JP5149157B2 - Olefin gasoline desulfurization method - Google Patents

Description

  Production of reformate gasoline that meets new environmental regulations requires a significant reduction in sulfur content. In accordance with current and future environmental standards, refiners in the European Community are expected to reduce the sulfur content in gasoline pools to values below 50 ppm in 2005 and to 10 ppm on January 1, 2009. Be strong. In addition, European refiners must also meet the standards for olefin compound content, which is less than 18% by volume since 2000.

  Among the gasoline bases used in refiners, cracked gasoline provides a large proportion of sulfur and olefins in commercial gasoline. The term “cracked gasoline” is a fraction from a coking device, visbreaking device or steam cracking or fluid catalytic cracking (FCC) device, the carbonization range of which typically contains 5 carbon atoms. It means from the boiling point of hydrogen to about 250 ° C.

  Catalytic cracked gasoline can constitute 30-50% by volume of the gasoline pool, which has a high olefin and sulfur content. Over 90% of the sulfur in reformed gasoline is generally attributed to gasoline from catalytic cracking. Desulfurization of gasoline, primarily FCC gasoline, is therefore clearly important in meeting these standards.

  Hydrocracking or hydrodesulfurization of catalytic cracked gasoline can reduce the sulfur content of the fraction when performed under conditions that are normal for those skilled in the art. However, the process has the major disadvantage of causing a very large drop in the octane number of the fraction due to a large proportion of olefins under hydroprocessing conditions as well as total hydrogenation or saturation.

Therefore, a method has been proposed that can significantly desulfurize FCC gasoline while maintaining the octane number at a level that meets standards. The process is mainly based on the principle of selective hydrodesulfurization aimed at converting sulfur-containing compounds to H ₂ S while limiting the hydrogenation of olefins to paraffins that induces a large loss of octane number. For example, U.S. Patent No. 6,057,049 describes a method of selective desulfurization of gasoline that can produce olefin gasoline that meets current sulfur content standards while minimizing the loss of octane number during hydrodesulfurization.

  Furthermore, an oligomerization process has been developed for producing gasoline having a high octane number from a hydrocarbon fraction containing olefins containing 3 to 6 carbon atoms. The method uses an acid catalyst that can oligomerize the olefin present in the feedstock to an isoolefin containing 6 to 12 carbon atoms having a high olefin number. The method can produce gasoline with a high octane number and a drastically reduced sulfur. However, such gasoline is nearly 100% by weight olefins.

  There are a number of industrial methods for producing gasoline by oligomerizing olefins containing 3 to 6 carbon atoms, which are described in [1].

Further, Patent Document 2 discloses a method for desulfurizing olefin gasoline without a large loss of octane number, and production of isoolefin gasoline containing 8 to 12 carbon atoms from sulfur-containing gasoline and selection of the isoolefin gasoline. Based on dynamic hydrodesulfurization, it has been proposed to produce desulfurized gasoline without loss of octane number. However, the process requires treating a sulfur-containing olefin gasoline with an end point that may be high over an acid catalyst, which has a detrimental effect on the stability of the catalyst and its deactivation. Can cause. The presence of compounds that can adversely affect the stability of the acid catalyst, such as sulfur-containing compounds, polyunsaturated compounds and nitrogen-containing compounds, is generally a heavy fraction of gasoline, particularly 7-12 carbon atoms. Is concentrated in the fraction mainly containing olefins containing.
French Patent Invention No. 2797639 International Publication No. 2005/019391 Pamphlet "Catalyse acido-basique" by C Marcilly, Technip Publishing, Volume 2, p. 475-495

(Summary of the Invention)
The present invention is a method for producing gasoline having a low sulfur content and a controlled olefin content,
A first step i) comprising contacting the olefin feedstock with an acid catalyst under conditions that may cause oligomerization of the olefins present in the feedstock to produce branched olefin gasoline;
A step ii) comprising mixing the branched olefin gasoline produced in step i) with a gasoline rich in sulfur and olefins;
The mixture thus constituted is treated on a hydrodesulfurization catalyst in the presence of hydrogen to convert the sulfur present in the feedstock to H ₂ S and at least partially hydrogenate the olefins Step iii)
A process comprising at least a step iv) of separating the formed H ₂ S.

  In the context of the present invention, the term “branched olefin gasoline” means a gasoline comprising at least 50% by weight, preferably at least 60% by weight, more preferably at least 65% by weight of branched olefins. Of these branched olefins, isoolefins are primarily present, but not the only one.

(Detailed description of the invention)
The present invention relates to a gasoline production plan with a low sulfur content and a controlled olefin content. The resulting gasoline also has a high octane number.

Olefin-rich hydrocarbon fractions, preferably hydrocarbons containing 3 to 6 carbon atoms per molecule (C ₃ -C ₆ fractions (ie C ₃ , C ₄ , C ₅ and C ₆ fractions) Which are mainly (ie, at least 40% by weight, preferably at least 70% by weight, more preferably at least 90% by weight) are treated over an acid catalyst to produce an oligomerization reaction, for example two Through quantification and / or trimerization, a gasoline containing a larger number of carbon atoms is produced. It is advantageous to only treat the hydrocarbon fraction containing the shortest olefin over an acid catalyst. The olefin fraction containing hydrocarbons containing 7 or more carbon atoms concentrates compounds that can deactivate the acid catalyst, such as basic nitrogen-containing compounds, sulfur-containing compounds, polyunsaturated compounds, and the like. Furthermore, olefins containing 7 or more carbon atoms, by oligomerization, form branched olefins containing more than 14 carbon atoms, which are too heavy to be incorporated into gasoline fractions. .

Further, the branched olefin gasoline produced by oligomerization of the olefin fraction may contain heavy oligomerization products derived from the trimerization reaction and containing more than 12 carbon atoms. Advantageously, this heavy fraction is separated to concentrate the unsaturated product and any polyunsaturated product, after which the C ₆ -C ₁₂ fraction is hydrogenated. The heavy C ₁₂ + fraction is usually separated by distillation. The heavy C ₁₂ + fraction can be processed in a hydrotreater or hydrotreater to improve performance as a base for aviation fuel (also called kerosene) or gas oil.

Thus obtained oligomerization gasoline, preferably, predominantly comprising hydrocarbons containing 5 to 12 carbon atoms per molecule _(C 5 _{-C 12} fraction).

  The olefin-rich hydrocarbon fraction (also referred to as olefin feed) is preferably an olefin gasoline containing at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt% olefin.

  The olefin feed processed in the oligomerization section (step i)) may come from catalytic cracking, coking or steam cracking equipment. It is generally preferred that the feedstock undergo a pretreatment step prior to step i) to reduce the amount of polyunsaturated compound, sulfur-containing compound and nitrogen-containing compound. These pretreatments can maximize the cycle time of the catalyst.

Diolefins present in the feed may cause catalyst deactivation by polymerization and gum formation. Polyunsaturated compounds can be extracted for improved performance in petrochemical applications. This extraction is generally performed by liquid-liquid extraction or extractive distillation using a polar solvent. For example, butadiene, from C ₄ fraction from steam cracking, acetonitrile, can be extracted with a solvent such as furfural or other polar solvents. Another possibility consists of converting diolefins to olefins by selective hydrogenation. In order to maximize the lifetime of the acid catalyst used to oligomerize the olefin, the amount of polyunsaturated compound in the feed entering the oligomerization unit is preferably less than 1% by weight, more preferably 0. Less than 5% by weight.

Nitrogen-containing compounds usually have basic properties and therefore neutralize the acid sites of the catalyst. The first basic compound that may be present in the C ₃ -C ₆ fraction is an amine. Nitrogen-containing compounds, if present in the feed, can be extracted by a water or acid wash step or by a selective hydrogenation step as described in FR-A-2 850 113. The nitrogen-containing compounds to be extracted are not only basic nitrogen-containing compounds known to deactivate acid catalysts by neutralizing acid sites such as amines; non-basic nitrogen-containing compounds such as nitriles In addition, the acid catalyst may be deactivated.

  However, the inventors have also deactivated the acid catalyst under certain conditions where non-basic nitrogen-containing compounds such as nitriles are also converted into basic compounds such as amines and then neutralize the acid sites. It was observed that it could be caused.

The sulfur-containing compounds present in the C ₃ -C ₆ fraction are mainly thiols. Thiols can react with olefins on acid catalysts to form sulfides with basic properties. The formed sulfide can thus degrade the activity of the acid catalyst.

  Thiols make them heavier using an extractive oxidation process to extract them in the form of disulfides, for example, the MEROX process (TM) or by addition to olefins on metal catalysts by thioesterification reactions. Can be removed. The amount of sulfur-containing compound in the form of thiol or sulfide in the olefin feed for the oligomerization apparatus is preferably less than 100 ppm by weight, more preferably less than 50 ppm by weight.

The feedstock thiophenes, if it contains more particularly the thiophene or methylthiophene, these compounds react with a portion of the olefins present in the olefin C ₃ -C ₆ distillate, heavier Alkylated thiophene compounds can be formed. Therefore, these compounds can optionally be removed from branched olefin gasolines by simple distillation.

  The catalyst used in step i) is an acid catalyst, preferably a supported inorganic acid such as phosphoric acid on silica, sulfonic acid on a polymer (eg ion exchange resin), mineral oxide (eg alumina, Amorphous silica alumina or zeolite).

  The compounds to be generated must be branched in order to maximize their octane number. For this purpose, an acid catalyst having an average pore size that is sufficiently large to allow the diffusion of highly branched molecules is preferably used. The acid catalyst used preferably has an average pore size of more than 0.5 nm, more preferably more than 0.7 nm. Preferably, amorphous silica alumina or ion exchange resin is used.

In the specific case where the catalyst is amorphous silica alumina, it is preferred to dry the olefin feed prior to contacting the olefin feed with the catalyst to obtain a feed containing less than 100 ppm, preferably less than 50 ppm water. The temperature at which the reactor is operated is 50-250 ° C., the HSV is 0.5-5 h ⁻¹ , and the pressure is such that the reaction mixture is maintained in the liquid phase in the reactor.

Branched olefin gasoline derived from the oligomerization process contains more than 90% by weight of olefins. In order to reduce the olefin content, this gasoline must be partially hydrogenated. Together with the desulfurization of sulfur-rich and olefin rich cracked gasoline, the gasoline, preferably it has been discovered that is possible to hydrogenate the C ₅ -C ₁₂ fraction is particularly advantageous. The branched olefin gasoline is therefore mixed with the cracked gasoline to be desulfurized (step ii)).

  The co-processing of branched olefin gasoline and cracked gasoline allows two gasoline bases to be processed in the same reaction section, thereby limiting the investment in refining. Furthermore, it has been surprisingly discovered that co-treatment of these two fractions can limit the octane loss associated with olefin hydrogenation during hydrodesulfurization and hydrogenation processes.

  The mixture constituted by branched olefin gasoline and cracked gasoline is therefore treated in a hydrodesulfurization step (step iii)). This mixture preferably comprises at least 5% by weight, more preferably at least 10% by weight and very particularly preferably at least 15% by weight of branched olefinic gasoline, based on the sum of the two gasolines.

  It is advantageous to extract light fractions containing olefins containing 5 or 6 carbon atoms from cracked gasoline. This fraction essentially contains saturated sulfur-containing compounds in the form of thiols and therefore does not require strict desulfurization. Thiols can be extracted primarily in two ways. The cracked gasoline is treated in a selective hydrogenation and thioesterification reactor, such as that described in FR-A-2 797 639, and then hydrocarbons containing 5 and possibly 6 carbon atoms are removed. It can be distilled to separate a light fraction that contains but does not contain sulfur. Another solution consists of treating the light fraction with an extractive MEROX ™ type method known to those skilled in the art that allows thiols to be selectively extracted.

The hydrodesulfurization step is carried out by contacting the gasoline mixture to be treated with hydrogen over a catalyst capable of converting sulfur-containing organic compounds to H ₂ S. However, it is advantageous to use a catalyst and operating conditions that can control the degree of olefin hydrogenation using a process that exhibits selective hydrodesulfurization.

  The hydrodesulfurization reactor operating conditions are those typically used to selectively desulfurize olefinic gasoline. For example, a temperature of 220 to 350 ° C. is used, and the pressure is preferably 0.1 to 5 MPa, more preferably 1 to 3 MPa.

The space velocity (expressed as the volume of liquid gasoline to be desulfurized per hour of catalyst volume; HSV) is preferably about 0.5 to 20 h ⁻¹ , more preferably ¹ to 10 h ⁻¹ , very preferably Is 2-8 h ⁻¹ .

  The ratio of the hydrogen flow rate to the gasoline flow rate to be desulfurized is preferably 50 to 800 liters / liter, more preferably 100 to 400 liters / liter.

  The hydrodesulfurization reactor contains at least one hydrodesulfurization catalyst, and the hydrodesulfurization catalyst preferably contains at least one group VIII element and at least one group VIB element as a porous carrier. Contains supported on.

  The Group VIII element is preferably iron, cobalt or nickel. The Group VIB element is preferably molybdenum or tungsten. The amount of Group VIII element expressed as an oxide is preferably 0.5 to 15% by weight, more preferably 0.7 to 10% by weight. The amount of the Group VIB element is preferably 1.5 to 60% by weight, more preferably 2 to 50% by weight.

  The porous support is preferably selected from the group constituted by silica, alumina, silicon carbide and mixtures of these components.

In order to control the hydrogenation of olefins, it is advantageous to use a support comprising alumina, preferably at least 70% by weight, more preferably at least 80% by weight alumina, with a specific surface area of less than 200 m ² / g. , Preferably less than 150 m ² / g, more preferably less than 100 m ² / g.

The porosity of the catalyst before sulfiding is such that the average pore diameter is preferably more than 20 nm, more preferably 20 to 100 nm. The surface density of the Group VIB metal is preferably 2 × 10 ⁻⁴ to 40 × 10 ⁻⁴ g, more preferably 4 × 10 ^{−4 to} 16 × 10, of the metal oxide per area (m ² ) of the support. it is ^-4 g / ^{m 2.}

  Since the Group VIB and Group VIII elements are active in hydrodesulfurization in a sulfurized form, the catalyst is generally contacted with the feed to be treated after undergoing a sulfurization step. Generally, the sulfiding is accomplished by heat treating the solid, during which it is contacted with a decomposable sulfur-containing compound that can produce hydrogen sulfide. Alternatively, the catalyst can be contacted directly with a gas stream comprising hydrogen sulfide. This step can be performed off-site or on-site, ie, inside or outside the hydrodesulfurization reactor.

  In some cases, prior to contact with the feedstock, the sulfurized catalyst also undergoes a carbon deposition step that deposits a negligible amount of carbon, preferably 2.8 wt% or less. This carbon deposition step aims to improve the selectivity of the catalyst by preferentially inhibiting the hydrogenation activity of the catalyst. Most preferably, the amount of deposited carbon is between 0.5 and 2.6% by weight. This carbon deposition step can be performed before, after, or during the catalytic sulfidation step.

  Selective hydrodesulfurization can be performed in one reactor containing one catalyst as described herein above. However, it may be advantageous to carry out this step in a plurality of reactors using a series of catalysts.

  In a particular embodiment of the invention, the hydrodesulfurization end step is inserted between steps iii) and iv) and comprises a catalyst, preferably at least one element selected from group VIII elements, It can be carried out in the presence of what is supported on a porous carrier such as alumina or silica. The amount of the Group VIII element is preferably 1 to 60% by weight, more preferably 2 to 20% by weight. The metal is introduced in the form of a metal body and then sulfided prior to use. This termination step is mainly performed to decompose saturated sulfur-containing compounds such as thiols and sulfides contained in the effluent from the first desulfurization step. If present, the termination step is preferably performed at a temperature above that for the desulfurization step.

  In another specific embodiment of the invention, the termination step may be performed on a hydrodesulfurization catalyst comprising at least one Group VIII element and one Group VIB element supported on a porous support. .

The Group VIII element is preferably iron, cobalt or nickel. The Group VIB element is preferably molybdenum or tungsten. The amount of Group VIII element, expressed as an oxide, is preferably 0.5 to 10% by weight, more preferably 0.7 to 5% by weight. The amount of Group VIB metal is preferably 1.5-50% by weight, more preferably 2-20% by weight.
The porous carrier is preferably selected from the group constituted by silica, alumina, silicon carbide or a mixture of these components. In order to minimize olefin hydrogenation, it is advantageous to use an alumina-based support having a specific surface area of less than 200 m ² / g, preferably less than 150 m ² / g, more preferably 100 m ² / g. .

  The porosity of the catalyst before sulfiding is preferably such that the average pore diameter is greater than 20 nm, preferably 20-100 nm.

The surface density of the Group VIB metal is preferably 2 × 10 ⁻⁴ to 40 × 10 ⁻⁴ g, preferably 4 × 10 ^{−4 to} 16 × 10 ^{− of the} metal oxide per area (m ² ) of the support. ⁴ g / m ² .

  The catalytic activity of the catalyst in this termination step is preferably 1 to 90%, more preferably 1 to 70%, preferably 1 to 50% of the catalytic activity of the first hydrodesulfurization catalyst (step iii) (conversion). Measured with respect to). If present, this termination step is preferably performed at a temperature higher than that of the first desulfurization step.

  The desulfurization process is generally performed in a reactor having a fixed bed of catalyst that may include multiple catalyst beds separated by a cold fluid injection zone, referred to as a cooling zone for controlling the temperature rise along the reactor. Is called.

At the end of the hydrodesulfurization process, the gasoline is cooled and liquefied. H ₂ S derived from converting the sulfur-containing organic compound is separated from the gasoline together with excess hydrogen (step iv)). H ₂ S dissolved in gasoline is preferably removed by stripping.

(Example 1 (comparison))
a) Production of branched gasoline An olefin C ₄ fraction from a catalytic cracker, indicated by α1, whose characteristics are shown in Table 1 is sold by Axens and consists of amorphous silica alumina with reference IP501 Treated on catalyst. In addition, this fraction contained 3 ppm sulfur and 1 ppm nitrogen. The operating conditions were as follows: the temperature was 140 ° C., the HSV was 1 h ⁻¹ and the pressure was 6 MPa. The reaction product was distilled to recover dimers and trimers containing 6-12 carbon atoms from the butene reaction. The resulting gasoline (denoted α2) contains more than 90% by weight of olefins, more than 90% of the olefins are branched olefins, with an octane number of 90.1 (motor octane number and research octane number). Calculated by taking the average). This average is commonly referred to as FON. This gasoline was therefore the branched olefin gasoline described in the present invention.

  This α2 gasoline is hydrogenated in the presence of a hydrogenation catalyst containing nickel supported on alumina using a hydrogenation method not in accordance with the present invention, and a part of the olefin is hydrogenated and hydrogenated. Gasoline could be incorporated into a mixture of commercial gasolines with an overall olefin content limited to 18%.

  The α3 gasoline obtained after partial hydrogenation contained 45% by volume of olefins and had a FON octane number of 90.5. Therefore, the hydrogenation of olefin gasoline had little effect on octane number.

b) Production of desulfurized catalytic cracking gasoline Catalytic cracking gasoline β1 containing 810 ppm sulfur, having a cut point of 60-170 ° C. and having a FON octane number of 86.4 is expressed as% of oxide. The catalyst was treated on a hydrodesulfurization catalyst containing 2.5% by weight cobalt and 12% by weight molybdenum on an alumina support having a specific surface area of 145 m ² / g. The gasoline was desulfurized under the following conditions: the temperature was 280 ° C., the pressure was 2 MPa, the HSV was 3 h ⁻¹ , and the ratio of the hydrogen flow rate to the gasoline flow rate to be desulfurized was 300 liters / hr. Liters. The resulting desulfurized gasoline β2 contained 12 ppm sulfur, 19.8 vol% olefin, and its FON octane number was 82.2.

c) Gasoline mixing 2.5 liters of gasoline α3 and 7.5 liters of gasoline β2 were mixed to produce gasoline for introduction into the gasoline pool. The resulting gasoline δ1 contained 26.1% by volume olefin, 10 ppm sulfur and its FON octane number was 84.2.

(Example 2: consistent with the present invention)
2.5 liters of branched olefin gasoline α2 and 7.5 liters of gasoline β1 obtained using the method described in Example 1 were mixed and then treated over a hydrodesulfurization catalyst. The hydrodesulfurization catalyst was the same as in Example 1. The gasoline was desulfurized under the following conditions: the temperature was 280 ° C., the pressure was 2 MPa, the HSV was 3 h ⁻¹ , and the ratio of the hydrogen flow rate to the gasoline flow rate to be desulfurized was 300 liters / hr. Liter (gasoline). The resulting desulfurized gasoline (δ2) contained 25.9 vol% olefin, 9 ppm sulfur, and had a FON octane number of 85.

  Simultaneous hydrodesulfurization of branched olefin gasoline and cracked gasoline (Example 2) therefore yields desulfurized gasoline with a better FON octane number than when the two gasolines are hydrogenated separately (Example 1). Can be made.

Claims (16)

A method for producing gasoline having a low sulfur content and a controlled olefin content,
Contacting gasoline containing at least 70% by weight of hydrocarbons containing 3 to 6 carbon atoms per molecule with an acid catalyst under conditions that may cause oligomerization of the olefins present in the feedstock; A first step i) comprising producing a branched olefin gasoline;
Step ii) consisting of mixing the branched olefin gasoline produced in step i) with gasoline rich in sulfur and olefins;
Treating the mixture configured as above on a hydrodesulfurization catalyst in the presence of hydrogen to convert the sulfur present in the feed to H ₂ S and at least partially hydrogenate the olefin; Step iii), and
A step iv) of separating the formed H ₂ S. The process according to claim 1, wherein the branched olefin gasoline obtained in step i) is distilled to recover a fraction mainly containing hydrocarbons containing 5 to 12 carbon atoms per molecule.   The method according to claim 1 or 2, wherein the gasoline to be treated in step i) undergoes a pretreatment step prior to the step to reduce the amount of polyunsaturated compound, sulfur-containing compound and nitrogen-containing compound.   4. A process according to any one of claims 1 to 3, wherein the gasoline treated in step i) comprises less than 100 ppm, preferably less than 50 ppm of sulfur in the form of a thiol or sulfide.   The catalyst used in step i) is composed of phosphoric acid on silica, supported inorganic acid such as sulfonic acid on polymer (ion exchange resin etc.), mineral oxide such as alumina, amorphous silica alumina or zeolite. The process according to any one of claims 1 to 4, which is an acid catalyst selected from:   The process according to claim 5, wherein the acid catalyst used is of the amorphous silica alumina type and has an average pore diameter of more than 0.5 nm.   6. The process according to claim 5, wherein the acid catalyst used is an ion exchange resin. The hydrodesulfurization step iii) is carried out at a temperature of 220-350 ° C., preferably a pressure of 0.1-5 MPa, a space velocity of about 0.5-20 h ⁻¹ , 50-800 liters / liter The method according to claim 1, wherein the method is performed at a ratio of a flow rate of hydrogen to a flow rate.   The process according to any one of claims 1 to 8, wherein the hydrodesulfurization catalyst comprises at least one Group VIII element and at least one Group VIB element supported on a porous support.   The method according to claim 9, wherein the amount of Group VIII element, expressed as an oxide, is 0.5 to 15% by weight and the amount of Group VIB element is 1.5 to 60% by weight. . The method according to claim 9 or 10, wherein the support comprises alumina and has a specific surface area of less than 200 m ² / g. 12. The method according to claim 9, wherein the surface density of the Group VIB metal is 2 × 10 ⁻⁴ to 40 × 10 ⁻⁴ grams of metal oxide per area (m ² ) of the support. .   The process according to any one of claims 9 to 12, wherein the hydrodesulfurization catalyst is contacted with the feed to be treated after undergoing a sulfidation step.   The process according to any one of claims 1 to 13, wherein the end of the hydrodesulfurization is inserted between step iii) and step iv).   The process according to claim 14, wherein the catalyst used in the termination step is a catalyst selected from Group VIII elements and comprising at least one element supported on a porous support.   The process according to claim 14, wherein the catalyst used in the termination step has a catalytic activity of 1 to 70% of the catalytic activity of the first hydrodesulfurization catalyst.