KR20150070968A - Catalytic reforming process - Google Patents

Abstract

The present invention relates to a method for manufacturing gasoline having an octane number over 95 from naphtha oil (1) including paraffin and naphthene. The method comprises the steps of: a) transferring the naphtha oil to a first catalytic reforming unit (2) to covert at least a part of the paraffin and/or the naphthene into an aromatic compound, and generate hydrogen; b) drawing a first distillate (3) and a hydrogen stream (4) from the first catalytic reforming unit (2); c) transferring the first distillate (3) to a separation unit (5) to separate hard hydrocarbon oil (6) containing linear paraffin and heavy hydro carbon oil (7) containing non-converted paraffin and/or naphthen; d) transferring the hard hydrocarbon oil to an isomerization unit (11) to generate isomers (12); e) transferring the heavy hydrocarbon oil to a second catalytic unit (8); and f) drawing a reformate (10) containing the aromatic compound from the second catalytic unit.

Description

Catalytic reforming process {CATALYTIC REFORMING PROCESS}

The present invention relates to a method for producing gasoline cuts starting from naphtha oil fraction and having a high octane number, which can be upgraded to a gasoline pool of a refinery.

The conventional purpose of the catalytic reforming unit is to convert naphthenic (cycloalkane) and paraffinic hydrocarbon compounds (n-paraffin and iso-paraffin) into aromatic hydrocarbon compounds. The main relevant reactions are naphthenic dehydrogenation, the aromatic cyclic hydrogen dehydrocyclization of paraffins, and possibly paraffin and naphthenic isomerization. Other reactions known as "side reactions " may occur, such as hydrocracking and hydrocracking of paraffins and naphthenes, hydrodealkylation of alkyl-aromatics not only generates light compounds and light aromatics, Thereby forming a coke on the surface of the coke.

The performance optimized for gasoline applications is the yield of liquid reformate and also the octane number of the reformate

Conventional feeds for the catalytic reforming unit are rich in paraffinic and naphthenic hydrocarbon compounds and relatively few aromatic hydrocarbon compounds. This is typically a naphtha obtained from distillation of natural gas condensate or crude oil treated by catalytic reforming.

In addition to these conventional feeds, other feeds containing heavy naphtha from variable amounts of aromatic, i.e., catalytic cracking (FCC), coke making, hydrocracking or steam cracking gasolines, are available at refineries. Such a feed having varying degrees of aromatic hydrocarbon compounds may be used to feed the catalytic reforming unit for the production of a gasoline base or an aromatic base.

The catalytic reforming unit generally comprises four reactors, including a fixed bed or a moving bed of reforming catalysts in succession.

Also included is a continuous catalyst regenerator in which the cokes deposited in the catalyst are removed in the form of CO ₂ by slow controlled combustion when the reforming unit is comprised of reactors with catalyst bed layers. This unit, known as a continuous regeneration unit, includes complex devices for moving the catalyst, which can then undergo a regeneration treatment and return to the reactors after performing their function alternately in the reactors.

Conventional document US2013 / 0026066 discloses a process for producing a gasoline base starting from naphtha oil fraction. The proposed layout consists of sending a naphtha feed to a fractionation unit that produces a light naphtha oil fraction and a heavy naphtha oil fraction. The light naphtha fraction is isomerized and the heavy naphtha fraction is separated again into paraffinic and non-paraffinic fractions. The paraffinic fraction is treated in the isomerization unit while the non-paraffinic fraction is sent to the catalyst reforming unit. Thus, the various streams produced by the process are sent to the gasoline pool of the refinery.

Thus, the layout described in this document involves paraffin / naphthene separation steps in heavy naphtha oil fractions which are difficult to carry out. Moreover, the layout describes the isomerization step for all of the heavy paraffins containing paraffins of the feed, in particular containing at least 7 carbon atoms. Isomerization of heavy paraffins is very difficult to perform and requires work at high temperatures with long residence times.

It is an object of the present invention to provide a gasoline base which is capable of orienting effluents freely towards generation of a gasoline base in accordance with purification requirements and which has optimized conversion conditions and which has a high octane number at a given treatment capacity, It is a flexible way to generate more.

For this purpose, starting from a naphtha oil fraction containing paraffins and naphthenes, a process is proposed for producing gasoline having an octane number greater than 95, the process comprising the steps of:

a) sending the naphtha oil fraction to a first catalytic reforming unit in which the naphtha oil fraction is contacted with the reforming catalyst to convert at least a portion of the paraffins and / or naphthenes to aromatics and also to produce hydrogen;

b) withdrawing a first effluent and a hydrogen stream from the first catalytic reforming unit;

c) C6 containing straight chain paraffins ^- C containing hydrocarbon fraction and non-converted paraffins and / or naphthenes ^- hydrocarbon fraction and non-converted paraffins and / or naphthenes C7 ⁺ C7 containing a hydrocarbon oil or a straight-chain paraffins containing Sending the first effluent to a separation unit to separate ₈ ⁺ hydrocarbon fractions;

d) converting said straight chain paraffins to branched chain paraffins and converting said straight chain paraffins to isomerization catalysts into isomerization units which are contacted with isomerization catalysts to produce isomeric gels which are sent to a gasoline pool, said C6 ^- hydrocarbon oils or said C7 ^- hydrocarbons Sending the oil;

e) the non-converted paraffins and / or naphthenes to convert the aromatic compounds, the first to the second catalytic reforming unit C7 ⁺ hydrocarbon fraction or the C ₈ ⁺ sending the hydrocarbon oil; And

f) withdrawing a reformate and a hydrogen stream containing an aromatic compound from the second catalytic reforming unit.

The process of the present invention can be used not only as a gasoline fraction (isomerate) rich in branching paraffins with high octane number, upgraded to gasoline pools, but also as a base for gasoline pools and possibly as a base for aromatic complex units The compound (reformate) can be used to produce a gasoline rich in oil. Thus, according to refining requirements, gasoline fractions rich in aromatic hydrocarbon compounds (reformate) are fully oriented towards the gasoline pool when gasoline is required, or when both gasoline bases and aromatic bases for petrochemistry are required, (At an arbitrary ratio) to the complex.

In addition, the method of the present invention is hard C6 ^- or C7 ^- fraction and a heavy C7 ⁺ or yield of the first step and the aromatic product, thanks to the execution of the step 2 for the reforming catalyst having an intermediate step of separating the C ₈ ⁺ fraction, respectively And in terms of capacity. The separation step can be used to recover hard C6 ^- or C7 ^- oil fractions containing hard straight chain paraffins which are difficult to convert to aromatics but are likely to isomerize to branched chain paraffins. As a result, C7 ⁺ or C ₈ ⁺ is a modification step the second catalyst carried out in a hydrocarbon oil, in particular, the order 1 to convert the catalyst modification step paraffin and / or naphthyl untranslated X during, and for example, hydrogenation of a paraffin and naphthene decomposition And to prevent undesired side reactions such as hydrodealkylation of the alkylaromatics which produces hydrocracking, compounds responsible for the formation of coke on the surface of the reforming catalyst. Moreover, it is unnecessary to unnecessarily increase the capacity of the production unit by the intermediate step, because the hard paraffinic compound which is difficult to be modified is separated, and only the heavy paraffinic and / Or only the naphthenic compound is treated.

In a preferred practice, the first reforming step is operated under conditions favoring dehydrogenation of the naphthene compound, which is easier to remove hydrogen and convert to aromatics than paraffin, for which a cyclic hydrogen elimination reaction has to be carried out. The second reforming step is then carried out under more severe conditions than in the first reforming step to promote the heavy paraffinic ring hydrogenation elimination reaction.

In one embodiment, when production of the gasoline base is to be promoted, the reformate is sent to the gasoline pool.

According to another embodiment in which an aromatic base is to be produced for petrochemicals and gasoline, a portion of the reformate is sent to the aromatic complex unit and another portion of the reformate is sent to the gasoline pool.

In certain embodiments, the naphtha fraction is pretreated in the hydrotreating unit prior to step a). As an example, the hydrotreating step is selected from the steps for hydrodemetallization of olefins and diolefins, hydrodesulphurization, hydrodenitrogenation and / or hydrogenation.

According to a preferred embodiment, prior to step a), the naphtha fraction is sent to a separate unit configured to separate the C4 ^- hydrocarbon fraction and the C5 ⁺ hydrocarbon fraction, and the C5 ⁺ fraction is sent to step a).

The first and second catalyst reforming steps a) and e) are carried out in the presence of hydrogen and under the following conditions:

420℃ 내지 600℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 420 ° C to 600 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

0.5 내지 8 h^-1 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도 (weight hourly space velocity).

A weight hourly space velocity expressed as a ratio of the mass flow rate of the feed to the mass of the catalyst, from 0.5 to 8 h ^-1 .

Preferably, the first catalyst reforming step a) is carried out under the following conditions:

420℃ 내지 500℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 420 ° C to 500 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

2.5 내지 8 h^-l 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도.

2.5 to 8 h ^-l, weight space velocity, expressed as the ratio of the mass flow rate of feed to the catalyst weight.

Preferably, the second catalytic reforming step e) is carried out under the following conditions:

500℃ 내지 600℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 500 ° C to 600 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

0.5 내지 2.5 h^-l 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도.

0.5 to 2.5 h ^-1 , expressed as the ratio of the mass flow rate of the feed to the mass of the catalyst.

According to the present invention, naphtha oil fractions are obtained from at least one of the following units: atmospheric distillation, FCC, coke making, steam cracking, hydrocracking, and natural gas condensate fractionation.

Preferably, the catalyst for reforming used in steps a) and e) comprises a support and a metal, such as platinum. Most preferably, the catalyst for catalyst modification is catalyzed by one of the following elements: Re, Sn, In, P, Ge, Ga, Bi, B, Ir, or rare earth.

In certain embodiments, the reforming catalyst comprises an alumina support, platinum, and optionally one or more promoters as described above. Preferably, the promoter element is tin.

According to a preferred embodiment, the catalyst for reforming of step a) has a chlorine content of less than 0.1% by weight, preferably less than 0.05% by weight, based on the total catalyst weight.

Preferably, the catalyst for reforming of step e) is present in an amount of from 0.8% to 1.5% by weight, preferably from 0.8% to 1.2% by weight, more preferably from 0.9% to 1.1% .

According to the present invention, the first and second catalytic reforming units may use a fixed bed reactor in a "semi-regenerative" mode or a moving bed reactor in a "continuous regeneration" mode. In the case of a fixed bed system, it comprises, for example, at least two reactors operating in parallel, wherein the first reactor is used to regenerate the catalyst and the second reactor is used for the reforming reaction.

According to a preferred embodiment of the present invention, the reforming unit functions in a "continuous regeneration" mode (continuous catalyst regeneration (CCR)). This type of unit is characterized by continuous in situ regeneration of a portion of the catalyst in a dedicated regenerator and continuous addition of regenerated catalyst to the reactor to effect the conversion reaction.

Thus, a "continuous regeneration" reforming reactor of this type comprises at least one reactor and a regenerator. Preferably, the reforming unit comprises two reactors and a catalyst regenerator, which are successively used to effect the conversion of paraffinic and naphthanic hydrocarbon compounds into aromatic compounds.

According to a preferred embodiment, when the catalysts are the same in the two reforming units, the first reforming unit is composed of at least one conversion reactor and the second reforming unit comprises at least one conversion reactor and regenerator, And moves toward the first reactor of the first catalytic reforming unit. This embodiment is advantageous because it means that the regenerator can be used to regenerate the catalyst used in the first and second reforming units.

When different catalysts are used in each of the first and second reforming units, they are composed of at least one conversion reactor and regenerator.

Other features and advantages of the present invention will become better understood and appreciated from the following description taken in conjunction with the accompanying drawings.

Figure 1 shows the layout of one embodiment of the method of the present invention.

To better understand the content, the term "naphtha" will hereinafter be used to denote an oil cut of any chemical composition, preferably with a distillation range of 50 [deg.] C to 250 [deg.] C. Any distribution of chemical families may be employed where PONA (paraffin is P, olefin is 0, naphthene is N, aromatic is A).

The term "gasoline" is used to denote an oil fraction having a distillation range similar to the distillation range of the naphtha and having an octane number greater than 95, preferably greater than 98.

The term "aromatic base" refers in a broad sense to a heavy aromatic such as xylene (para-xylene, meta-xylene, ortho-xylene), ethylbenzene, toluene and benzene and possibly monomeric styrene, cumene or straight chain alkylbenzene May also be used.

The term "reformate" is used for gasoline fractions having a high octane number produced by catalytic reforming.

The treated hydrocarbon feed

In the following, the term "naphtha ", alone or in combination with other naphtha, is used to denote a feed that can be treated by the process of the present invention. This feed is a hydrocarbon oil fraction rich in paraffinic and naphthenic compounds and having relatively few aromatic hydrocarbon compounds. The naphtha feed is obtained, for example, from atmospheric distillation of crude oil or natural gas condensate. The process of the present invention can also be applied to heavy naphtha or cracked gasoline from catalytic cracking (FCC), coke making, hydrocracking. This feed having a variable aromatic hydrocarbon compound content may be used to feed the catalytic reforming unit for the production of a gasoline base or an aromatic base.

1 shows a layout of the present invention. The aforesaid naphtha feed 1 is sent to a first catalytic reforming unit 2 comprising at least one reactor having a bed of catalytic reforming catalyst, for example as a fixed bed or as a moving bed. The first reforming unit operates in the presence of a catalyst that can be used to optimize the conversion of naphthene (cycloalkane) and / or paraffinic hydrocarbon compounds to aromatic hydrocarbon compounds and under operating conditions. In order to limit the formation of coke in the reforming catalyst, the reforming step is carried out in the presence of hydrogen.

The catalyst used in this first reforming unit 2 comprises a carrier and an active metal phase, such as platinum. Preferably, the metal, especially platinum, is associated with another element (accelerator) selected from Re, Sn, In, P, Ge, Ga, Bi, B, Ir and rare earths, or any combination of these elements. The carrier is preferably alumina.

This first catalytic reforming unit is operated under the following operating conditions:

420℃ 내지 600℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 420 ° C to 600 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

0.5 내지 8 h^-l 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도.

From 0.5 to 8 h ^-l, weight space velocity, expressed as the ratio of the mass flow rate of feed to the catalyst weight.

In a preferred embodiment, the first catalytic reforming unit is operated under conditions that promote the dehydrogenation reaction of naphthene present in the naphtha feed. The reactions for the cyclic hydrogen elimination reaction of paraffins to aromatics are slower than the naphthenic dehydrogenation reactions and thus paraffins are scarcely converted in this first reforming step. Therefore, the first reforming step is preferably carried out under the following conditions:

420℃ 내지 500℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 420 ° C to 500 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

2.5 내지 8 h^-l 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도.

2.5 to 8 h ^-l, weight space velocity, expressed as the ratio of the mass flow rate of feed to the catalyst weight.

In this preferred embodiment, it is preferred that the reforming catalyst comprises an alumina support and a chlorine content of less than 0.1 wt.%, Preferably less than 0.05 wt.%, Based on the catalyst weight. According to a highly preferred embodiment, the catalyst for the first reforming step is platinum / tin of the alumina type with a chlorine content of less than 0.1% by weight, preferably less than 0.05% by weight, based on the total catalyst weight.

The first catalytic reforming unit 2 comprises in particular an effluent 3 containing an aromatic hydrocarbon compound obtained from the conversion of naphthene and / or paraffin (preferably naphthene) and a non-converted nonaromatic compound, as well as a hydrogen stream 4). The hydrogen stream 4 is sent, for example, to the hydrotreating unit of the refinery or sent to the second catalytic reforming unit.

The effluent 3 is sent to a cut point separation unit 16, for example a fractionation tower. The separation unit 16 separates the effluent 3 into two fractions: an oil (6: C6 ^- ) oil containing a hydrocarbon containing up to 6 carbon atoms and a hydrocarbon containing 7 or more carbon atoms (7: C6 ⁺ ), or alternatively, an oil (6; C7 ^- ) containing a hydrocarbon containing up to 7 carbon atoms and at least 8 carbon atoms including a hydrocarbon-containing fraction; are designed to be separated into (7 fractions labeled C ₈ ^+). The C6 ^- or C7 ^- hydrocarbon oil rich in linear hard paraffins is then treated in the isomerization unit 11 from which a high octane gasoline fraction (isomerate) is produced and sent to the gasoline pool through line 12. Isomerization units can be used to transform n-paraffins (straight chain paraffins) with lower octane number into iso-paraffins (branched chain paraffins) with higher octane number. Since the isomerization reaction is slightly exothermic and at a pressure of 0.2 to 0.8 MPa and from 1 to 3 h ^-l space velocity (hourly space velocity; the HSV = volume flow rate of feed (㎥ / h) / volume catalyst (㎥)) Lt; RTI ID = 0.0 > 110 C < / RTI > The method of the invention by the hard C6 isomerization reaction to consume less energy than the reforming ^reaction is to increase the octane number of a hydrocarbon oil fraction ^- or C7. In practice, hard paraffins are difficult to convert to aromatics, and this transformation therefore requires high temperatures involving hydrodialkylation which leads to the formation of coke in the catalyst and undesired reactions of polycondensation.

As also seen in Figure 1, heavy paraffins and possibly the C7 ⁺ or C ₈ + hydrocarbon fraction containing non-converted naphthenes is, the second is sent to catalytic reforming unit (8), reformate for high octane number from there (10) and hydrogen stream (9) are produced. This second catalytic reforming step is intended to convert non-converted non-aromatic hydrocarbon compounds (paraffins and / or naphthenes) into aromatic hydrocarbon compounds.

In order to limit the formation of coke in the reforming catalyst, the reforming step is carried out in the presence of hydrogen.

The operating conditions used in the second catalyst reforming step are as follows:

420℃ 내지 600℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 420 ° C to 600 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

0.5 내지 8 h^-l 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도.

From 0.5 to 8 h ^-l, weight space velocity, expressed as the ratio of the mass flow rate of feed to the catalyst weight.

Because of the fractionation step, it is possible to operate this second catalyst reforming step under more stringent conditions in order to convert the hard paraffin to aromatics, taking into account that hard paraffins of hard C7 ^- oil are not sent to the second catalytic reforming unit Do. Thus, the second reforming step is operated at a higher temperature and / or a longer residence time than in the first reforming step:

500℃ 내지 600℃ 의 평균 반응기 입구 온도;

An average reactor inlet temperature of 500 ° C to 600 ° C;

0.3 내지 1 MPa 의 압력;

A pressure of 0.3 to 1 MPa;

0.2 내지 8 mol/mol 의 H₂/공급물 몰 비;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

0.5 내지 2.5 h^-l 의, 촉매 질량에 대한 공급물의 질량 유량의 비로서 표현되는 중량 공간 속도.

0.5 to 2.5 h ^-1 , expressed as the ratio of the mass flow rate of the feed to the mass of the catalyst.

The reforming catalyst used in the second reforming step may be the same as that used in the first reforming step. Preferably, a catalyst comprising an alumina support and an active metal phase, such as platinum, is used. Preferably, the metal, particularly platinum, is associated with one or more elements (accelerators) selected from Re, Sn, In, P, Ge, Ga, Bi, B, Ir and rare earths, or any combination of these elements. Most preferably, the catalyst for the second catalyst modification is present in an amount of from 0.8% to 1.5% by weight, preferably from 0.8% to 1.2% by weight, more preferably from 0.9% to 1.1% Respectively. In a preferred embodiment, the catalyst in the second reforming step comprises an alumina support, platinum and tin, and is present in an amount of from 0.8% to 1.5% by weight, preferably from 0.8% to 1.2% by weight, more preferably from 0.9% And a chlorine content of from about 1% to about 1.1% by weight.

In a preferred embodiment, in the first reforming unit, the catalyst having activity toward dehydrogenation of platinum / tin naphthene in the alumina type has a chlorine content of less than 0.1 wt%, preferably less than 0.05 wt% And in the second reforming unit, a catalyst having a high activity of paraffinic cyclic hydrogen elimination reaction of platinum / tin in the alumina type is used in an amount of 0.8 to 1.5 wt%, preferably 0.8 to 1.2 wt% %, More preferably 0.9% to 1.1%, by weight of the composition.

As shown in Fig. 1, the high octane reformate 10 obtained from the second catalytic reforming unit 8 is entirely transferred to the gasoline pool via line 16. [ Alternatively, a portion of the reforming oil is sent to the gasoline pool and another portion is sent to the aromatics complex.

"Aromatic complex" means a process for the transalkylation or disproportionation of various fractions and / or aromatics, regardless of adsorption, distillation, extraction distillation, liquid-liquid extraction or crystallization A combination of units for the isomerization of xceline with or without a conversion unit not related to aromatic rearrangement, a selective or other aromatic dialkylation or alkylation unit, or with the desilylation of ethylbenzene. The products from the aromatic complexes are predominantly petrochemical intermediates such as benzene, para-xylene, ortho-xylene, meta-xylene, xylene oil, ethylbenzene, monomer styrene, cumene or straight chain alkylbenzenes or toluene or heavy aromatic oils Which is a constituent of the gasoline base.

Optionally, as shown in Figure 1, the naphtha feed (1) is fed to the first catalyst reforming step (1) such that the naphtha feed is in specifications in terms of sulfur, nitrogen and / or olefinic and diolefinic compound contents, Is processed in the hydrotreating unit (15) before being sent to the < / RTI >

According to an alternative embodiment (not shown), the naphtha fraction is sent to a separation unit, for example a distillation column, which is configured to separate C4 ^- hydrocarbon oil fraction and C5 ⁺ hydrocarbon fraction, and the C5 ⁺ fraction is used for catalyst modification Is sent to the first step a).

Yes

The following example compares two process layouts: a layout according to the invention (according to FIG. 1), and a layout not according to the invention without a cut-point separation unit.

In both cases, the feed considered had the following composition:

In a process not according to the invention, the naphtha feed was sent to a catalytic reforming unit consisting of four reactors in series, from which a high octane number of reformate and a hydrogen stream were produced. The composition of the effluent obtained from the outlet of the fourth reactor is shown in Table 1 below.

In the process according to the invention, the naphtha feed was sent to a first catalytic reforming unit (2) consisting of two reactors. The effluent (3) from the first catalytic reforming unit (2) was sent to the aromatic separation unit 5, the aromatic separation unit is rigid C7 ^- gave the oil and heavy oil C ₈ ^+. The light C7 ^- fraction was sent to the isomerization unit 11 from which gasoline fractions (isomerates) with high octane number were produced. Heavy C ₈ ⁺ oil fractions were sent to a second catalytic reforming unit 9 consisting of two reactors from which a gasoline fraction 10 (reformate) having a hydrogen stream and a high octane number was produced. This latter was mixed with isomerate; The composition of the mixture is shown in Table 1 below.

In these two cases, the catalytic reforming units were operated under the same conditions:

평균 반응기 입구 온도 = 520℃

Average reactor inlet temperature = 520 ° C

중량 공간 속도 = 2 h^-l (본 발명의 방법 A 의 경우, 케이스 A 와 (본 발명에 따르지 않은) 케이스 B 사이에서 촉매의 양을 일정하게 유지하기 위해 동일한 유량으로 처리하지 않은 제 2 개질 유닛을 위해 중량 공간 속도가 다시 계산되었다는 점에 유의해야 한다)

Weight space velocity of 2 h = ^-l (the case of the method A of the invention, A case with (the second reforming unit is not treated in the same flow rate in order to maintain a constant amount of catalyst between the case B not according to the present invention) It should be noted that the weighted space velocity was recalculated)

상대 압력 = 0.5 MPa

Relative pressure = 0.5 MPa

H₂/공급물 몰 비 = 2.

H ₂ / feed molar ratio = 2.

The catalyst used in the examples was platinum / tin in a chlorinated alumina catalyst.

Isomerization of the hard C7 ^- olefins was carried out in the presence of platinum and hydrogen in a chlorinated alumina isomerization catalyst and under the following conditions:

평균 반응기 입구 온도 = 120℃

Average reactor inlet temperature = 120 ° C

공간 속도 = 1.2 h^-l

Space velocity = 1.2 h ^-l

상대 압력 = 0.30 MPa

Relative pressure = 0.30 MPa

H₂/공급물 몰 비 = 0.2.

H ₂ / feed molar ratio = 0.2.

Table 1 below compares the production of recycle octane value (RON), hard reformate (C5 ⁺ ) and the coke content in the catalyst of the fourth reforming reactor when the layout of the present invention and the layout not according to the present invention are operated do.

As a result of implementing the layout of the present invention, a gain of 2.4% in C5 ⁺ yield was obtained as compared with the layout not according to the present invention.

Further, in the case of the layout of the present invention, a reduction of 1 wt% of coke in the catalyst of the fourth reactor was observed.

Treating the effluent obtained from the first catalytic reforming unit in the cut-point distillation means that the conditions for the deformation of each fraction can be adjusted. Since hard paraffin is difficult to modify, the reforming step requires stringent operating conditions, which may lead to severe cracking and formation of hard compounds (C1-C4). In the layout of the present invention, it is advantageous that the hard paraffin of the C7 ^- fraction is sent to the characterization stage, where cracking is limited because the temperature condition is milder; This is why it is observed that the yield of the hard compound is reduced and the C5 ⁺ yield is increased.

In addition, the layout of the present invention can be used to reduce the cost of conventional catalytic reforming equipment, since isomerization units require lower investment and consume less energy to operate.

Claims (13)

A process for producing gasoline starting from a naphtha fraction (1) comprising paraffins and naphthenes, having an octane number of more than 95,
a) feeding the naphtha oil fraction to a first catalytic reforming unit (2) in which the naphtha oil fraction is contacted with the reforming catalyst to convert at least a portion of the paraffin and / or naphthene to an aromatic compound and to produce hydrogen step;
b) withdrawing the first effluent (3) and the hydrogen stream (4) from the first catalytic reforming unit (2);
c) C6 containing straight chain paraffins ^- hydrocarbon fraction 6 and the non-converted paraffins ^- hydrocarbon fraction 6 and the non-converted paraffins and / or naphthenes containing C7 ⁺ hydrocarbon fraction (7) or C7 containing straight chain paraffins which and / or steps to remove the C ₈ ⁺ hydrocarbon fraction (7) containing the naphthenic, sending the first effluent (3) to the separation unit (5);
d) an isomerization unit (11) in which said straight chain paraffin is brought into contact with said isomerization catalyst to convert said straight chain paraffins to branched chain paraffins and to produce an isomerate (12) Feeding the C6 ^- hydrocarbon oil fraction or the C7 ^- hydrocarbon oil fraction to the reaction vessel;
e) the non-converted paraffins and / or for converting naphthenes to aromatics, the second catalytic reforming unit 8 in the C7 ⁺ hydrocarbon fraction or the C ₈ ⁺ sending the hydrocarbon oil;
f) withdrawing a reformate (10) containing an aromatic compound from the second catalyst reforming unit (8); And
g) sending all of the reforming oil 10 to the gasoline pool 17 or sending part of the reforming oil 10 to the aromatic complex unit 14 and transferring another part of the reforming oil 10 to the gasoline pool 17 To the gasoline pool 17
≪ / RTI > The method according to claim 1,
Wherein the naphtha fraction is pretreated in the hydrotreating unit (15) before step a). 3. The method according to claim 1 or 2,
Wherein the naphtha fraction is sent to a separation unit configured to separate C4 ^- fraction and C5 ⁺ fraction, and wherein the C5 ⁺ fraction is sent to step a). 4. The method according to any one of claims 1 to 3,
The step a) of the first catalyst modification and the step e) of the second catalyst modification,

An average reactor inlet temperature of 420 ° C to 600 ° C;

A pressure of 0.3 to 1 MPa;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

From 0.5 to 8 h ^-l, weight space velocity, expressed as the ratio of the feed mass flow rate for the catalyst mass (weight hourly space velocity)
Lt; / RTI > 5. The method according to any one of claims 1 to 4,
Wherein the first catalyst reforming step a)

An average reactor inlet temperature of 420 ° C to 500 ° C;

A pressure of 0.3 to 1 MPa;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

Of from 2.5 to 8 h ^-l, weight space velocity, expressed as the ratio of the feed mass flow rate for the catalyst mass
Lt; / RTI > 6. The method according to any one of claims 1 to 5,
The step e) of the second catalyst modification comprises:

An average reactor inlet temperature of 500 ° C to 600 ° C;

A pressure of 0.3 to 1 MPa;

A H ₂ / feed molar ratio of 0.2 to 8 mol / mol;

0.5 to 2.5 h ^-l, the weight space velocity, expressed as the ratio of the mass flow rate of feed to the catalyst mass
Lt; / RTI > 7. The method according to any one of claims 1 to 6,
Wherein the naphtha oil fraction is obtained from at least one of the following units: atmospheric distillation, FCC, coke making, steam cracking, hydrocracking, and natural gas condensate fractionation. 8. The method according to any one of claims 1 to 7,
Wherein the catalyst for reforming used in steps a) and e) comprises an alumina carrier and platinum. 9. The method of claim 8,
Wherein the reforming catalyst is promoted by one of the following elements: Re, Sn, In, P, Ge, Ga, Bi, B, Ir, or rare earth. 10. The method according to claim 8 or 9,
Wherein the catalyst for catalyst modification of step a) has a chlorine content of less than 0.1% by weight, preferably less than 0.05% by weight, based on the total catalyst weight. 11. The method according to any one of claims 8 to 10,
Wherein the catalyst for step (e) has a chlorine content of from 0.8% to 1.5% by weight, preferably from 0.8% to 1.2% by weight, more preferably from 0.9% to 1.1% by weight, based on the total catalyst weight . 12. The method according to any one of claims 1 to 11,
Wherein the first and second catalytic reforming units are operated in the continuous regeneration mode using the same catalyst,
Wherein the first catalytic reforming unit comprises at least one reactor and the second catalytic reforming unit comprises at least one reactor and a catalyst regenerator wherein the regenerated catalyst moves in a reactor of the first catalytic reforming unit. 12. The method according to any one of claims 1 to 11,
Wherein the first and second catalytic reforming units use different catalysts and also operate in a continuous regeneration mode,
Wherein the first catalytic reforming unit comprises at least one reactor and a catalyst regenerator, and wherein the second catalytic reforming unit comprises at least one reactor and a catalyst regenerator.

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