EP2488612A1

EP2488612A1 - Method for producing distillate from a hydrocarbon feed, comprising alcohol condensation

Info

Publication number: EP2488612A1
Application number: EP10785108A
Authority: EP
Inventors: Nikolai Nesterenko; Delphine Minoux; Sander Van Donk; Jean-Pierre Dath
Original assignee: Total Raffinage Marketing SA
Current assignee: TotalEnergies Raffinage France SAS
Priority date: 2009-10-13
Filing date: 2010-10-13
Publication date: 2012-08-22
Also published as: FR2951161B1; CN102666805A; FR2951161A1; WO2011045534A1; US20120271085A1

Abstract

The invention relates to a method for converting a hydrocarbon feed containing C3-C10 olefins into a distillate, whereby the quantities of olefins having a chain length that is too short can be reduced in order to be exploited (typically C10 or even less) and the C10+ molecule yields can be increased, while controlling the exothermicity of the oligomerisation reactions. This effect is obtained by oligomerising the hydrocarbon feed in the presence of at least one part of the products resulting from the pre-conversion, by means of condensation, of light oxygen molecules (comprising at least one alcohol having at least two carbon atoms) which can originate from biomass.

Description

PROCESS FOR PRODUCTION OF DISTILLATE

FROM A HYDROCARBONATED LOAD COMPRISING ALCOHOL CONDENSATION

The invention relates to a process for the production of distillate by oligomerization from a hydrocarbon feedstock comprising a condensation of an alcohol comprising at least two carbon atoms. In particular, it is a process for the production of distillate by oligomerization of a hydrocarbon feedstock and at least one light organic oxygen compound comprising a step of pre-conversion of light oxygenates by condensation.

More particularly, the invention relates to a process for converting a feed rich in olefins C3-C10 to a product rich in distillates, especially middle distillates.

By distillate is meant hydrocarbons having 10 or more carbon atoms, middle distillates comprising 10 to 20 carbon atoms and distilling in the temperature range of 145 ° C to 350 ° C. Among the distillates, there will be distinguished olefins C10-C12 (jet fuel) and Cl 2+ (diesel).

Typically, C3-C10 olefin-rich feedstocks are treated by catalytic oligomerization processes to increase the olefin chain length. The product obtained then undergoes a fractional distillation to separate gasoline (C5-C9), jet fuel (jet in English) (C10-C12) and diesel (C12 +).

The majority of the methods described in the bibliography propose solutions for oligomerizing a charge rich in oleins and more particularly in olefins C3-C4. These olefins can be converted to oligomers under relatively mild conditions where the contribution of the cracking reaction is negligible. The effect of the presence in the feed of a wider olefin range in combination with an amount of inert or semi-inert material (paraffins, naphthenes and aromatics) makes the application of conventional oligomerization processes less efficient.

Due to the different reactivity of the C3-C10 olefins and especially because of the low reactivity of C5-C10 olefins, it may be necessary to work at a higher temperature to improve the direct yield in an oligomerization process. Operating at a higher temperature can lead to cracking and the aromatization of oligomers already formed from more reactive olefins as a part of the olefins of the charge still remains unconverted. In this case, the products of the C3-C10 olefin oligomerization processes contain significant amounts of olefins which have too short chain length (less than 10 carbon atoms). These olefins are not directly usable and must be recycled in the process to increase their chain length. This recycling, which can reach 75% of the produced effluent, increases the complexity and the costs of the installations. In addition, recycling requires an additional step in the separation of olefins with a short chain length of the corresponding paraffins. The fact that these molecules have close IPBs (initial distillation point) does not make it possible to use distillation and requires the use of more sophisticated separation methods.

There is therefore a need to reduce or eliminate these recycles by increasing the yield of distillates and more particularly of middle distillates C10-C20.

This invention provides a solution for improving the oligomerization process of the olefin feed containing a large amount of inert material (paraffins, naphthenes and aromatics) and olefins with different reactivities.

The presence of an oxygenated molecule as a precursor of water leads to the moderation of the acidity of the oligomerization catalyst limiting the cracking reaction and gives a solution for managing the exothermicity of the oligomerization reaction.

Because of the lower reactivity of heavy olefins relative to light olefins in oligomerization, the presence of an oxygenated molecule as a precursor of a lightly generated olefin can lead to a higher conversion of the heavy olefins resulting in a product whose chain length is more important.

Oxygenates comprising one or two carbon atoms (alcohols, aldehydes and the corresponding ethers, including DEE) in their structure are cheaper and more available than oxygenates C3 + (propanol, butanol, etc.). Nevertheless, the presence of ethanol or DEE in the reaction mixture for oligomerization can lead to the rapid deactivation of an acid catalyst. In addition, the incorporation ethylene generated in the liquid effluent from ethanol over an acid catalyst requires very different conditions compared to olefins C3-C10. Transforming methanol into hydrocarbons is an exothermic reaction. A combination of two exothermic reactions (oligomerization and conversion of methanol to hydrocarbons) is not always favorable. A step of precarversion of light oxygenates to heavy oxygenates and hydrocarbons, by condensation on basic catalysts before oligomerization makes it possible to use an inexpensive oxygen for oligomerization, which avoids the disadvantages described above.

Furthermore, the oligomerization reactions of olefins are highly exothermic, which requires control of the temperature of the oligomerization units. This control can be carried out using a unit implementing a system of several reactors, with cooling devices between the reactors.

In addition, the trend is currently to encourage the development of biofuels, in particular by encouraging the incorporation of fuel or agricultural products into fuels. One of the main sources of biofuel is bio-ethanol from biomass. However, it is currently difficult to prepare distillates in C10 +, in particular unbranched, from bioethanol. Known methods require high recycling rates, high investment in C2 extraction equipment and high purge: a significant amount of bio-ethanol is thus found in the form of light fraction with low added value.

The aim of the invention is to overcome these drawbacks by proposing a process for converting a hydrocarbon feedstock containing C 3 -C 10 olefins into a distillate which makes it possible to reduce the quantities of olefins with a chain length that is too short to be exploited (typically C 10, or even less) and increase the yields of C10 + molecules, while controlling the exothermicity of the oligomerization reactions. This effect is obtained by carrying out the oligomerization of the hydrocarbon feedstock in the presence of at least a portion of the products resulting from the pre-conversion of light oxygen molecules (comprising at least one alcohol comprising at least two carbon atoms, for example ethanol) by condensation, the latter being able to come from the biomass. The invention thus allows a notable reduction of the recycles, or even their removal.

The alcohol may be subjected to condensation alone or in the presence of methanol, DME, DEE, formaldehyde, acetaldehyde or ethylene glycol (oxygen molecules with one or two carbon atoms).

For this purpose, a first object of the invention relates to a process for the production of distillate, in particular of middle distillates, by conversion of a hydrocarbon feedstock containing C3-C10 olefins, comprising a first step of pre-conversion of oxygenated molecules. by light condensation, these light oxygen molecules comprising at least one alcohol comprising at least two carbon atoms, and a second oligomerization step, in which the hydrocarbon feedstock is oligomerized in at least one oligomerization reactor in the presence of at least one a part of the effluent from the first stage.

By light oxygen molecules is meant molecules comprising one to four carbon atoms.

Thus, to carry out the first pre-conversion step, at least one light oxygenated molecule consisting of an alcohol comprising at least two carbon atoms, which may be mixed with other oxygen molecules comprising one or two carbon atoms, will be chosen.

In particular, when the hydrocarbon feed is oligomerized in an installation comprising several reactors in series, the presence of a portion of the effluent from the first step is not mandatory at the inlet of the first reactor. The condensation effluent may be injected in the middle of the first reactor and / or at the inlet of the second reactor, for example.

Preferably, the total weight ratio between the effluent from the first step injected into the oligomerization plant and the hydrocarbon feedstock is from 0.0001 to 1000, preferably from 0.005 to 100.

The effluent resulting from the condensation obtained can then be conveyed to a separation zone in order to extract a portion of the water, ethylene, ethanol, and other unconverted light oxygen molecules. Advantageously, the effluent from the condensation is treated by selective hydrogenation in order to convert the di-olefins, more particularly butadienes, to the corresponding olefins.

The alcohol comprising at least two carbon atoms, for example ethanol, used in the first step can in particular be derived from biomass, for example by alcoholic fermentation or by the syn-gas (synthesis gas) pathway.

Preferably, the first step of pre-conversion of oxygen molecules by condensation comprising an alcohol containing at least two carbon atoms, such as ethanol, produces in particular propanol, isobutanol, n-butanol, heavier alcohols, and corresponding olefins.

It has been discovered that the oligomerization of a C3-C10 hydrocarbon feedstock in the presence of an effluent resulting from this condensation makes it possible to increase the yield of C10 + distillate.

In addition, in the second oligomerization step the incorporation of C 3 + alcohols into the products of the oligomerization reactions is by dehydration reactions of the alcohols to the corresponding olefins. Since these dehydration reactions are endothermic, the thermal equilibrium of the oligomerization process is thus improved, the exothermicity of the oligomerization reactions providing the energy necessary for the dehydration of the alcohols present. It is thus easier to manage the exothermicity of the oligomerization which makes it possible to optimize the conversions of each reaction zone and to reduce the total energy expenditure, as well as the corresponding investments.

It can be envisaged that the effluent from the first stage, after the selective hydrogenation, is added wholly or partially to the hydrocarbon feedstock in the second stage. For example, the weight ratio of the effluent from the first step and the hydrocarbon feed may be from 0.0001 to 1000, preferably from 0.005 to 100.

1st step: Condensation of alcohol

Advantageously, the first condensation step comprises contacting the light oxygen molecules in the aqueous phase, comprising at least one alcohol having at least two carbon atoms, for example ethanol, with at least one basic catalyst, at a temperature and a pressure sufficient to obtain a liquid effluent containing at least 40% by weight, preferably at least 50% by weight, molecules with three or more carbon atoms, and less than 10% by weight ethylene.

The effluent residue comprises unconverted oxygen molecules. Either these molecules are recycled to the condensation reactor, or they are provided for oligomerization with the effluent residue.

Alcohol, for example ethanol, may be subjected to condensation alone or in the presence of methanol, DME, DEE, formaldehyde, acetaldehyde or ethylene glycol (oxygen molecules with one or two carbon atoms), or mixtures thereof. .

The alcohol, for example ethanol, in the aqueous phase may optionally be diluted with an inert gas such as N 2 or CO 2.

The production of heavy alcohols (3 and more carbon atoms) from light alcohols (1-2 carbon atoms), and more particularly 1-butanol from ethanol on a basic catalyst is known in the literature like the reaction called "Guerbet's reaction".

Guerbet syntheses have typically been used to prepare higher molecular weight branched chain alcohols from lower molecular weight starting materials. An example of Guerbet synthesis, consisting of a dimerization of an alcohol, is described in US 4,518,810. Another example of Guerbet synthesis, consisting of the condensation of two different alcohols, is described in US 2,050. 788.

The main by-products of the ethanol condensation are 1-butene, 1,3-butadiene, heavy alcohols (5 or more carbon atoms), traces of ethylene, unconverted ethanol, aldehydes and water.

Ethylene and other light gases, such as ethane, can then be easily separated from heavier hydrocarbons and oxygenates (5 or more carbon atoms) forming the liquid phase, for example by flash separation. A possible excess of water can then be eliminated. Before being brought into contact with the hydrocarbon feedstock during the oligomerization step, the effluent from the first step may undergo selective hydrogenation of the aldehydes to alcohols, especially heavy alcohols, and dienes to olefins.

This selective hydrogenation will preferably be carried out before separation.

On oligomerization, the heavy alcohols (5 or more carbon atoms) will dehydrate to the corresponding olefins. Thus, the by-products of the condensation form olefins or precursors of olefins, which improve the quality of the hydrocarbon feedstock to be oligomerized by increasing its olefin content.

Advantageously, the first step may be carried out at a temperature of 150 to 500 ° C. and at a pressure of 0.1 to 40 MPa.

A basic catalyst suitable for the first step of the present process will be either a Bronsted base, which has the ability to accept protons, or a Lewis base, which has a pair of free electrons with which it can form a covalent bond with an atom, a molecule or an ion.

Preferably, the catalyst will contain at least two metal oxides, chosen from the group II, III metal oxides (including the series of lanthanides and actinides) and group IV.

These metal oxides can be combined in different ways to produce the active mixed metal oxide.

These active metal oxides can be prepared according to very different methods, preferably from the precursor metal salts of group II, group III and / or group IV.

But any other source of metal oxide (such as oxychlorides, alkoxides or nitrates) is also included.

A first method of preparation of this mixed metal oxide is to impregnate the precursor of the metal oxide on an already preformed metal oxide, the latter may have undergone prior hydrothermal treatment. The resulting solid is then dried and then calcined in an oxidizing atmosphere, preferably at a temperature of temperature of at least 400 ° C., for example from 600 to 900 ° C., typically from 650 to 800 ° C. to form the mixed metal oxide active. The calcination time is from 0 to 48 hours, more precisely from 0.5 to 24 hours, for example from 1 to 10 hours. In the context of the subject of this invention, the calcination was carried out at 700 ° C. for 1 to 3 hours.

A second method for the preparation of this mixed metal oxide can be achieved by combining a first aqueous solution preferably containing the group II, III or IV metal precursor, with a second solution, preferably aqueous, containing the precursor of the metal of another group (II, III or IV). The mixing of these two solutions takes place under conditions generating the co-precipitation of the hydrated precursor of the mixed metal oxide. The addition of a precipitating agent is sometimes required. Such a precipitating agent will be sodium hydroxide or ammonium hydroxide. The co-precipitation temperature is chosen to be less than 200 ° C, preferably 20 to 200 ° C. The resulting gel then undergoes hydrothermal treatment in a sealed cylinder under the following conditions: a pressure above atmospheric pressure, at a temperature above 100 ° C, for a period of 20 days, up to 3 days.

The hydrated precursor of the recovered mixed metal oxide either by filtration or centrifugation is washed and dried. The solid is then calcined in an oxidizing atmosphere, preferably at a temperature of at least 400 ° C., for example 600 to 900 ° C., typically 650 to 800 ° C., to form the mixed active metal oxide. The calcination time is from 0 to 48 hours, more precisely from 0.5 to 24 hours, for example from 1 to 10 hours. In the context of the invention, the calcination was carried out at 700 ° C. for 1 to 3 hours. Other suitable types of basic catalysts include, but are not limited to, hydroxides, carbonates, silicates, phosphates, aluminates, and combinations thereof. The compounds constituting the appropriate catalysts mentioned above will preferably be selected from Groups 1, Group 2 and rare earths of the Periodic Table. Preferably, cesium, rubidium, magnesium, lithium, barium, potassium and lanthanum will be chosen. Other catalysts which can be used are mixed metal oxide catalysts which, in addition to having basic properties, exhibit oxidation-reduction properties under the operating conditions used for the conversion of the oxygenated compounds into olefinic product. Typically, the catalyst will comprise at least one transition metal oxide, preferably two, generally periods 4, 5 or 6 of the Periodic Table, with preference being given to the transition metals Ag, Cu, Ce, Zn, Cd, Ti , V, Cr, Mo, Mn, Fe, Co, Ni. However, other metal oxides may be employed in the composition of mixed oxides, such as group IV metal oxides including zirconium, group I (alkaline) including sodium, potassium, cesium, group II (alkaline earth) including more specifically magnesium, calcium or barium. The rare earth oxides (scandium, yttrium, lanthanum and those of the lanthanide series (for example cerium)) are also included, as well as the thorium oxide of the actinide series. The oxido-reducing nature of these mixed metal oxides under the operating conditions employed is explained by the existence of multiple valence states of the metal, a characteristic well known to most transition metals. It is the operating conditions prevailing in the process that condition the valence state of the mixed valence metal constituting the mixed metal oxide. Also, it is not impossible that according to the operating conditions prevailing in the process, the valence state of the metal constituting the mixed metal oxide described above, varies according to the place and time considered in the process. process.

The operating conditions of the process (temperature, pressure, catalyst / charge ratio or WHSV) are described in the following paragraphs. On the other hand, the operating conditions necessary for the oxidation-reduction character to intervene are much more difficult to define with a single parameter or even with a simple combination of parameters.

The catalyst adapted for the first step of the process according to the invention has a CO2 adsorption capacity at 100 ° C of at least 0.03 mg / m ² , although the upper limit in CO2 adsorption capacity does not not critical, this kind of catalyst has a CO2 adsorption capacity at 100 ° C less than or equal to 10 mg / m ² . Typically, the catalyst suitable for the first step of the invention has a CO2 adsorption capacity at 100 ° C of 0.01 to 1 mg / m ² .

In terms of specific surface area (measured according to the ASTM D3663 method), the suitable catalysts have a specific surface area of at least 10 m ² / g, more specifically a surface area of 20 to 250 m ² / g. Typically, the catalyst of the invention has a specific surface area of 25 to 280 m ² / g. A basic catalyst suitable for the reaction described above may also be supported on a support, as is commonly practiced by those skilled in the art. As a support, alumina, titanium, silica, zirconia, zeolites, charcoal, clays, lamellar hydroxides, hydrotalcites, and any combination thereof may be employed without these examples being limiting.

2nd step: oligomerization

The hydrocarbon feedstock used may be a mixture of hydrocarbon effluents containing C3-C10 olefins from refinery or petrochemical processes (FCC, steam cracker, etc.). The feed may be a mixture of cuts comprising, C3 FCC, FCC C4, LCCS, LLCCS, Pygas, LCN, etc. blended so that the linear olefin content in the C5- (C3-C5 hydrocarbons) cut compared to the total charge C3-C10 is at most 40% by weight.

The total olefin content in the C5- (C3-C5) fraction relative to the total C3-C10 feedstock provided for oligomerization may be greater than 40% by weight if the iso-olefins are present in an amount of at least 0.5% by weight.

The total content of linear olefins may be greater than 40% by weight relative to the total charge C3-C10 if the linear olefins

C6 + (C6, C7, C8, C9, C10) are present in an amount of at least 0.5% by weight.

This feed may in particular contain olefins, paraffins and aromatic compounds in all proportions in accordance with the rules described above.

The hydrocarbon feedstock will preferably contain a small amount of dienes and acetylenic hydrocarbons, advantageously less than 100 ppm of diene, preferably less than 10 ppm of C3-C5 dienes. For this purpose, the hydrocarbon feedstock will for example be treated by a selective hydrogenation optionally combined with adsorption techniques.

The hydrocarbon feedstock will preferably contain a small amount of metals, preferably less than 50 ppm, preferably less than 10 ppm. For this purpose, the hydrocarbon feedstock will for example be treated by a selective hydrogenation optionally combined with adsorption techniques.

Advantageously, the feed used has undergone a partial extraction of the isoolefins it contains, for example by treatment in an etherification unit, thus allowing a concentration of linear olefins.

In general, the commercially available olefinic feeds cause a deactivation of the oligomerization catalyst faster than expected. Although the reasons for such deactivation are not well known, it is believed that the presence of certain sulfur compounds is at least partly responsible for this decrease in activity and selectivity. In particular, it appears that the aliphatic thiols, sulfides and disulfides of low molecular weight are particularly troublesome.

It is thus established that the allowable sulfur content in a feed of an oligomerization process must be low enough so that the activity of the catalyst used is not inhibited. In general, the sulfur content is less than or equal to 100 ppm, preferably less than or equal to 10 ppm, or even less than or equal to 1 ppm.

The removal of these sulfur compounds requires hydro-treatment steps which increase the total cost of the process, and which can lead to a decrease in the amount of olefins. This loss can be very disadvantageous for C5-C10 cuts typically containing from 200 to 400 ppm of sulfur.

There is therefore also a need to develop an oligomerization process that allows the treatment of olefinic feeds commercially available without prior severe hydrotreatment.

It is common practice to add water to the feed of a catalytic oligomerization process. This addition of water allows in particular to control the temperature of the oligomerization reactor, in particular during the startup of the reactor, when the catalyst is fresh and the strongest exothermicity. The presence of oxygen-containing precursor compounds in the feed used for the process according to the invention has the advantage of increasing the sulfur tolerance of the oligomerization catalysts. The life of the catalyst can thus be increased. Because of the oxygenate contents used, the water formed during oligomerization represents more than 0.25% by weight of the hydrocarbon feedstock.

By way of example, in order to prevent the catalytic activity of the catalyst from being substantially inhibited, the nitrogen content of the hydrocarbon feedstock is not greater than 1 ppm by weight (calculated on an atomic basis) preferably not more than 0.5 ppm, more preferably 0.3 ppm. Similarly, by way of example, the chloride content of the hydrocarbon feedstock is not greater than 0.5 ppm by weight (calculated on an atomic basis), preferably not more than 0.4 ppm, more preferably at 0.1 ppm.

For this purpose, the hydrocarbon feedstock used may have undergone prior treatment, for example partial hydrotreatment, selective hydrogenation and / or selective adsorption.

Furthermore, the presence of effluent from the condensation in the feed of the oligomerization step increases the partial pressure of olefins, which improves the efficiency of the oligomerization process.

A first family of catalysts that may be used may comprise acidic catalysts of either amorphous or crystalline aluminosilicate or silicoaluminophosphate type, in protonated form (H +), chosen from the following list and containing or not containing alkaline elements or rare earth elements:

MFI (ZSM-5, Silicalite-1, Boralite C, TS-1), MEL (ZSM-1 1, Silicalite-2, Borthite D, TS-2, SSZ-46), ASA (amorphous silica-alumina), M SA (silica-mesoporous alumina), FER (Ferrierite, FU-9, ZSM-35), MTT (ZSM-23), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), TON (ZSM -

22, Theta-1, NU-10), EUO (ZSM-50, EU-1), ZSM-48, MFS (ZSM-57), MTW, MAZ, SAPO-11, SAPO-5, FAU, LTL, BETA MOR, SAPO-40, SAPO- 37, SAPO-41 and the family of microporous materials composed of silica, aluminum, oxygen and possibly boron.

The zeolite may be subjected to various treatments before use, which may be: ion exchange, modification with metals, steaming, acid treatments or any other method of dealumination, passivation deposition of silica, or any combination of the above-mentioned treatments.

The content of alkali or rare earth is 0.05 to 10% by weight, preferably 0.2 to 5% by weight. Preferably, the metals employed are Mg, Ca, Ba, Sr, La, Ce used alone or in a mixture.

A second family of usable catalysts also includes phosphorus-modified zeolites optionally containing an alkali or a rare earth. In this case, the zeolite can be chosen from the following list:

MFI (ZSM-5, Silicalite-1, Boralite C, TS-1), MEL (ZSM-1 1, Silicalite-2, Borthite D, TS-2, SSZ-46), ASA (amorphous silica-alumina), M SA (silica-mesoporous alumina), FER (Ferrierite, FU-9, ZSM-35),

MTT (ZSM-23), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), TON (ZSM-

22, Theta-1, NU-10), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48,

MTW, MAZ, FAU, LTL, BETA MOR.

The zeolite may be subjected to various treatments before use, which may be: ion exchange, modification with metals, steaming, acid treatment or any other method of dealumination, surface passivation by silica deposition, or any combination of the above-mentioned treatments.

A third family of usable catalysts comprises bifunctional catalysts, comprising a support, among the following list: MFI (ZSM-5, silicalite-1, boralite C, TS-1), MEL (ZSM-1 1, silicalite-2, boralite D, TS-2, SSZ-46), ASA (amorphous silica-alumina), MSA (mesoporous silica-alumina), FER (Ferrierite, FU-9, ZSM-35), MTT (ZSM-23), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), TON (ZSM-22, Theta-1,

NU-10), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48, MTW, MAZ, BETA, FAU, LTL, MOR, and the microporous materials of the ZSM-48 family constituted silicon, aluminum, oxygen and optionally boron. MFI or MEL (Si / Al> 25), MCM-41, MCM-48, SBA-15, SBA-16, SiO2, Al2O3, hydrotalcite or a mixture thereof.

a metal phase (Me) at a height of 0.1% by weight, the metal being selected from among the following elements: Zn, Mn, Co, Ni, Ga, Fe, Ti, Zr, Ge, Sn and Cr used alone or in mixture. These metal atoms can be inserted into the tetrahedral structure of the support via the tetrahedral unit [MeO2]. The incorporation of this metal can be carried out either by adding this metal during the synthesis of the support or incorporated after synthesis by ion exchange or impregnation, the metals then being incorporated in the form of cations, and not integrated within the structure. support structure.

The catalyst may be a mixture of the previously described materials in the three families of catalyst. In addition, the active phases may also be combined with other constituents (binder, matrix) giving the final catalyst increased mechanical strength, or an improvement in activity. If the hydrocarbon feed is oligomerized in an installation comprising several reactors in series, the reactors of the series can be loaded with the same catalyst or a different one.

Advantageously, the second step will be carried out under a reducing atmosphere, for example under H 2.

In particular, the presence of a reducing atmosphere, and possibly water, makes it possible to improve the stability of the catalyst used.

The second step of the process according to the invention has the advantage of being able to be implemented in an existing oligomerization installation.

For example, a multi-reactor plant can be used in which the exothermicity of the reaction can be controlled so as to avoid excessive temperatures. Preferably, the maximum temperature difference within the same reactor will not exceed 75 ° C.

The reactor (s) may be of the isothermal or adiabatic type with a fixed or moving bed. The oligomerization reaction can be carried out continuously in a configuration comprising a series of parallel-bed fixed-bed reactors, wherein when one or more reactors are in operation, the other reactors undergo a catalyst regeneration operation.

The totality of the effluent resulting from the condensation can be added to the feedstock before it enters the oligomerization reactor (s), or in part before it enters the oligomerisation reactor (s). the remaining part being added to the oligomerization reactor (s), for example as quenching.

When several oligomerization reactors are used, the effluent can be added at the inlet or in the second reactor or subsequent reactors.

The process may be implemented in one or more reactors.

Preferably, the process will be implemented by means of two separate reactors. The reaction conditions of the first reactor will be selected to convert a portion of the low carbon (C3-C5) olefinic compounds to intermediate (C6 +) olefins.

Advantageously, the first reactor will comprise a first catalytic zone and will operate at high temperature, for example greater than or equal to 250 ° C, and moderate pressure, for example less than 50 bars.

The second reactor will preferably operate at temperatures and pressures selected so as to promote the oligomerization of heavy olefins distillate. The effluent from the first reactor, comprising the unreacted olefins, the intermediate olefins, water and optionally other compounds such as paraffins and optionally a reducing gas, then undergoes oligomerization in this second reactor comprising a second catalytic zone, which makes it possible to obtain a heavier hydrocarbon effluent, rich in distillate.

Advantageously, the first reactor will operate at a lower pressure, a temperature and a higher hourly space velocity relative to the second reactor.

It may be possible to use the pressure difference between the two reactors to perform a flash separation step.

The second step can be implemented under the conditions described below.

The debitability of the oligomerization reactant (s) will advantageously be sufficient to permit relatively high conversion without being too low in order to avoid undesirable parallel reactions. The hourly space velocity (WHSV) of the charge, for example, will be from 0.1 to 20 h -1, preferably from 0.5 to 15 h -1, more preferably from 1 to 8 h -1. .

The temperature at the inlet of the reactor (s) will advantageously be sufficient to allow a relatively high conversion, without being very high in order to avoid undesirable parallel reactions. The temperature at the inlet of the reactor will be, for example, from 150 to 400.degree. C., preferably from 200.degree.-350.degree. C., more preferably from 220 to 350.degree. The pressure through the oligomerization reactor (s) will advantageously be sufficient to allow a relatively high conversion, without being too low in order to avoid undesirable parallel reactions. The pressure through the reactor will be, for example, from 8 to 500 bara (0.8 to 50 MPa), preferably from 10 to 150 bara.

(1 to 15 MPa), more preferably 14 to 49 bara (bar, absolute pressure) (1.4 to 4.9 MPa).

The effluent from the oligomerization step is then conveyed to a separation zone, in order to separate, for example, the fractions in aqueous fraction, C5-C9 (gasoline), C10-C12 (jet) and C12 + ( diesel). Fractions C5-C9, C10-C12 and Cl2 + may undergo a drying step.

Thus, the invention makes it possible in particular to obtain a jet fuel (C10-C12, "jet") from alcohols of vegetable origin.

The light C1-C4 fractions can also be separated and purged or optionally recycled with the hydrocarbon feedstock.

The C10-C12 and Cl2 + fractions separated from the effluent from the oligomerization process can be hydrogenated to saturate the olefinic compounds and hydrogenate the aromatic compounds. The product obtained has a high cetane number, and excellent properties for use as jet, diesel or the like. The invention is now described with reference to the examples and accompanying drawings, which are not limiting, drawings in which:

FIG. 1 represents the degree of conversion to C5 olefins of Examples 2 and 3, as well as the temperature as a function of the test duration (TOS);

FIG. 2 represents the simulated distillation curves of the liquid organic phases of the effluent of Example 2 (reaction temperature: 260 ° C.), of the feedstock of Example 3 (reaction temperature: 300 ° C.), after 10 and 24 hours;

- Figures 3 and 4 show schematically different embodiments of the method according to the invention. In each of Figures 3 and 4:

OS represents an oligomerization zone, FIG. 4 comprising two oligomerization zones, OS and OS2,

S represents a separation zone,

SHP represents a zone of selective hydrogenation and / or selective adsorption,

- PreC, represents a pre-conversion zone,

- P represents a purification zone.

In these figures, discontinuous features represent process options.

Each oligomerization zone represents, for example, an oligomerization reactor

The diagram shown in FIG. 3 corresponds to a process in which the feedstock consisting of C 3 -C 10 hydrocarbon compounds is treated in an OS oligomerization zone. The effluent leaving this zone OS is conveyed in the separation zone S.

In this zone S, the water is removed and the olefins are separated into C2-C4, C5-C9 (gasoline), C10-C12 (jet) and diesel (C12 +). Some of the C2-C4 light olefins may optionally be recycled to the SO oligomerization zone.

Ethanol (optionally mixed with DDE), after being purified in zone P, is treated in the PreC pre-conversion zone. The effluent from the PreC zone undergoes a selective hydrogenation (SHP) before entering the OS oligomerization zone, either in mixture with the hydrocarbon feedstock, or in the OS zone itself. Unconverted ethylene, water and unconverted ethanol (and possibly DDE) can be extracted from the effluent from the PreC area, with unconverted ethanol (and possibly DDE) being recycled in the process. PreC area

The diagram shown in FIG. 4 corresponds to a process which differs from that represented in FIG. 3 only by the presence of a second oligomerization zone OS2. The hydrocarbon feed C3-C10 is treated in this second zone OS2 before being treated in the zone OS. In this embodiment, the C2-C4 olefins separated in the separation zone are recycled to the second zone OS2 with the hydrocarbon feedstock. EXAMPLES

EXAMPLE 1 Preparation of Catalyst A

A sample of MFI zeolite (Si / Al = 82) with a crystal size of 0.2-0.3 μπι provided by Zeolyst Int. as NH4 was calcined at 550oC for 6 hours to convert to H + form. The product thus obtained is called catalyst A.

EXAMPLE 2: oligomerization test in the presence of butanol 20 ml (12.8 g) of the catalyst A in the form of grains (35-45 mesh) were loaded into a fixed-bed tubular reactor having an internal diameter of 11 mm. Prior to testing, the catalyst was activated at 550 ° C under nitrogen flow for 6 hours. After activation the reactor was cooled to 40 ° C. The catalyst was contacted with the feed at 40 ° C and atmospheric pressure for 1 hour.

Then the pressure was raised to the reaction value and the reactor was heated to 200 ° C with a speed of 30 ° C / hour. The temperature was maintained for 12 hours at 200 ° C and was subsequently increased to 260 ° C and 300 ° C (30 ° C / hour).

The charge used for this oligomerization test is a cut

LLCCS containing 83% by weight of C5 hydrocarbons (of which 59% by weight of olefins and 41% by weight of paraffins). The linear olefin content in C5- cuts was 27.2% by weight. The mixture comprising 85% by weight of LLCCS and 15% by weight of 1-butanol was contacted with Catalyst A under the following conditions:

Reactor inlet temperature: 260, 300 ° C

Pressure P: 40 barg

Hourly space velocity (pph): 1 hr-1.

(P (barg) = P bar - Patm (~ lbar))

The analysis of the products obtained was performed online by gas chromatography, the chromatograph being equipped with a capillary column.

At the outlet of the reactor, the gaseous phase, the liquid organic phase and the aqueous phase were separated. No recycling is done. The catalyst showed a very low deactivation which can be compensated for by increasing the temperature with a large increase in the gas phase (FIG. 1).

The simulated distillation curve for the liquid organic phase is shown in FIG.

Table 1 below shows the conversion rates and yields obtained.

Table 1

This Table 1 illustrates the possibility of producing a heavy hydrocarbon fraction rich in distillate from a feed containing a gasoline cut and 15% butanol. The feed contained several olefins of different reactivities. The results show an almost total conversion of butanol to hydrocarbons, little cracking (gaseous phase) despite a relatively high temperature for oligomerization, and the transformation of a significant amount (65.6%) of olefins distilling above 150 ° C from a real load.

EXAMPLE 3 (Comparative): oligomerization test in the presence of

DEE

20 ml (12.8 g) of the 35 -45 mesh catalyst were loaded into a fixed bed tubular reactor having an internal diameter of 11 mm. Before the tests, the catalyst was activated at

550 ° C under nitrogen flow for 6 hours. After activation, the The reactor was cooled to 40 ° C. The catalyst was contacted with the feed at 40 ° C at atmospheric pressure for 1 hour. Then, the pressure was raised to the reaction value and the reactor was heated to 200 ° C with a speed of 30 ° C / hour. The temperature was maintained for 12 hours at 200 ° C and was subsequently increased to 260 ° C and 300 ° C (30 ° C / hour).

The feed used for this oligomerization test is an LLCCS section containing 83% by weight of C5 hydrocarbons (59% by weight of olefins and 41% by weight of paraffins).

The mixture comprising 85% by weight of LLCCS and 15% by weight of DEE was contacted with Catalyst A under the following conditions:

Reactor inlet temperature: 260, 300 ° C

Pressure P: 40 barg

Hourly space velocity (pph): 1 hr-1.

At the outlet of the reactor, the gaseous phase, the liquid organic phase and the aqueous phase were separated. No recycling is done.

The catalyst showed a very rapid deactivation which can not be compensated for by increasing the temperature (FIG. 1).

The simulated distillation curve measured for the liquid organic phase is shown in FIG.

Figures 1-2 demonstrate the strongest deactivation and the most important temperature necessary to obtain the complete conversion of olefins to C5 in the presence of DEE. On the other hand, the precursor of ethanol to butanol leads to a lower deactivation rate and a higher conversion to C5 olefins.

Claims

A process for the production of distillate, hydrocarbons having 10 or more carbon atoms, especially of middle distillates, by conversion of a hydrocarbon feed containing C 3 -C 10 olefins, comprising a first step of pre-conversion of light oxygen molecules by condensation, these light oxygen molecules comprising at least one alcohol comprising at least two carbon atoms, and a second oligomerization step, wherein the hydrocarbon feedstock is oligomerized in at least one oligomerization reactor in the presence of at least a part. effluent from the first stage.

2. Method according to claim 1, wherein the alcohol comprising at least two carbon atoms, for example ethanol, is derived from biomass.

3. Method according to claim 1 or 2, wherein the light oxygen molecules comprise in addition to the alcohol comprising at least two carbon atoms, oxygen molecules with one or two carbon atoms selected from methanol, DME, DEE, formaldehyde, acetaldehyde, ethylene glycol or mixtures thereof.

4. Method according to one of claims 1 to 3, wherein the first condensation step comprises contacting, in the aqueous phase, light oxygen molecules with at least one basic catalyst, at a temperature and pressure sufficient to obtain a liquid effluent containing at least 40% by weight, preferably at least 50% by weight, of C3 + molecules, and less than 10% by weight of ethylene.

5. Method according to one of claims 1 to 4, wherein the effluent from the first step is conveyed into a separation zone in order to extract, at least in part, the unreacted light oxygen molecules. , ethylene and other light gases.

The process according to one of claims 1 to 4, wherein the effluent from the first step is treated by selective hydrogenation to convert the aldehydes to heavier alcohols and the diolefins to olefins.

7. Method according to one of claims 1 to 6, wherein the first step is carried out at a temperature of 150 to 500 ° C and a pressure of 0.1 to 40 MPa.

8. Method according to one of claims 1 to 7, wherein the catalyst used for the first step of the invention has a CO2 adsorption capacity at 100 ° C of 0.03 to 10 mg / m ² , preferably from 0.01 to 1 mg / m ² .

9. Method according to one of claims 1 to 8, wherein the catalyst used for the first step of the invention has a specific surface area of at least 10m ² / g, more specifically from 20 to 250 m ² / g, preferably 25 to 280 m ² / g.

10. Method according to one of claims 1 to 9, wherein the total weight ratio between the effluent from the first step and the hydrocarbon feedstock is from 0.0001 to 1000, preferably from 0.005 to 100.

1. Method according to one of claims 1 to 10, wherein, in the second step, the total of effluent from the first step is added to the hydrocarbon feedstock.

12. Process according to any one of claims 1 to 1 1, wherein the total amount of effluent to be added to the hydrocarbon feedstock is added thereto before entering the reactor (s). oligomerization.

13. A process according to any one of claims 1 to 1 1, wherein a portion of the amount of effluent to be added to the hydrocarbon feedstock is added thereto before entering the reactor (s) d oligomerization, the remaining portion being added to the oligomerization reactor (s).

14. Process according to one of claims 1 to 13, in which, during the second step, the hourly space velocity of the hydrocarbon feedstock is from 0.1 to 20 h -1, preferably from 0.5 to 15. h-1, more preferably from 1 to 8 h-1.

15. Method according to one of claims 1 to 14, wherein, during the second step, the pressure through the oligomerization reactor (s) is from 8 to 500 bara, preferably from 10 to 150 bara, from still preferred from 14 to 49 bara.

16. Process according to one of claims 1 to 15, in which the effluent from the oligomerization stage is conveyed to a separation unit in order to separate the C5-C9, C10-C12 and C12 + fractions. .