(19)
(11)EP 2 673 247 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 11799908.6

(22)Date of filing:  30.11.2011
(51)Int. Cl.: 
C07C 2/66  (2006.01)
C10G 63/02  (2006.01)
C10G 69/12  (2006.01)
C10G 29/20  (2006.01)
C10G 57/00  (2006.01)
(86)International application number:
PCT/US2011/062648
(87)International publication number:
WO 2012/108926 (16.08.2012 Gazette  2012/33)

(54)

PROCESS FOR REDUCING THE BENZENE CONTENT OF GASOLINE

VERFAHREN ZUR VERMINDERUNG DES BENZOLGEHALTES VON BENZIN

PROCÉDÉ DE RÉDUCTION DE LA TENEUR EN BENZÈNE D'UNE ESSENCE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 07.02.2011 WO PCT/US2011/023912

(43)Date of publication of application:
18.12.2013 Bulletin 2013/51

(73)Proprietor: Badger Licensing LLC
Boston, MA 02111 (US)

(72)Inventors:
  • HWANG, Shyh-Yuan H.
    Needham, MA 02494 (US)
  • BIRKHOFF, Ronald
    Houston, TX 77008 (US)
  • GUARINO, Richard F.
    Fairhaven, MA 02719 (US)
  • MOY, J., Erik
    South Grafton, MA 01560 (US)
  • PETERS, Joseph, C.
    Quincy, MA 02169 (US)

(74)Representative: Abel & Imray 
Westpoint Building James Street West
Bath BA1 2DA
Bath BA1 2DA (GB)


(56)References cited: : 
US-A- 4 343 957
US-A1- 2008 171 900
US-A- 5 491 270
US-B1- 6 835 862
  
  • Pierre LEPRINCE: "Le raffinage du pétrole - 3.Procédés de transformation", 1 January 1998 (1998-01-01), Technip, Paris, XP002670362, vol. 3 page 266; table 7.1 page 164 - page 165 page 167; table 4.15
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

FIELD



[0001] This invention relates to a process for reducing the benzene content of gasoline.

BACKGROUND



[0002] Benzene is considered to be environmentally hazardous. As a result, the State of California and the United States Environmental Protection Agency have instituted regulations to limit the amount of benzene which may be present in gasoline. As of January 2011, the US MSAT-2 (Mobile Source Air Toxics) regulation requires reduction of this annual average benzene content in gasoline to no greater than 0.62 volume %.

[0003] One known route for reducing the benzene content of gasoline is to selectively alkylate the benzene using a lower olefin. For example, Holtermann et al U.S. Patent No. 5,149,894 describes a process for converting benzene to alkylated benzenes in a gasoline blend stock. The process involves contacting a benzene-containing gasoline blend stock with a C2 to C4 olefin stream in the presence of a catalyst containing the zeolite, SSZ-25, to produce an alkylated light hydrocarbon stream with reduced benzene content.

[0004] Cheng et al. U.S. Patent No. 5,545,788 describes a process for the production of a more environmentally suitable gasoline by removing a substantial portion of benzene in gasoline by alkylation of reformate. The process involves alkylation using a light olefin feed at low temperature over the zeolite catalyst, MCM-49.

[0005] US 5,491,270 discloses a process for alkylating a benzene-rich gasoline boiling range hydrocarbon feedstream by contacting the benzene-rich stream with a C5 + olefin stream in a fluidized bed with solid, shape selective aluminosilicate catalyst particles to produce an effluent gasoline stream having a reduced benzene content, in which the aromatics which are present are substantially entirely C10- alkylated aromatics.

[0006] Umansky el al. U.S. Patent No. 7,476,774 describes a process where light olefins including ethylene and propylene are extracted from refinery off-gases, such as from a catalytic cracking unit, into a light aromatic stream, such as a reformate containing benzene and other single ring aromatic compounds, which is then reacted with the light olefins to form a gasoline boiling range product containing alkylaromatics. The alkylation reaction is carried out in the liquid phase with a catalyst which preferably comprises a member of the MWW family of zeolites, such as MCM-22, using a fixed catalyst bed.

[0007] US 6 835 862, US 2008/171900A and US 4 343 957 each disclose methods of producing ethylbenzene and/or cumene by alkylation of an aromatic feed stream.

[0008] However, in addition to limiting the benzene level in gasoline, current and ongoing regulations restrict the content of residue, which consists of heavy hydrocarbon components with boiling points outside the gasoline boiling range. The US standard specification for automotive spark-ignition engine fuel (ASTM D4814) requires that the residue (heavies) in the gasoline product is no more than 2 volume %. As benzene regulations become more stringent, meeting the heavies level becomes an increasing problem because the light olefins used to alkylate the benzene in the gasoline can undergo undesirable competing reactions, such as olefin oligomerization to produce, for example, C6 to C8 olefins. Subsequent aromatic alkylation reactions result in the formation of heavy components, with boiling points outside of the typical gasoline boiling range. This problem is particularly pronounced with gasoline feeds which contain significant quantities of C6 to C8 olefins since these olefins further contribute towards the production of heavy hydrocarbons boiling above the gasoline range.

[0009] According to the present invention, it has now been found that the undesirable formation of heavy components in the alkylation of benzene-containing gasoline streams containing significant quantities of C6 to C8 olefins can be reduced by introducing a once-through alkylation pre-reactor upstream of a main recirculating alkylation reactor.

SUMMARY



[0010] In one aspect, the invention resides in an process for alkylating benzene contained in a benzene-containing refinery gasoline stream, such as a reformate or a light naphtha, said benzene-containing refinery gasoline stream comprising from 4 to 40 volume % benzene and said process comprising contacting said benzene-containing refinery gasoline stream under alkylation conditions with an alkylating agent selected from one or more C2 to C5 olefins in at least a first alkylation reaction zone and a second alkylation reaction zone connected in series to produce an alkylated effluent, which has reduced benzene content as compared with said refinery gasoline stream, wherein all of the refinery gasoline stream is introduced into the first alkylation reaction stage, wherein an aliquot of the alkylated effluent from the second reaction zone is recycled and introduced to the second, but not the first, alkylation reaction zone, and wherein the refinery gasoline stream comprises at least 0.1 volume % of at least one C6 to C8 olefin.

[0011] Conveniently, the alkylated effluent contains at least 50 % less, such as at least 75 % less, for example at least 87 % less, benzene as compared with said refinery gasoline stream.

[0012] Conveniently, the weight ratio of recycled alkylated effluent to feed introduced into said second alkylation reaction stage is at least 0.05.

[0013] Typically, the alkylated effluent comprises less than 2 volume %, such as less than 0.62 volume %, benzene. Generally, the alkylated effluent comprises no more than 2 volume % of compounds having a boiling point greater than 236 °C at atmospheric pressure.

[0014] In one embodiment, the contacting in the at least one alkylation reaction zone takes place in the presence of a catalyst comprising an MWW zeolite and the alkylating agent is propylene.

[0015] The refinery gasoline stream may be substantially in the liquid phase during said contact of the refinery gasoline stream with the alkylating agent in the alkylation reaction zone.

BRIEF DESCRIPTION OF THE DRAWINGS



[0016] Figure 1 is a schematic diagram of a process for reducing the benzene content of gasoline in accordance with one embodiment of the invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS



[0017] Benzene-containing refinery gasoline streams which may be alkylated to decrease benzene content include streams comprising benzene and alkylbenzenes. Examples of such streams include reformates and naphtha streams, especially light naphtha streams (typically boiling in the range from about 40 °C to about 150 °C). Blends of benzene-containing refinery gasoline streams may also be alkylated. The benzene-containing refinery gasoline streams employed in the present process comprise from 4 volume % to 40 volume % benzene.

[0018] Reformates have high octane number attributable to their high aromatics content. However, high concentrations of benzene in reformate, e.g., in excess of 4 volume %, can limit reformate utility as a blending component where environmental considerations require low benzene levels in gasoline product. Various efforts to reduce benzene content in reformate, e.g., selective hydrogenation, high temperature fluid-bed MBR, and reformate alkylation with methanol all suffer from octane losses or total liquid product losses associated with undesired cracking of C5+ non-aromatics.

[0019] The present invention relates to a process whereby benzene-containing reformates and other benzene-containing refinery gasoline streams are treated to reduce benzene content by alkylation. Undesirable alkylation of higher boiling aromatics, such as xylenes, may be minimized.

[0020] Alkylating agents for use in the present process are olefins having 2 to 5 carbon atoms, such as ethylene, propylene, butenes, and pentenes. Mixtures of light olefins are especially useful as alkylating agents in the alkylation process of this invention. Accordingly, mixtures of ethylene, propylene, butenes, and/or pentenes which are major constituents of a variety of refinery streams, e.g., fuel gas, gas plant off-gas containing ethylene, propylene, etc., naphtha cracker off-gas containing light olefins, refinery FCC propane/propylene streams, and FCC off-gas, etc., are useful alkylating agents herein. Compositions of examples of olefin containing streams suitable for use as alkylating agents are described, for example, in U.S. Patent No. 7,476,774.

[0021] The alkylation process may be conducted such that the organic reactants, i.e., the alkylatable aromatic compound and the alkylating agent, are brought into contact with a zeolite catalyst composition under alkylation conditions effective to produce an alkylated effluent which has reduced benzene content as compared with said refinery gasoline stream and is essentially free (that is contains less than 0.1 wt%) of the alkylating agent. Generally, the alkylated effluent contains at least 50 % less, such as at least 75 % less, for example at least 87 % less, benzene as compared with said refinery gasoline stream.

[0022] Suitable alkylation conditions may include a temperature of from about 0 °C to about 500 °C, for example, between about 50 °C and about 300 °C, and a pressure of from about 0.2 to about 250 atmospheres, for example, from about 1 to about 50 atmospheres. The feed weight hourly space velocity (WHSV) will generally be between 0.1 hr-1 and 500 hr-1, for example, from 0.5 hr-1 to 100 hr-1. The latter WHSV is based upon the total weight of active catalyst (and binder if present).

[0023] The alkylation process is conducted in at least two alkylation reaction zones which are connected in series and which each typically contain a fixed bed of the catalyst composition. All of the refinery gasoline stream is introduced into the first alkylation reaction zone, while the C2 to C5 alkylating agent is supplied, generally in equal amounts, to each alkylation reaction zone. An aliquot of the alkylated effluent is recycled to the second, but not the first, alkylation reaction zone. Generally, weight ratio of recycle to feed at the inlet of said second alkylation reaction zone is at least 0.05:1, such as from about 0.1:1 to about 10:1.

[0024] As used herein, the term "aliquot" is used in its commonly accepted sense to mean a portion of the alkylated effluent, which has not been subjected to fractionation or other operations to alter its composition and so has the same composition as the total effluent.

[0025] The reactants may be in the vapor phase or the liquid phase or in a mixture of liquid and vapor phases. The reactants may be neat, i.e., free from intentional admixture or dilution with other material, or they can be brought into contact with the zeolite catalyst composition with the aid of carrier gases or diluents such as, for example, hydrogen or nitrogen.

[0026] One embodiment of the present process is shown in Figure 1, in which a gasoline feed containing benzene and at least one C6 to C8 olefin is supplied by line 11 to a first alkylation reaction zone 13, which is connected in series to a second alkylation reaction zone 14 by line 15. Propylene is supplied to the process through line 16 and is divided equally between, and fed to, the reaction zones 13, 14 by lines 17, 18 respectively.

[0027] The first and second alkylation reaction zones 13, 14 each house a fixed bed of alkylation catalyst 19, 21 and the outlet of the second alkylation zone 14 is connected to the inlet of zone 14 by line 22 and a recycle loop 23 comprising line 24, pump 25 and line 26.

[0028] In practice, the first alkylation reaction zone 13 is maintained under conditions such that part of the benzene in the gasoline feed reacts with the propylene introduced into zone 13 through line 17 mainly to produce cumene. The partially alkylated gasoline product then exits the zone 13 and is transported by line 15 to the second alkylation reaction zone 14, which is also maintained under conditions such that part of the benzene in the gasoline feed reacts with the propylene introduced through line 18 again mainly to produce cumene. The alkylated effluent then exits the second alkylation zone 14 through line 22 and part of the effluent is recovered via line 27 for use as a gasoline blending stock and part is recycled to the inlet of the second alkylation reaction zone 14 by recycle loop 23.

Catalyst System



[0029] The catalyst system used in the alkylation of the present process is preferably one based on a zeolite of the MWW family because these catalysts exhibit excellent activity for the desired aromatic alkylation reaction using light olefins, especially propylene. It is, however, possible to use other molecular sieve catalysts for this alkylation, including catalysts based on ZSM-12 as described in U.S. Patent Nos. 3,755,483 and 4,393,262 for the manufacture of petrochemical cumene from refinery benzene and propylene or catalysts based on zeolite beta as described in U.S. Patent No. 4,891,458, all of which are reported to have activity for the alkylation of light aromatics by propylene.

MWW Zeolite



[0030] The MWW family of zeolite materials has achieved recognition as having a characteristic framework structure which presents unique and interesting catalytic properties. The MWW topology consists of two independent pore systems: a sinusoidal ten-member ring [10 MR] two dimensional channel separated from each other by a second, two dimensional pore system comprised of 12 MR super cages connected to each other through 10 MR windows. The crystal system of the MWW framework is hexagonal and the molecules diffuse along the [100] directions in the zeolite, i.e., there is no communication along the c direction between the pores. In the hexagonal plate-like crystals of the MWW type zeolites, the crystals are formed of relatively small number of units along the c direction as a result of which, much of the catalytic activity is due to active sites located on the external surface of the crystals in the form of the cup-shaped cavities. In the interior structure of certain members of the family such as MCM-22, the cup-shaped cavities combine together to form a supercage. The MCM-22 family of zeolites has attracted significant scientific attention since its initial announcement by Leonovicz et al. in Science 264, 1910-1913 [1994] and the later recognition that the family includes a number of zeolitic materials such as PSH 3, MCM-22, MCM-49, MCM-56, SSZ-25, ERB-1, ITQ-1, and others. Lobo et al. AlChE Annual Meeting 1999, Paper 292J.

[0031] The relationship between the various members of the MCM-22 family have been described in a number of publications. Significant members of the family are MCM-22, MCM-36, MCM-49, and MCM-56. When initially synthesized from a mixture including sources of silica, alumina, sodium, and hexamethylene imine as an organic template, the initial product will be MCM-22 precursor or MCM-56, depending upon the silica: alumina ratio of the initial synthesis mixture. At silica:alumina ratios greater than 20, MCM-22 precursor comprising H-bonded vertically aligned layers is produced whereas randomly oriented, non-bonded layers of MCM-56 are produced at lower silica:alumina ratios. Both these materials may be converted to a swollen material by the use of a pillaring agent and on calcination, this leads to the laminar, pillared structure of MCM-36. The as-synthesized MCM-22 precursor can be converted directly by calcination to MCM-22 which is identical to calcined MCM-49, an intermediate product obtained by the crystallization of the randomly oriented, as-synthesized MCM-56. In MCM-49, the layers are covalently bonded with an interlaminar spacing slightly greater than that found in the calcined MCM-22/MCM-49 materials. The as-synthesized MCM-56 may be calcined itself to form calcined MCM-56 which is distinct from calcined MCM-22/MCM-49 in having a randomly oriented rather than a laminar structure. In the patent literature MCM-22 is described in U.S. Patent No. 4,954,325 as well as in U.S. Patent Nos. 5,250,777; 5,284,643 and 5,382,742. MCM-49 is described in U.S. Patent No. 5,236,575; MCM-36 in U.S. Patent No. 5,229,341 and MCM-56 in U.S. Patent No. 5,362,697.

[0032] A preferred zeolitic material for use as the MWW component of the catalyst system is MCM-22 or MCM-49.

Catalyst Matrix



[0033] In addition to the zeolitic component, the catalyst will usually contain a matrix material or binder in order to give adequate strength to the catalyst as well as to provide the desired porosity characteristics in the catalyst. High activity catalysts may, however, be formulated in the binder-free form by the use of suitable extrusion techniques, for example, as described in U.S. Patent No. 4,908,120. When used, matrix materials suitably include alumina, silica, silica alumina, titania, zirconia, and other inorganic oxide materials commonly used in the formulation of molecular sieve catalysts. For use in the present process, the level of zeolite, such as MCM-22 or ZSM-5 type (intermediate pore size) zeolite, in the finished matrixed catalyst will be typically from 20 to 70% by weight, and in most cases from 25 to 65% by weight. In manufacture of a matrixed catalyst, the active ingredient will typically be mulled with the matrix material using an aqueous suspension of the catalyst and matrix, after which the active component and the matrix are extruded into the desired shape, for example, cylinders, hollow cylinders, trilobe, quadlobe, etc. A binder material such as clay may be added during the mulling in order to facilitate extrusion, increase the strength of the final catalytic material and to confer other desirable solid state properties. The amount of clay will not normally exceed 10% by weight of the total finished catalyst. Unbound (or, alternatively, self-bound) catalysts are suitably produced by the extrusion method described in U.S. Patent No. 4,582,815, to which reference is made for a description of the method and of the extruded products obtained by its use. The method described there enables extrudates having high constraining strength to be produced on conventional extrusion equipment and accordingly, the method is suitable for producing the catalysts which are silica-rich. The catalysts are produced by mulling the zeolite with water to a solids level of 25 to 75 wt % in the presence of 0.25 to 10 wt % of basic material such as sodium hydroxide. Further details are to be found in U.S. Patent No. 4,582,815.

Gasoline Product



[0034] Even with a refinery gasoline feed comprising at least 4 volume % benzene, the present process allows the production of a gasoline product which contains less than 2 volume %, typically less than 0.62 volume %, benzene and generally no more than 2 volume % of compounds having a boiling point greater than 236 °C at atmospheric pressure. In addition, it is to be appreciated that, unlike conventional processes for alkylating aromatics with C2 to C5 olefins, the entire alkylated product of the present process is intended for use as a gasoline blending component, without fractionation to separate the product into monoalkylated species, polyalkylated species and unreacted aromatic feed.

[0035] The invention will now be more particularly described with reference to the following non-limiting Examples.

Comparative Example 1



[0036] A sample of MCM-49 alkylation catalyst was tested with a feed containing 15% benzene, 4% toluene, 1% 1-hexene and 80% n-heptane. Propylene was used as the alkylating agent. In one embodiment of the invention, a single stage alkylation reactor was used as the base case to represent an alkylation reaction system, with a reactor inlet temperature of 200 °C, and with a reactor effluent recycle to feed recirculation ratio of 4:1.

Example 2



[0037] An alkylation pre-reactor was placed upstream of the alkylation reaction system of the base case described in Comparative Example 1. The data listed in Table 1 below show that a once-through pre-reactor placed upstream of the main circulating reactor reduces the heavies make substantially.

[0038] The benefit of a combination of an alkylation pre-reactor with any other configuration of the alkylation reaction system is possible and a similar benefit in reduced heavies make is projected.
Table 1
Reactor ConfigurationBenzene ConversionHeavies Make (volume %)
1-Stage Circulating Reactor (Comparative Example 1) 75% 1.3%
87% 2.1%
93% 3.2%
97% 5.5%
     
Once-Through Pre-Reactor Followed By 1-Stage Circulating Reactor (Example 2) 84% 1.2%
90% 1.8%
95% 3.2%



Claims

1. A process for alkylating benzene contained in a benzene-containing refinery gasoline stream, said benzene-containing refinery gasoline stream comprising from 4 to 40 volume % benzene and said process comprising contacting said benzene-containing refinery gasoline stream under alkylation conditions with an alkylating agent selected from one or more C2 to C5 olefins in at least a first alkylation reaction zone and a second alkylation reaction zone connected in series to produce an alkylated effluent, which has reduced benzene content as compared with said refinery gasoline stream, wherein all of the refinery gasoline stream is introduced into the first alkylation reaction stage, wherein an aliquot of the alkylated effluent from the second reaction zone is recycled and introduced to the second, but not the first, alkylation reaction zone, and wherein the refinery gasoline stream comprises at least 0.1 wt % of at least one C6 to C8 olefin.
 
2. A process according to claim 1, wherein the alkylated effluent contains at least 50 % less benzene as compared with said refinery gasoline stream.
 
3. A process according to claim 1 or claim 2, wherein the alkylated effluent contains at least 75 % less benzene as compared with said refinery gasoline stream.
 
4. A process according to any one of claims 1 to 3, wherein the alkylated effluent contains at least 87 % less benzene as compared with said refinery gasoline stream.
 
5. A process according to any one of claims 1 to 4, wherein the weight ratio of recycled alkylated effluent to feed introduced into said second alkylation reaction stage is at least 0.05.
 
6. A process according to any one of claims 1 to 5, wherein said refinery gasoline stream is a reformate or a light naphtha.
 
7. A process according to any one of claims 1 to 6, wherein said alkylating agent is propylene.
 
8. A process according to any one of claims 1 to 7, wherein said alkylated effluent comprises less than 2 volume % benzene.
 
9. A process according to any one of claims 1 to 8, wherein said alkylated effluent comprises less than 0.62 volume % benzene.
 
10. A process according to any one of claims 1 to 9, wherein said alkylated effluent comprises no more than 2 volume % of compounds having a boiling point greater than 236 °C at atmospheric pressure.
 
11. A process according to any one of claims 1 to 10, wherein the alkylation reaction in each of said first and second alkylation reaction zones takes place in the presence of a catalyst comprising an MWW zeolite.
 
12. A process according to any one of claims 1 to 11, wherein said refinery gasoline stream is substantially in the liquid phase during said contacting.
 


Ansprüche

1. Verfahren zum Alkylieren von Benzol, das in einem benzolhaltigen Raffineriebenzinstrom enthalten ist, wobei der benzolhaltige Raffineriebenzinstrom 4 bis 40 Vol.-% Benzol umfasst und das Verfahren In-Kontakt-Bringen des benzolhaltigen Raffineriebenzinstroms unter Alkylierungsbedingungen mit einem Alkylierungsmittel ausgewählt aus einem oder mehreren C2- bis C5-olefinen in mindestens einer ersten Alkylierungsreaktionszone und einer zweiten Alkylierungsreaktionszone, die in Reihe verbunden sind, umfasst, um alkyliertes Austrittsmaterial herzustellen, das einen verringerten Benzolgehalt im Vergleich zu dem Raffineriebenzinstrom aufweist, wobei Alles von dem Raffineriebenzinstrom in die erste Alkylierungsreaktionsstufe eingeführt wird, wobei ein Aliquot des alkylierten Austrittsmaterials aus der zweiten Reaktionszone zurückgeführt und in zweite, aber nicht die erste Alkylierungsreaktionszone eingeführt wird, und wobei der Raffinerie-benzinstrom mindestens 0,1 Gew.-% von mindestens einem C6- bis C8-Olefin umfasst.
 
2. Verfahren nach Anspruch 1, bei dem das alkylierte Austrittsmaterial im Vergleich mit dem Raffineriebenzinstrom mindestens 50% weniger Benzol enthält.
 
3. Verfahren nach Anspruch 1 oder Anspruch 2, bei dem das alkylierte Austrittsmaterial im Vergleich mit dem Raffineriebenzinstrom mindestens 75% weniger Benzol enthält.
 
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem das alkylierte Austrittsmaterial im Vergleich mit dem Raffineriebenzinstrom mindestens 87% weniger Benzol enthält.
 
5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem das Gewichtsverhältnis von zurückgeführtem, alkyliertem Austrittsmaterial zu dem Einsatzmaterial, das in die zweite Alkylierungsreaktionsstufe eingeführt wird, mindestens 0,05 beträgt.
 
6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem der Raffineriebenzinstrom Reformat oder leichtes Naphta ist.
 
7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem das Alkylierungsmittel Propylen ist.
 
8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem das alkylierte Austrittsmaterial weniger als 2 Volumen-% Benzol umfasst.
 
9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem das alkylierte Austrittsmaterial weniger als 0,62 Volumen-% Benzol umfasst.
 
10. Verfahren nach einem der Ansprüche 1 bis 9, bei dem das alkylierte Austrittsmaterial nicht mehr als 2 Volumen-% an Verbindungen umfasst, die einen Siedepunkt über 236°C bei Atmosphärendruck aufweisen.
 
11. Verfahren nach einem der Ansprüche 1 bis 10, bei dem die Alkylierungsreaktion in jeder der ersten und zweiten Alkylierungsreaktionszonen in Gegenwart eines Katalysators erfolgt, der MWW-Zeolith umfasst.
 
12. Verfahren nach einem der Ansprüche 1 bis 11, bei dem der Raffineriebenzinstrom während des In-Kontakt-Bringens im Wesentlichen in der flüssigen Phase vorliegt.
 


Revendications

1. Procédé pour alkyler du benzène contenu dans un courant d'essence de raffinerie contenant du benzène, ledit courant d'essence de raffinerie contenant du benzène comprenant 4 à 40 % en volume de benzène, ledit procédé comprenant la mise en contact dudit courant d'essence de raffinerie contenant du benzène, dans des conditions d'alkylation, avec un agent d'alkylation qui est un ou plusieurs choisis parmi les oléfines en C2 à C5 dans au moins une première zone de réaction d'alkylation et une deuxième zone de réaction d'alkylation connectées en série pour produire un effluent alkylé, qui a une teneur en benzène réduite en comparaison avec ledit courant d'essence de raffinerie, où tout le courant d'essence de raffinerie est introduit dans le premier étage de réaction d'alkylation, où une aliquote de l'effluent alkylé provenant de la deuxième zone de réaction est recyclée et introduite dans la deuxième, mais pas la première, zone de réaction d'alkylation, et où le courant d'essence de raffinerie comprend au moins 0,1 % en poids d'au moins une oléfine en C6 à C8.
 
2. Procédé selon la revendication 1, dans lequel l'effluent alkylé contient au moins 50 % de benzène en moins que ledit courant d'essence de raffinerie.
 
3. Procédé selon la revendication 1 ou la revendication 2, dans lequel l'effluent alkylé contient au moins 75 % de benzène en moins que ledit courant d'essence de raffinerie.
 
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel l'effluent alkylé contient au moins 87 % de benzène en moins que ledit courant d'essence de raffinerie.
 
5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le rapport en poids de l'effluent alkylé recyclé à la charge introduite dans ledit deuxième étage de réaction d'alkylation est d'au moins 0,05.
 
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel ledit courant d'essence de raffinerie est un reformat ou un naphta léger.
 
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel ledit agent d'alkylation est le propylène.
 
8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel ledit effluent alkylé comprend moins de 2 % en volume de benzène.
 
9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel ledit effluent alkylé comprend moins de 0,62 % en volume de benzène.
 
10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel ledit effluent alkylé comprend au plus 2 % en volume de composés ayant un point d'ébullition supérieur à 236°C sous la pression atmosphérique.
 
11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel la réaction d'alkylation dans chacune desdites première et deuxième zones de réaction d'alkylation a lieu en présence d'un catalyseur comprenant une zéolite MWW.
 
12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel ledit courant d'essence de raffinerie est pratiquement en phase liquide durant ladite mise en contact.
 




Drawing






REFERENCES CITED IN THE DESCRIPTION



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