLO fraction after filtration, the hydrotreating stage a) The operating conditions are as follows: a temperature between 300 ° C and 420 ° C, and more preferably between 340 ° C and 390 ° C, including an absolute pressure between 5 MPa and 20 MPa, preferably between 8 MPa and 18 MPa, contained in 0.1 h ^-1 to 2.5h ^-1, the preferred space velocity of the hydrocarbon feed was in the range of 0.3h ^-1 to 0.8h ^-1 (LHSV feed was defined as the volumetric flow rate at standard conditions (1 atm and 15 ℃) of Divided by the total volume of the hydrotreating catalyst, and comprising between 100 and 3000 standard cubic meters (Nm ³ ) / m ^ 3 (m ³ ), preferably between 200 Nm ³ /m ³ and 2000 Nm ³ /m ³ , More preferably, the feed of the liquid feed between 300 Nm ³ /m ³ and 1500 Nm ³ /m ³ is mixed with a certain amount of hydrogen. A method for producing a marine fuel using HCO or a CLO-based feedstock as a starting material, wherein the paraffin fraction used in the mixing stage c) is derived from hydrogenation of a feed produced by atmospheric or vacuum direct distillation. Treatment or hydrocracking process, or from a conversion process. A method of producing a marine fuel using HCO or a CLO-based feed as a starting material, as claimed in claim 1, wherein, in the co-processing, the hydrotreating stage treatment is used alone or in relation to the total, in addition to the HCO or CLO feed One of the following feeds used in a mixture of feedstock (HCO+ co-processed feedstock) in a ratio of up to 30% by weight: gasoline from normal pressure or vacuum direct distillation from catalytically cracked LCO, from cokered gasoline, from Viscosified gasoline, gasoline from hydroconversion (hydrogenation and/or hydrocracking residues).