CN104178211B

CN104178211B - The selective desulfurization of FCC gasoline

Info

Publication number: CN104178211B
Application number: CN201410424806.3A
Authority: CN
Inventors: 加里·G·波德巴拉克; 阿维德·尤德齐斯; 普尔维斯·K·霍; 马赫什·苏布拉马尼扬; 路易斯·西蒙斯
Original assignee: Catalytic Distillation Technologies
Current assignee: Catalytic Distillation Technologies
Priority date: 2010-11-12
Filing date: 2011-11-11
Publication date: 2016-08-24
Anticipated expiration: 2031-11-11
Also published as: CA2817065A1; CN102559257A; WO2012064466A3; CN102559257B; CA2817065C; MY165010A; US20120048778A1; WO2012064466A2; CN104178211A; MX2013005213A

Abstract

The invention discloses the selective desulfurization of FCC gasoline.Disclosing for by high terminal Petroleum, such as ASTM D 86 terminal is the method for the naphtha cut desulfurization higher than 450 °F, higher than 500 °F or higher than 550 °F and containing the sulphur compound that is obstructed.

Description

The selective desulfurization of FCC gasoline

The application be filing date on November 11st, 2011, Application No. 201110356890.6, The divisional application of the Chinese patent application of invention entitled " selective desulfurization of FCC gasoline ".

Cross-Reference to Related Applications

The application is the company of the US Pat Appl Ser 12/862,845 that on August 25th, 2010 submits to Continuous part application, its content is fully incorporated to this by quoting.

Technical field

Embodiment disclosed herein relates generally to a kind of for having high ASTM D86 terminal The method of the desulfurization of gasoline fraction such as FCC naphtha.More specifically, embodiment party disclosed herein Case relates to one and is less than by weight to produce total sulfur content for having high terminal naphtha desulfurization The gasoline fraction of 20ppm.In some embodiments, the total sulfur content of gasoline fraction can be by weight Gauge is less than 10ppm.Can additionally provide gasoline product in other embodiments disclosed herein The control of terminal.

Background technology

Petroleum distillate stream comprises multiple organic chemical components.Generally, these streams are by their boiling range institute Limit, and boiling range determines composition.The process of these streams also affects composition.Such as, catalytic cracking is carried out Or the product of autothermal cracking process comprises alkene (olefin(e), alkynes and the polyunsaturated compounds ratio of high concentration Such as alkadienes) and saturated hydrocarbons (alkane).It addition, these components can be in the various isomers of compound Any one.

From the untreated Petroleum of crude still or the composition of straight-run naphtha mainly by crude oil The impact in source.Petroleum from paraffinic crude oil origin has more saturated straight chain or ring-type Compound.As general rule, most " desulfurization (sweet) " (low-sulfur) crude oil and Petroleum are all Paraffinic.Cycloalkanes crude oil comprises more unsaturation, ring-type and multi-ring compound.More high-sulfur contains The crude oil of amount trends towards being cycloalkane.The process of different straight-run naphthas can be depended on they by Slightly different in the composition caused by crude oil origin.FCC gasoline is the product of catalytic cracking, and Also referred to as cat cracked naphtha, it can be further processed.The gasoline of cracking, especially urge Change the gasoline of cracking, be generally of sufficiently high octane, and their most important purpose of refine it One includes removing of sulphur compound.

In addition to possible distillation or solvent extraction for removing valuable aromatic products, reformation Petroleum or reformate are not usually required to further process.Due to the described stone brain for the method The pretreatment of oil and the stringency of method itself, the Petroleum of reformation there is no sulphur pollution.

Owing to wherein comprising the compound of olefinic and aromatics, therefore from the cracking stone brain of cat cracker Oil has relatively high octane number.In some cases, this fraction can together with the octane of signal portion To account for the half of the gasoline in oil refining pond (refinery pool).Although concentration of olefin in the oil Add octane number, but alkene is generally limited they concentration in the oil, because it is known that they It is contributive for being formed for smog.A kind of attractive alternative is to add in gasoline product Alcohol is with a liter high olefin content, thus rises high-octane rating.The alcohol of such as methanol and ethanol etc can be used As additive.

Cat cracked naphtha (gasoline-range material) has currently comprised the aobvious of the gasoline products pond of the U.S. Write part (> 1/3), and it provide the sulfur of largest portion.In order to defer to product specification or guarantee with Environmental planning is consistent, it may be necessary to remove these sulphur impurities commonly by hydrotreating.Some are used Family needs the sulfur of final products less than 50ppm or at below 10ppm.

Various methods for gasoline-range hydrocarbon-fraction desulfurization can include United States Patent (USP) 5,510,568, 5,595,634、5,779,883、5,597,476、5,837,130、6,083,378、6,946,068、6,592,750、 6,303,020、6,413,413、6,338,793、6,503,864、6,495,030、6,444,118、6,824,676、 7,351,327,7,291,258,7,153,415,6,984,312 and 7,431,827, etc..

High end point FCC gasoline is typically dense than normal boiling range catalytically cracked gasoline has higher sulfur Degree, this needs the higher conversion of sulphur compound to meet sulfur requirement.But, owing to higher concentration is many Substituted benzothiophene (methyl benzothiophene relative to being in normal boiling range catalytically cracked gasoline), right The hydrotreating of high terminal Petroleum becomes challenging.This is owing at polysubstituted benzothiophene In sulphur atom be obstructed bigger and react more slow with hydrogen compared with the sulphur atom in methyl benzothiophene Slow the fact.

In addition to supply higher octane blending ingredients, the Petroleum of cracking is often used as other technique ratio Such as the source olefins in etherificate, oligomeric and alkylation.Naphtha cut is carried out hydrogenation treatment to remove sulfur The olefin(e) compound that also will make in fraction of condition in some are saturated, thus reduce octane and cause The loss of source alkene.It is typically used in and from high end point of fraction, removes the severe operating conditions of sulfur can draw Play the transition loss of alkene.

Additionally, for high end point FCC gasoline hydrodesulfurization method exist need, including side Method has: makes the olefin(e) centent of Petroleum keep to a certain degree, makes to be lost in Petroleum processing procedure Alkene during hydrogenation and recombinant mercaptans are formed minimizes.

Summary of the invention

In one aspect, embodiment disclosed herein relates to a kind of for making full boiling range catalytic cracking stone The method of cerebrol desulfurization, described method comprises the steps: that (a) is by complete to (1) boiling range naphtha stream and (2) Hydrogen is fed to the first distillation column reactor, described (1) full boiling range naphtha stream comprise alkene, alkadienes, Mercaptan and other organosulfur compound and there is the ASTM D86 final boiling point of at least 350 °F；(b), Simultaneously carrying out (i) and (ii) in described first distillation column reactor, wherein, (i) is in described full boiling range Alkadienes in Petroleum and mercaptan in the presence of group VIII metallic catalyst at the first distillation column The rectifying section of reactor contacts, thus occurs to react as follows: the part of (A) mercaptan and alkadienes A part be reacted to form thioether, and/or the part of (B) alkadienes occurs anti-with a part for hydrogen Alkene, and (ii) should be formed, by full boiling range cracked naphtha fractional distillation be the product of distillation containing C5 hydrocarbon and The first heavy naphtha containing sulphur compound；(c) using the first heavy naphtha as first the bottomsstream Reclaim from the first distillation column reactor；D first the bottomsstream and hydrogen are fed to after-fractionating by () In tower reactor；E () is simultaneously carried out (i) and (ii) in described after-fractionating tower reactor, wherein, I () makes at least some of of the organosulfur compound in described first the bottomsstream and hydrogen at hydrogenation React with by other in the rectifying section of described after-fractionating tower reactor in the presence of desulphurization catalyst A part for organosulfur compound changes into hydrogen sulfide, and the first heavy naphtha is separated into by (ii) Two heavy naphtha and ASTM D86 terminal the first middle stone in the range of 270 °F to 400 °F Cerebrol；F described first medium naphtha, unreacted hydrogen and hydrogen sulfide are distillated by () as the second tower top Thing reclaims from after-fractionating tower reactor；G () is by the second scheelite containing the organosulfur compound that is obstructed Cerebrol reclaims from after-fractionating tower reactor as second the bottomsstream；H () evaporates at the bottom of the second tower Go out thing and hydrogen is fed to accommodate in the first fixed bed reactors of Hydrobon catalyst；I () will be obstructed Organosulfur compound contacts to be subject to Hydrobon catalyst with hydrogen in the first fixed bed reactors That hinders organosulfur compound changes into hydrogen sulfide at least partially；And (j) reclaims from the first fixed bed The effluent of reactor.In some embodiments, second the bottomsstream can be with diesel hydrocarbon fraction Described first fixed bed reactors combine to process.

On the other hand, embodiment disclosed herein relates to a kind of for making full boiling range catalytic cracking stone The method of cerebrol desulfurization, described method comprises the steps:

A complete to (1) boiling range naphtha stream and (2) hydrogen are fed to the first distillation column reactor by (), described (1) boils entirely Journey Petroleum comprises alkene, alkadienes, mercaptan and other organosulfur compound and has at least The ASTM D86 final boiling point of 350 °F；

B () is simultaneously carried out in the first distillation column reactor,

I () makes the alkadienes in full boiling range naphtha stream and mercaptan at group VIII metallic catalyst In the presence of in the rectifying section of the first distillation column reactor contact, thus occur as follows Reaction:

(A) part for mercaptan forms thioether with the part reaction of alkadienes, and / or

(B) part for alkadienes forms alkene with the part reaction of hydrogen；With

(ii) it is the product of distillation containing C5 hydrocarbon and containing sulfur by full boiling range cracked naphtha fractional distillation First heavy naphtha of compound；

C first heavy naphtha is returned from the first distillation column reactor by () as first the bottomsstream Receive；

D first the bottomsstream and hydrogen are fed to after-fractionating tower reactor by ()；

E () is simultaneously carried out in after-fractionating tower reactor,

(i) in the presence of Hydrobon catalyst, organic by first the bottomsstream At least some of and the hydrogen of sulphur compound is in the rectifying section of after-fractionating tower reactor Reaction, changes into hydrogen sulfide with the part by other organosulfur compound described, With

(ii) described first heavy naphtha is separated into the second heavy naphtha and ASTM D86 is whole The first medium naphtha o'clock in the range of 270 °F to 400 °F；

(f) using the first medium naphtha, unreacted hydrogen and hydrogen sulfide as the second overhead from Two distillation column reactors reclaim；

(g) using containing be obstructed organosulfur compound the second heavy naphtha as second the bottomsstream from After-fractionating tower reactor reclaims；

H second the bottomsstream and hydrogen are fed to accommodate the first of Hydrobon catalyst and fix by () Bed reactor；

(i) will be obstructed organosulfur compound and hydrogen with Hydrobon catalyst at the first fixed bed reactors Middle contact, to change into hydrogen sulfide at least partially by the organosulfur compound that is obstructed；

J effluent from the first fixed bed reactors is reclaimed by ()；

K () separates unreacted hydrogen and hydrogen sulfide from the effluent from the first fixed bed reactors；

L () separates unreacted hydrogen and hydrogen sulfide from the second overhead；

M at least some of of second overhead and hydrogen are fed to accommodate hydrodesulfurization catalytic by () In second fixed bed reactors of agent, with by the sulphur compound in described second overhead extremely A few part changes into hydrogen sulfide；

N effluent from the second fixed bed reactors is reclaimed by ()；

O () separates at least some of of hydrogen sulfide from the effluent from the second fixed bed reactors, To form the naphtha cut that sulfur content reduces.

On the other hand, embodiment disclosed herein relates to a kind of for full boiling range catalytic cracking stone brain The method of the devulcanization of oil, described method comprises the following steps:

A complete to (1) boiling range naphtha stream and (2) hydrogen are fed to the first distillation column reactor by (), described (1) is complete Boiling range naphtha stream comprises alkene, alkadienes, mercaptan and other organosulfur compound and has at least The ASTM D86 final boiling point of 350 °F；

B () is simultaneously carried out in the first distillation column reactor,

I () makes the alkadienes in full boiling range naphtha stream and mercaptan at group VIII metal catalytic Contact in the rectifying section of the first distillation column reactor in the presence of agent, thus occur Following reaction:

(B) part for alkadienes forms alkene with the part reaction of hydrogen；With

E () is simultaneously carried out in after-fractionating tower reactor,

J effluent from the first fixed bed reactors is reclaimed by ()；

L second overhead is partly condensed by (), and from the condensation portion of the second overhead The uncooled part comprising unreacted hydrogen and hydrogen sulfide of middle separation the second overhead；

(m) by the condensation portion of the second overhead to be fed to after-fractionating tower at least partially anti- Answer in device as backflow；

N () is by the effluent (k) separated, the uncooled part of the second overhead and at least some of The second overhead of condensation be fed in fractionating column separate unreacted hydrogen and hydrogen sulfide, from And reclaim the bottomsstream hydrocarbon-fraction；

O the bottomsstream hydrocarbon-fraction and hydrogen are fed to accommodate the second of Hydrobon catalyst by () In fixed bed reactors, with by least some of conversion of the sulphur compound in the bottomsstream hydrocarbon-fraction Become hydrogen sulfide；

P effluent from the second fixed bed reactors is reclaimed by ()；

Q () separates at least some of of hydrogen sulfide from the effluent from the second fixed bed reactors, To form the naphtha cut that sulfur content reduces；And

R () is from following one or more middle formation gasoline: at least some of and (ii) of (i) naphtha cut Distillation fraction at least some of, the total sulfur content of wherein said gasoline by weight less than about 20 ppm S。

On the other hand, embodiment disclosed herein relates to a kind of for by full boiling range naphtha stream desulfurization The method changed, described method comprises the steps:

B () is simultaneously carried out in the first distillation column reactor,

I () makes the alkadienes in full boiling range naphtha stream and mercaptan at group VIII metal catalytic Contact in the rectifying section of the first distillation column reactor in the presence of agent, thus occur as follows Reaction:

(C) part for alkadienes forms alkene with the part reaction of hydrogen；With

(ii) by full boiling range cracked naphtha fractional distillation be the product of distillation containing C5 hydrocarbon and containing sulfuration First heavy naphtha of compound；

E () is simultaneously carried out in after-fractionating tower reactor,

(f) using the first medium naphtha, unreacted hydrogen and hydrogen sulfide as the second overhead from After-fractionating tower reactor reclaims；

(g) using containing the second heavy naphtha of organosulfur compound of being obstructed as second the bottomsstream Reclaim from after-fractionating tower reactor；

H second the bottomsstream and hydrogen are fed to accommodate Hydrobon catalyst by () first solid Fixed bed reactor；

J effluent from the first fixed bed reactors is reclaimed by ()；

M at least some of of second overhead and hydrogen are fed to accommodate hydrodesulfurization and urge by () In second fixed bed reactors of agent, with by the sulphur compound in described second overhead Change into hydrogen sulfide at least partially；

N effluent from the second fixed bed reactors is reclaimed by ()；

O () separates at least some of of hydrogen sulfide from the effluent from the second fixed bed reactors, Thus form separation H₂The naphtha cut of S；

P () will separate H₂The naphtha cut fractional distillation of S, to form heavy naphtha fraction and intermediate range Gasoline fraction；With

Q heavy naphtha fraction is recycled to the second fixed bed reactors by () at least partially；And

R () is from following one or more middle formation gasoline: (i) product of distillation at least some of, (ii) Naphtha cut at least some of, and (iii) from the first fixed bed reactors effluent at least A part, the total sulfur content of wherein said gasoline is less than about 20ppm S by weight.

In some embodiments, processed high terminal Petroleum can have greater than about 470 °F ASTM terminal；The ASTM terminal of the most greater than about 470 °F；At other The ASTM terminal of greater than about 500 °F in embodiment；The most greater than about 525 °F ASTM terminal；And in yet other embodiments the ASTM terminal of greater than about 550 °F.

Other aspects and advantages of the present invention will become bright from following explanation and appended claims Aobvious.

Accompanying drawing explanation

Fig. 1 is the method for naphtha cut hydrodesulfurization according to embodiment disclosed herein The simple flow figure of schematic form of an embodiment.

Fig. 2 is the method for naphtha cut hydrodesulfurization according to embodiment disclosed herein The simple flow figure of schematic form of an embodiment.

Fig. 3 is the method for naphtha cut hydrodesulfurization according to embodiment disclosed herein The simple flow figure of schematic form of an embodiment.

Detailed description of the invention

In one aspect, embodiment disclosed herein relates to a kind of for high end point FCC gasoline The method of devulcanization.Embodiment disclosed herein relates generally to a kind of have height for making The method of the FCC naphtha devulcanization of ASTM D86 terminal, described high ASTM D86 terminal ratio The most greater than about 350 °F, higher than 400 °F, higher than 450 °F, higher than 470 °F, higher than 500 °F, Higher than 525 °F or higher than 550 °F.More specifically, embodiment disclosed herein relates to making high terminal Naphtha desulfurization is with the method preparing the total sulfur content gasoline fraction by weight less than 20ppm. In some embodiments, the total sulfur content of gained gasoline fraction can be less than 10ppm by weight. Other embodiments disclosed herein can additionally provide the control of the terminal to gasoline product.

" recombinant mercaptans " refers to as used in this article: be not the mercaptan in the charging of this method, But by H produced by the hydrogenation of sulfur-containing compound in this method₂The reaction of the alkene in S and charging The mercaptan of product.Therefore, recombinant mercaptans need not be destroyed with by the hydrodesulfurization of this method Part I Those mercaptan identical, although they can be identical.

In scope of the present application, wording " catalytic distillation reactor assembly " represents catalytic reaction and product The equipment that the separation of thing occurs at least in part simultaneously wherein.This equipment can include that Conventional catalytic steams Evaporate tower reactor, wherein react and distill and occur under boiling conditions simultaneously, or include combining at least The distillation column of one side reaction device, wherein side reaction device can be as Liquid-phase reactor or boiling point reactors Operate.Although described two kinds of catalytic distillation reactor assemblies all can be better than traditional liquid phase Reaction then separate and preferred, but catalytic distillation tower reactor can have the advantage that parts Number (piece count) reduces, capital cost reduces, the catalyst productivity of every pound of catalyst increases, Heat removal efficiency high (reaction heat can be absorbed into the heat of gasification for mixture) and there is shifting balance Potentiality.Dividing wall type (divided wall) distillation column, wherein at least the one of divided wall column can also be used Part comprises catalytic distillation structure, and described dividing wall type distillation column is considered herein as " catalysis Distillation reactor system ".

Hydrocarbon charging for method disclosed herein can be the sulfur-bearing stone of boiling in gasoline-range Oil distillate, including FCC gasoline, coking pentane/hexane, coking naphtha, FCC naphtha, straight The mixture of two or more in evaporating gasoline, pyrolysis gasoline and flowing containing these.Such gasoline Mixed flow typically have by ASTM D86 distillation measured in the range of 0 °F to 470 °F Normal boiling point.Such charging includes that typical case has about C₆Pumice to the boiling range of 330 Cerebrol；Typical case has about C₅To full range (full range) Petroleum of the boiling range of 420, about The more heavy naphtha fraction of boiling in the range of 260 °F to 412 °F, or at about 330 °F to 470 °F The heavy naphtha of the high terminal of boiling in above scope.

Method disclosed herein is additionally adapted to the devulcanization of " high terminal " petroleum distillate, described " high Terminal " to be defined herein as ASTM D86 terminal be the Petroleum of at least 450 °F to petroleum distillate Fraction.The increase of Petroleum terminal changes the gasoline behavior for hydrodesulfurization, because gasoline Sulfur content increases along with terminal and dramatically increases, so that substantial amounts of existing technique is improper.Additionally, The fraction of higher terminal typically comprises polysubstituted sulphur compound, as it has been described above, include polysubstituted Benzothiophene.The sulfur-containing compound of these high terminals is herein referred to as " be obstructed sulphur compound ", Because poor activity is much in hydrodesulfurization metallization processes for these compounds.In some embodiments, may be used At least 450 °F can be had with the high end point gasoline fraction processed according to processes disclosed herein ASTM D86 terminal；The ASTM D86 terminal of at least 470 °F in other embodiments；? The ASTM D86 terminal of at least 500 °F in other embodiment；The most at least The ASTM D86 terminal of 510 °F；The ASTM D86 of at least 520 °F in other embodiments Terminal；The ASTM D86 terminal of at least 525 °F in other embodiments；And again other The ASTM D86 terminal of at least 550 °F in embodiment.In other embodiments, Ke Yigen The high end point gasoline fraction processed according to embodiment disclosed herein can have at about 450 °F to about ASTM D86 terminal in the range of 550 °F；Can have in other embodiments about ASTM D86 terminal in the range of 470 °F to about 550 °F；And in yet other embodiments In can have the ASTM D86 terminal in the range of about 500 °F to about 520 °F.

Organosulfur compound is mainly as mercaptan, aromatic heterocycle chemical combination present in these gasoline fractions Thing and disulphide occur.The relative quantity of each depends on many factors, be the most much refinery, Technique and charging feature.Typically, more heavy distillat contains more substantial sulphur compound, and these The major part of sulphur compound is the form of aromatic heterocycle compounds.Additionally, usually mixed by gasoline Some stream such as FCC naphtha comprise a large amount of heterocyclic compound.These jeterocyclic chemistries containing significant quantity The gasoline stream of compound is typically difficult to utilize many art methods to process.Point out the most routinely For hydrotreating method so that the harshest operating condition of gasoline stream desulfurization, these operate bar Part causes the loss of olefin(e) centent and big loss of octane (octane penalty).For high end point gasoline The existing method of catalytic distillation successfully do not remove the sulfur of requirement, reason is high terminal The sulfide linkage that is obstructed in Petroleum is difficult to be interrupted.Owing to aromatic heterocycle sulphur compound has and at hydrocarbon substrate In the similar adsorption property of aromatic compounds, the suction that the alternative therefore processed as hydrogen is used Subsidiary formula method has extremely low removing efficiency.

Can be included by the aromatic heterocycle compounds that method disclosed in this application removes: alkyl Substituted thiophene, phenylmercaptan., alkylthrophene, benzothiophene and polysubstituted benzothiophene.Miscellaneous at aromatics Particularly interesting in cycle compound is thiophene, 2-methylthiophene, 3 methyl thiophene, 2-ethyl Thiophene, benzothiophene and dimethyl benzothiophene.Can be removed by method disclosed in this application The mercaptan gone generally comprises 2-10 carbon atom, and the material ratio of example is if any 1-ethyl mercaptan, 2- Propanethiol, 2-butyl mercaptan, 2-methyl-2-propanethiol, amyl hydrosulfide, hexyl mercaptan, heptanthiol, spicy thioalcohol, Nonyl mercaptan and phenylmercaptan..

Sulfur in these gasoline stream can be the one in some molecular forms, including phenylmercaptan., sulfur Alcohol and disulphide.For given gasoline stream, sulphur compound trends towards the higher boiling part at stream (that is, the more heavy distillat of stream) concentrate, be wherein obstructed sulphur compound with higher concentration raise boiling point The most greater than about 350 °F, be especially more than about 450 °F and also the most greater than about 500 °F existence. Sulfur in the higher boiling part of stream may be more difficult to remove, and reason is polysubstituted benzothiophene Concentration raise.It is enriched in the high terminal naphtha stream being obstructed in sulphur compound especially and may adapt to root Process according to embodiment disclosed herein, meet, with preparation, the gasoline-range product that required sulfur specifies Thing.

Use the total sulfur content by weight usually more than 50 of the gasoline stream of method disclosed herein process Ppm, and typically in the range of about 150ppm to the most thousand of ppm sulfur.For bag The fraction greater than about 520 °F of boilings containing at least 5 volume %, sulfur content can exceed that by weight Count about 1000ppm, and 5000 to 10000ppm by weight may be up to, or the highest.

In addition to sulphur compound, including the naphtha feed of FCC naphtha can include paraffin, Cycloalkane and aromatic hydrocarbon, and open chain olefins and cycloolefin, alkadienes and there is the cyclic hydrocarbon of olefinic side chains. In some embodiments, can be used for the charging of the pressure naphtha in method described herein can contain Total olefin concentration in the scope of about 5 to 60 weight %；In other embodiments, containing about Total olefin concentration in the range of 25 to 50 weight %.

Normally, method described herein can be at one or more catalytic distillation reactor assemblies Middle process Petroleum or gasoline fraction.Each catalytic distillation reactor assembly can have one or many The individual one accommodated in hydrogenation catalyst, thioetherification catalyst and/or Hydrobon catalyst or many The reaction zone planted.Such as, reactive distillation zone can be included in stripping section and make change heavier in charging Compound hydrodesulfurization, or be included in rectifying section and make compound hydrodesulfurization lighter in charging, or It is included in both.Hydrogen can also be fed to catalytic distillation reactor assembly, and at some In embodiment, a part for hydrogen can be fed under each corresponding reaction zone.

In each catalytic distillation reactor assembly, make the step that naphtha feed and hydrogen catalysis react Can carry out under the following conditions: temperature in the range of 100 °F to 1000 °F, about 0.1 Pressure to 500 psig, wherein based on feed rate ratio and the granule being wrapped in structure Shape catalyst, at 2 to 2000scf/bbl, at 0.1 to 10hr^-1In the range of weight (hourly) space velocity (WHSV) (WHSV) the hydrogen dividing potential drop in the case of is in the range of 0.01 to 100psi.If using advanced person's (wherein catalyst is to have the catalyst of described structure rather than by described structure to special catalytic structure What body was secured in place is wrapped the form of pellet), the liquid hourly space velocity (LHSV) (LHSV) of this system should When about with the LHSV's of the catalytic distillation antigravity system of the graininess just mentioned or granular base In the scope that scope is identical.In other embodiments, at hydrodesulfurizationof of naphtha distillation column reactor The condition in reactive distillation zone in system is: temperature in the range of 450 °F to 700 °F, Gross pressure in the range of 75 to 300psig, the hydrogen dividing potential drop in the range of 6 to 75psia, The WHSV of the Petroleum in the range of about 1 to 5 and at the hydrogen feed rate ratio of 10-1000scf/bbl.

Distillation column reactor be operated in distillation reaction district in produce liquid and gas simultaneously.The phase of steam When major part is hydrogen, and a part of steam is the hydrocarbon from hydrocarbon charging.Catalytic distillation has carried Going out, the mechanism of the effectiveness producing this technique is the condensation of a part of steam in response system, its The hydrogen that in the liquid of condensation, occlusion is sufficient, thus obtain hydrogen in the presence of a catalyst and the sulfuration of necessity Close contact between compound, to cause their hydrogenation.Specifically, sulfur species is enriched in In liquid, and alkene and H₂S is enriched in steam, thus allow sulphur compound high conversion and The low-conversion of olefin species.

As in any distillation, in catalytic distillation reactor assembly, there is thermograde.Under tower End comprises higher boiling point material, and is therefore at temperature more higher than the upper end of tower.Comprise and be easier to The relatively low boiler cut of the sulphur compound removed suffers relatively low temperature at the top of tower, so can carry For bigger selectivity, i.e. required olefin(e) compound is not hydrocracked or the most saturated.Higher boiling Point part suffers higher temperature in the lower end of distillation column reactor, so that sulphur-containing cyclic is compound cracking Open loop also makes sulfur hydrogenate.Reaction heat only produces and more boils, but does not the most make Temperature rises.Therefore, it can by regulator control system pressure obtain reaction rate and products distribution big Amount controls.

Additionally can be located in one or more fixed bed reactor systems in method disclosed herein Gypsum Fibrosum cerebrol or gasoline fraction, or its selection part.Each fixed bed reactor system can include The reactor of one or more serial or parallel connections, each reactor has one or more accommodating The reaction zone of one or more Hydrobon catalysts.Such fixed bed reactors can be as gas phase Reactor, Liquid-phase reactor or mixed phase (V/L) reactor run, and can include traditional consolidating Fixed bed reactor, trickle bed reactor, pulse-flow reactor, and well known by persons skilled in the art Other type of reactor.Operating condition in fixed bed reactor system can depend on one or Multiple reaction phases, the boiling range of processed naphtha cut, catalyst activity, selectivity, the life-span, With the sulfur for removing needed for each order of reaction, and other factors.

Flowed by the component of processes disclosed herein and provide the abundant place to high terminal naphtha stream Reason, thus be reduced to meet specification and regulation by the total sulfur content of stream.Additionally, process chart provides Process to the high olefin content part of Petroleum under less harsh conditions, maintains the biggest portion The alkene inclusions divided, and thus remain antiknock component.

With reference now to Fig. 1, it illustrates an embodiment of hydrodesulfurization disclosed herein Simplification of flowsheet figure.Hydrogen and Petroleum or other organic sulfur-containing hydrocarbon that the sulphur compound that is obstructed may be comprised Charging, can be fed to the first catalytic distillation reactor assembly 10 via flow line 6 and 8 respectively, Described first catalytic distillation reactor assembly 10 has one or more for hydrocarbon described in hydrotreating The reactive distillation district 12 of charging.As indicated, catalytic distillation reactor assembly 10 includes at least one The individual top being positioned at tower and the reactive distillation district 12 above feed entrance, be used for processing charging In light hydrocarbon components.

Reaction zone 12 can include that one or more are for diene hydrogenation, for mercaptan and alkadienes Reaction (thioetherification), and/or the catalyst for hydrodesulfurization.Such as, react at the first catalytic distillation Condition in device system 10 can provide for the thioetherification of alkadienes and/or the condition of hydrogenation and C in feeding from hydrocarbon₅/C₆Part removes the condition of mercaptan sulfur.C5/C6 portion compared to charging The C5/C6 part dividing the Petroleum of the sulfur content with minimizing can be as the product 16 that sides stream from urging Change in distillation reactor system 10 and reclaim.

Overhead fraction can return from catalytic distillation reactor assembly 10 via flow line 18 Receive, and light hydrocarbon, unreacted hydrogen and hydrogen sulfide can be comprised.First overhead 18 can With cooled, such as use heat exchanger 14 to cool down, and be fed to stripper 20.At vapour In stripper 20, the hydrogen sulfide that can will be contained in overhead fraction separates with hydrocarbon with unreacted hydrogen, The most unreacted hydrogen and hydrogen sulfide take out from stripper 20 via flow line 22.The hydrocarbon of condensation Can take out from stripper 20, and be fed to the first catalysis steaming via flow line 24 and pump 26 Evaporate reactor assembly 10 as all or part of backflow.

The C5/C6 taken out from catalytic distillation reactor assembly 10 via flow line 16 sides stream product Thing can comprise the alkene being much present in hydrocarbon charging.Additionally, two in C5/C6 fraction Alkene can be hydrogenated in the processing procedure in catalytic distillation reactor assembly 10.Thus, this Hydrogenation, the C5/C6 of the desulfurization product that sides stream can use in various techniques.Various embodiment party In case, the C5/C6 product that sides stream is used as gasoline mixed fraction, is hydrogenated and is used as gasoline Mixing raw material, and as the raw material produced for ether, and other possible purposes.C5/C6 evaporates Point process especially or final use can depend on various factors, including as raw-material alcohol can Acquired, and the most admissible concentration of olefin for specified permission, etc..

Heavy naphtha, such as, C7+ boiling range component, it is included in reaction zone 12 any of formation Thioether and other sulfur various in hydrocarbon feeds and be obstructed sulphur compound, can be as the bottomsstream Fraction reclaims from catalytic distillation reactor assembly 10 via flow line 20.React at catalytic distillation Device system 10 tower in stripping section include reaction zone in the case of, or entering reaction zone 12 In the case of C7+ component is boiled, the bottomsstream fraction of recovery can at least partly be taken off Sulfur.

Then the bottomsstream fraction reclaimed via flow line 20 is fed to the second catalytic distillation Reactor assembly 30, described second catalytic distillation reactor assembly 30 comprises one or more receiving There is the reaction zone of one or more Hydrobon catalysts.Hydrogen can be fed to urge via flow line 28 Change distillation reactor system 30.

In some embodiments, catalytic distillation reactor assembly 30 can comprise instead in rectifying section Answer district 32, for making at least some of of described organosulfur compound in hydrocarbon charging react with hydrogen, Thus at least one of organosulfur compound is changed into hydrogen sulfide.Catalytic distillation reactor assembly 30 can operate under certain condition, to promote above-mentioned reaction and hydrocarbon to be fed separation and attach most importance to simultaneously Naphtha cut and ASTM D86 terminal in the range of about 270 °F to about 400 °F first in Between naphtha cut, described first medium naphtha fraction reclaims via flow line 36 and evaporates as tower top Going out thing to reclaim, described heavy naphtha fraction reclaims via flow line 54 as the bottomsstream fraction.

If it is required, catalytic distillation reactor assembly 30 can every at the rectifying section of tower and stripping section One includes distillation reaction district 32,34, so that steaming when heavy end moves downwards through catalysis Can be at least by partly hydrodesulfurization when evaporating reactor assembly 30.In this case, hydrocarbon is permissible Via flow line 28b descending most charging below reaction zone, or it is alternatively possible to warp the most respectively Fed below reactive distillation district 32 and 34 is respective by flow line 28a and 28b.

The overhead product reclaimed from catalytic distillation reactor assembly 30 via flow line 36 Middle distillate hydrocarbon and hydrogen sulfide and unreacted hydrogen can be comprised.Then overhead fraction is permissible Processed, to separate hydrogen and hydrogen sulfide.Such as, overhead fraction can be via using heat exchange The indirect heat exchange of device 40 and partial condensation, and be fed to " tympanites due to heat " 42 so that condensate with not The steam of condensation separates, and described uncooled steam includes hydrocarbon, hydrogen sulfide and hydrogen.Condensate can be through Being reclaimed from drum 42 by flow line 48, one part can be as flowing backward through by pump 46 and flow line 38 are fed to catalytic distillation reactor 30.The remainder of condensate can enter via flow line 51 Expect, and uncooled steam can be fed to " cold drum " 50 via flow line 44.Cold drum 50 is then Can by hydrogen and hydrogen sulfide (it reclaims via flow line 52) with heavy hydrocarbon components (via flow line 68 Reclaim) separate.

The bottomsstream product reclaimed via flow line 54 can have at a relatively high sulphur concentration.So And, it practice, it for make technique have in reaction zone 34 minimum catalyst thus The sulfur leaving high concentration in the bottomsstream product is useful, because this makes to be available for urging Recombinant mercaptans shape in the upper part changing distillation column reactor 30 and the overhead recovery system being correlated with The concentration of the hydrogen sulfide become minimizes.

The bottomsstream fraction reclaimed from catalytic distillation reactor assembly 30 via flow line 54 is (being in temperature of boiling again) of heat, and do not comprise the hydrogen sulfide of pronounced amount, reason is reactive distillation The counter-current flow mode of technique.Then the bottomsstream fraction reclaimed via flow line 54 is fed To fixed bed reactors 60 to carry out other hydrotreating.If necessary or desired, relative to molten The hydrogen other for the hydrogen in the bottomsstream of solution can be fed to fixed bed via flow line 58 Reactor 60.The dividing potential drop of the hydrogen in fixed bed unit is typically greater than about 20psi, such as about Between 25psi to about 350psi, thus it is any sulfur that is obstructed in the heavy ends of hydrocarbon charging 8 Compound removes sulfur and extra driving force is provided.Height can be used in fixed bed reactors 60 Hydrogen concentration because most alkene has been separated and via flow line 16 and 36 reclaim. Additionally, selective hydrodesulfrization catalyst such as Co/Mo catalyst is in fixed bed reactors 60 Use be possible to prevent the saturated of aromatic compounds, thus avoid adjoint loss of octane.Fixed bed is anti- The hydrodesulfurization permission answering device 60 and the produced sulphur compound that is obstructed processes the former of the highest terminal Material, the most even terminal raw material more than 550 °F.

Heavy petrol effluent from fixed bed reactors 60 can reclaim via flow line 62.So After, effluent can be fed to drum 64 via flow line 62, to separate sulfur from liquid hydrocarbon effluent Change hydrogen and unreacted hydrogen.Hydrogen and hydrogen sulfide can take out from drum 64 via flow line 66.Have The hydrocarbon effluent of the sulphur concentration reduced can reclaim via flow line 82.

In some embodiments, the hydrocarbon effluent reclaimed via flow line 82 can be with a kind of or many Kind lighter fraction merges, and reclaims via flow line 16 and 68, for use as gasoline blendstock or For further processing, this will be described below.In other embodiments, heavy hydrocarbon fractions can To process together with the heavy hydrocarbon fractions of the such as diesel hydrocarbon fraction etc fed via flow line 70, To reduce heavy distillat and the sulfur content of diesel oil distillate further.

With reference now to Fig. 2 and 3, it is shown that the letter of the embodiment of hydrodesulfurization disclosed herein Metallization processes flow chart, the most identical numeral represents identical part.Hydrogen and sulfuration of being obstructed can be comprised The Petroleum of compound or the charging of other organic sulfur-containing hydrocarbon can be fed to via flow line 6 and 8 respectively First catalytic distillation reactor assembly 10, described first catalytic distillation reactor assembly 10 has one Individual or multiple reactive distillation districts 12 for hydrocarbon being carried out hydrotreating.As indicated, catalysis Distillation reactor system 10 includes that at least one is positioned at the top of tower and above feed entrance Reactive distillation district 12, to process the light hydrocarbon components in charging.

Reaction zone 12 can include one or more hydrogenation, mercaptan and alkadienes anti-for alkene Should (thioetherification) and/or the catalyst of hydrodesulfurization.Such as, at the first catalytic distillation reactor assembly 10 In condition can be alkadienes thioetherification and/or hydrogenation provides and for from hydrocarbon charging C₅/C₆Part removes mercaptan sulfur and provides.C5/C6 part compared to charging has the sulfur of reduction The C5/C6 part of the Petroleum of content can be as the product 16 that sides stream from catalytic distillation reactor system System 10 recovery.

Overhead fraction can be via flow line 18 from catalytic distillation reactor assembly 10 times Receive, and light hydrocarbon, unreacted hydrogen and hydrogen sulfide can be comprised.First overhead 18 can Such as to use heat exchanger 14 to cool down, and it is fed to stripper 20.In stripper 20, The hydrogen sulfide that can will be contained in overhead fraction separates with hydrocarbon with unreacted hydrogen, the most unreacted Hydrogen and hydrogen sulfide take out from stripper 20 via flow line 22.The hydrocarbon of condensation can be from stripper 20 Take out and be fed in the first catalytic distillation reactor assembly 10 make via flow line 24 and pump 26 For all or part of backflow.

The C5/C6 taken out from catalytic distillation reactor assembly 10 via flow line 16 sides stream product Thing can comprise a lot of alkene being present in hydrocarbon charging.It addition, the diene in C5/C6 fraction Hydrocarbon can be hydrogenated in the processing procedure in catalytic distillation reactor assembly 10.The most this hydrogenation The C5/C6 of the desulfurization product that sides stream can be recycled in various technique.Various embodiment party In case, the C5/C6 product that sides stream is used as gasoline mixed fraction, is hydrogenated and is used as gasoline Mixing raw material, and with acting on the raw material that ether produces, and other possible purposes.C5/C6 evaporates Special handling or the final use divided can depend on various factors, including obtaining of the alcohol as raw material Obtain property, and the most admissible concentration of olefin for specified permission, etc..

Heavy naphtha, such as, C7+ boiling range component, it is included in reaction zone 12 any sulfur formed Ether and other sulfur various in hydrocarbon feeds and be obstructed sulphur compound, can make via flow line 20 Reclaim from catalytic distillation reactor assembly 10 for the bottomsstream fraction.In catalytic distillation reactor system System 10 in exhausting section of column include reaction zone in the case of, or entering reaction zone 12 In the case of C7+ component is seethed with excitement, the bottomsstream fraction of recovery can be taken off at least in part Sulfur.

It is anti-that the bottomsstream fraction reclaimed via flow line 20 is then fed to the second catalytic distillation Device system 30, described second catalytic distillation reactor assembly 30 is answered to comprise one or more receiving one Plant or the reaction zone of multiple Hydrobon catalyst.Hydrogen can be fed to catalysis via flow line 28 and steam Evaporate reactor assembly 30.

In some embodiments, catalytic distillation reactor assembly 30 can comprise in rectifying section Reaction zone 32, for making at least one of organosulfur compound in hydrocarbon charging react with hydrogen, from And at least one of organic sulfur compound is changed into hydrogen sulfide.Catalytic distillation reactor assembly 30 can To operate under certain condition, to promote above-mentioned reaction and hydrocarbon charging to be separated into heavy naphtha simultaneously Fraction and ASTM D86 terminal the first middle stone brain in the range of about 270 °F to about 400 °F Oil distillate, wherein said first medium naphtha fraction returns as overhead via flow line 36 Receive, and described heavy naphtha fraction reclaims as the bottomsstream fraction via flow line 54.

If it is required, catalytic distillation reactor assembly 30 can every at the rectifying section of tower and stripping section One includes distillation reaction district 32,34, so that heavy end can pass downwardly through catalysis at it By hydrodesulfurization at least in part during distillation reactor system 30.In this case, hydrogen is permissible Via flow line 28b charging below the most beneath reaction zone, or alternatively can steam in reactivity Evaporate district 32 and 34 respective below, the most respectively via flow line 28a and 28b feed.

The bottomsstream product reclaimed via flow line 54 can have the sulfur of at a relatively high concentration.So And, actually this is for making technique have the catalyst of minimum thus at tower in reaction zone 34 It is favourable for having high sulphur concentration in end distillation product, because this makes to be available in catalysis In the top of distillation column reactor 30 and relevant overhead recovery system, recombinant mercaptans is formed The concentration of hydrogen sulfide minimize.

The bottomsstream fraction reclaimed from catalytic distillation reactor assembly 30 via flow line 54 It is hot (being in temperature of boiling again), and does not wraps due to the countercurrent flow mode of reactive distillation technique Hydrogen sulfide containing pronounced amount.The bottomsstream fraction reclaimed via flow line 54 is then fed to solid Fixed bed reactor 60 carries out other hydrotreating.Relative to the hydrogen being dissolved in the bottomsstream Other hydrogen can be fed to fixed bed reactors 60 via flow line 58.In fixed bed unit The dividing potential drop of hydrogen be greater than about 20psi, such as between about 25psi to about 350psi, thus be from Any sulphur compound that is obstructed in heavy ends in hydrocarbon charging 8 removes sulfur and provides other driving Power.High hydrogen concentration can be used, because most alkene is separated in fixed bed reactors 60 And reclaim via flow line 16 and 36.Additionally, selective hydrodesulfrization catalyst such as Co/Mo Catalyst use in fixed bed reactors 60 is possible to prevent the saturated of aromatic compounds, thus keeps away Exempt from adjoint loss of octane.The hydrogenation of fixed bed reactors 60 and the produced sulphur compound that is obstructed takes off Sulfur permission processes the raw material of the highest terminal, processes terminal the most in some embodiments and exceedes The raw material of 550 °F.

Heavy petrol distillation from fixed bed reactors 60 can reclaim via flow line 62.? In some embodiments, a part of effluent in flow line 62 can be such as via flow line 61 entrances being recycled to reactor 60.Then, distillation can be fed to via flow line 62 Drum 64, makes hydrogen sulfide and unreacted hydrogen separate from liquid hydrocarbon effluent.Hydrogen and hydrogen sulfide are permissible Take out from drum 64 via flow line 66.The hydrocarbon effluent of the sulphur concentration with reduction can be via Flow line 82 reclaims.

The overhead product reclaimed from catalytic distillation reactor assembly 30 via flow line 36 Middle distillate hydrocarbon and hydrogen sulfide and unreacted hydrogen can be comprised.Overhead fraction is the most permissible Processed to separate hydrogen and hydrogen sulfide.Such as, overhead fraction can be via using heat exchanger The indirect heat exchange of 40 and partial condensation, and it is fed to " tympanites due to heat " 42 so that condensate is with uncooled Steam separate, described uncooled steam comprises hydrocarbon, hydrogen sulfide and hydrogen.Condensate can be via stream Sending pipe 48 to reclaim from drum 42, one part can be via pump 46 and flow line 38 as flowing back into Expect catalytic distillation reactor 30.The remainder of condensate can feed via flow line 51, And uncooled steam can be fed to " cold drum " 50 via flow line 44.Then, cold drum 50 can With by hydrogen and hydrogen sulfide (reclaiming via flow line 52) with middle and heavy hydrocarbon components (via flow line 68 reclaim) separate.

In some embodiments of hydrodesulfurization disclosed herein, it can reclaim de-aptly Hydrocarbon stream after sulfur, this hydrocarbon stream includes midbarrel and heavy end simultaneously.With reference now to Fig. 1, necessary Time, the heavy petrol effluent of the separation reclaimed from drum 64 via flow line 82 can be fed to cold Drum 50, additionally to remove hydrogen and hydrogen sulfide, and returns together with midbarrel via flow line 68 Receive for further processing.Heavy petrol effluent can alternatively with midbarrel drum 50 times Trip merges.

Merge heavy and midbarrel then can feed via flow line 68 and hydrogen is via stream Pipe 72 is sent to be fed to accommodate the second fixed bed reactors 74 of Hydrobon catalyst.The weight of desulfurization Gasoline fraction thus can serve as heavy inert diluent, at the second fixed bed reactors 74 In the hydrodesulfurization of midbarrel.Second fixed bed reactors 74 may be particularly useful in and remove mercaptan With the recombinant mercaptans sulfur formed in overhead system and be present in midbarrel.Then, from The effluent of two fixed bed reactors 74 can be fed to stripper 80 via flow line 76 so that hydrogen With the centre of hydrogen sulfide (reclaiming via flow line 78) and hydrodesulfurization and heavy naphtha (via stream Pipe 84 is sent to reclaim) separate.

In some embodiments, method disclosed herein can provide the centre reclaimed as product The control of the terminal of gasoline fraction.With reference now to Fig. 2, midbarrel can via flow line 68 also And hydrogen is fed to accommodate the second fixed bed reactors of Hydrobon catalyst via flow line 72 In 74.Then effluent from the second fixed bed reactors 74 can feed via flow line 76 To stripper 80, so that the middle vapour of hydrogen and hydrogen sulfide (reclaiming via flow line 78) and hydrodesulfurization Oil distillate (reclaiming via flow line 84) separates.

Then middle gasoline fraction can be fed to knockout tower 92, with the middle vapour of fractional distillation hydrodesulfurization Oil distillate, thus reclaim lightweight medium naphtha fraction and via flow line via flow line 94 86 reclaim heavy naphtha fraction.The control of the terminal of medium naphtha fraction can be by knockout tower The operating condition used in 92 controls.The medium naphtha fraction with higher terminal can separate Tower 92 use higher temperature and/or lower pressure realize.

In some embodiments, the heavy naphtha fraction reclaimed via flow line 86 can be with recirculation It is used as heavy inert diluent as above to fixed bed reactors 74.Via flow line 82 from A part for the heavy gasoline that drum 64 reclaims can also be fed to the second fixed bed via flow line 90 Reactor 74 is for use as diluent, thus is the end of the medium naphtha reclaimed via flow line 94 The additionally control of point provides heavy hydrocarbon, and the control for the temperature of boiling again in knockout tower 92 provides weight Material.When needing, the heavy hydrocarbon being recycled to fixed bed reactors 74 from knockout tower 92 is permissible Take out via flow line 98, and reclaim together with the heavy gasoline fractions in flow line 82.

In the structure shown in Fig. 2, the heavy end reclaimed via flow line 82 can serve as diesel oil Gasoline fraction.In this case, it can make the aromatic compounds in heavy gasoline fractions aptly Thing is saturated.Therefore, purifier can select Ni/Mo catalyst, Co/Mo catalyst, Ni/W Catalyst or their mixture are loaded in fixed bed reactors 60, advise with the diesel oil of satisfied locality Lattice.

In order to produce the gasoline product with low sulfur content of high terminal, the most in some embodiments It is by weight less than 50ppm, and is less than 20ppm or 10ppm in other embodiments Sulfur, can have less than about 150 by weight via flow line 68 from the hydrocarbon that drum 50 reclaims The target sulphur concentration of the sulfur of ppm.In some embodiments, the hydrocarbon reclaimed via flow line 68 Target sulphur concentration can be by weight the sulfur less than 125ppm；It is in other embodiments Sulfur less than 100ppm by weight；And be 50ppm by weight in yet other embodiments Sulfur to 100ppm.

Can every at catalytic distillation reactor assembly 10,30 and fixed bed reactor system 60,74 The operating condition used in one provides in table 1 below.Such condition can be used for realizing described in detail above Target product sulphur concentration.

Table 1

The catalyst that can use in the first catalytic distillation reactor column can be characterised by as thioether Change catalyst or be alternatively used as hydrogenation catalyst.In the first catalytic distillation reactor column, alkadienes Reaction with sulphur compound is selective relative to hydrogen with the reaction of olefinic bonds.Preferably catalyst is Palladium as shown in United States Patent (USP) 5,595,643 and/or nickel or Ni/Pd double bed (this United States Patent (USP) It is incorporated herein by reference in 5,595,643) because in the first catalytic distillation reactor column, sulfur Implement together with removing being intended that of the preservation with alkene.Although metal deposits usually used as oxide, But can be to use other form.In hydrogenation process, nickel considered to be in sulphided form.

Another catalyst being suitably used for thioetherification reaction can be at 7 to 14 mesh alumina balls 0.34 weight %Pd, this catalyst is supplied by Sud-Chemie, and named G-68C.Urge Agent can also is that the form of the ball with diameter similar.They can be loaded directly into the one way of standard In fixed bed reactors, it includes carrier and reactant distribution structures body.But, in their routine In form, they form block the compactest for operation in catalytic distillation reactor assembly tower Body, thus must prepare with the form of catalytic distillation structures.Catalytic distillation structures must be able to rise The effect of catalyst and play a part mass transfer media.Catalyst must suitably be supported in tower and Separate to serve as catalytic distillation structures.

In the case of without wishing to be bound by any specific theory, catalyst is considered as in operation The hydride of the palladium produced.Hydrogen ratio in catalytic reactor must be enough to make catalyst keep activity Form because hydrogen due to hydrogenation from catalyst loss, but be held below causing the overflow of tower (flooding) level, this is considered as terminology used in this article " hydrogen of effective dose ".Logical Chang Di, hydrogen is at least 1.0 to 1.0 with the mol ratio of the alkadienes in charging and acetylene class, and excellent Select 2.0 to 1.0.

Second and the catalytic distillation reactor column subsequently used in embodiment disclosed herein with In catalytic fixed bed reaction zone, the purpose of catalyst can be to destroy sulphur compound to produce containing sulfuration The hydrocarbon stream of hydrogen, this hydrogen sulfide is easily and Component seperation heavier in hydrocarbon stream.As it has been described above, hydrogen and sulfuration Hydrogen can separate with heavy hydrocarbon components in stripper.Occur after the first catalytic distillation reactor column These catalytic reactions focus on the destructive hydrogen implementing sulfide and other organosulfur compound Change.

The catalyst of Hydrobon catalyst is can be used as in the reaction zone of catalytic distillation reactor assembly The single group VIII metal being included on suitable carrier, such as cobalt, nickel, palladium, or and other The group VIII metal of metal such as molybdenum or tungsten combination, such as cobalt, nickel, palladium, described suitable load Body can be aluminium oxide, silica-alumina, titania-zirconia, or the like.Normally, Metal provides as the oxide form of the metal being supported on extrudate or sphere, and this is obstructed It is commonly used for distillation structure body.Alternatively, catalyst can be wrapped in suitable catalytic distillation structures In, described catalytic distillation structures is characterised by that the fixed bed that can accommodate typical case's manufacture of wide scope is urged Agent size.

Catalyst can comprise V, VIB, group VIII metal or its mixture from periodic chart Component.The combination of distillation column reactor system can reduce deactivating of catalyst, and can provide Operation than the fixed bed hydrogenation reactor longer time of prior art.Group VIII metal is all right The overall average activity increased is provided.Containing vib metals such as molybdenum and group VIII metal such as The catalyst of cobalt or nickel is preferred.Be suitable for the catalyst of hydrodesulfurization reaction include cobalt-molybdenum, nickel- Molybdenum and nickel-tungsten.Metal is generally to be supported on such as aluminium oxide, silica-alumina etc. at the bottom of neutral radical Oxide form exist.Metal in use or passes through to be exposed to containing sulfuration before the use Stream and the hydrogen of compound and be converted into sulfide.

Catalyst can also be catalyzed the hydrogenation of alkene and the alkadienes being included in light cracked naphtha, And the isomerisation degree making some monoolefines is less.Hydrogenation, the especially list in lighter fraction The hydrogenation of alkene is probably undesirable.

It is 1.5:10 that catalyst is typically in a diameter of 1/8,1/16 or 1/32 inch and L/D The form of extrudate.Catalyst can also be the spherical formula with similar diameter.They can be direct Be loaded in standard single pass fixed bed reactors, described standard single pass fixed bed reactors include carrier and Reactant distribution structures body.But, in they conventionally forms, they are formed at catalytic distillation Block too closely for operation in reactor assembly tower, thus must be with catalytic distillation structures Prepared by form.As it has been described above, catalytic distillation structures has allowed for the work of catalyst and mass transfer media With.Catalyst must suitably be loaded and is spaced in tower, to serve as catalytic distillation structures.

In some embodiments, catalyst is accommodated in such as United States Patent (USP) 5, disclosed in 730,843 Structure in, this United States Patent (USP) is incorporated herein.In further embodiment, Catalyst is accommodated in multiple silk screen (wire mesh) pipe, described wire mesh tube close at either end and Across laid on screen fabric sheet such as demister.Then described and pipe are rolled into bundle to be loaded into steaming Evaporate in tower reactor.This embodiment is described in such as United States Patent (USP) 5, in 431,890, the described U.S. Patent is incorporated herein.Other useful catalytic distillation structures is disclosed in United States Patent (USP) 4,731,229,5,073,236,5,431,890 and 5, in 266,546, these United States Patent (USP)s described are passed through Quote and be each incorporated herein.

Can also above with respect to the Hydrobon catalyst described by the operation of catalytic distillation reactor assembly In fixed bed catalytic reactor.In the embodiment selected, for fixed bed catalytic reactor In catalyst can include the Hydrobon catalyst that only promotes mercaptan species desulfurization, mercaptan substance kind In being easiest to be converted into the species of hydrogen sulfide.Including high temperature and the fixed-bed catalytic of high hydrogen molfraction It is saturated that condition in reactor contributes to alkene.For keeping olefin(e) centent under these conditions and inciting somebody to action For mercaptan is converted into hydrogen sulfide, suitable catalyst can include using low-down molybdenum co-catalysis Raney nickel, or the Raney nickel entirely without promoter；And use low-down copper to help to urge The molybdenum catalyst changed, or the molybdenum catalyst entirely without promoter.Such catalyst may tool There is relatively low hydrogenation activity, thus promote the de-of mercaptan species in the case of significantly loss alkene Sulfur.

Effluent stream from catalytic distillation reactor assembly can condense in one or more levels, makes Hydrocarbon separates with hydrogen sulfide and hydrogen.As it has been described above, it can advantageously use the cold drum system of tympanites due to heat Limit the formation of recombinant mercaptans.The hydrogen reclaimed can be compressed and is recycled to specifically described herein adding In the various piece of hydrogen desulphurization system.

As it has been described above, heavy hydrocarbon is used as the fixed bed reaction in embodiment disclosed herein Diluent in device 74.Dilution can cause the driving force for back reaction (recombinant mercaptans formation) Reduce and contribute to alkene and preserve.Heavy gasoline fractions recirculation can dilute that to be fed to fixed bed anti- Answer the alkene in the overhead fraction of device and hydrogen sulfide.This can reduce for carrying in fixed bed reactors The amount of the hydrogen required for confession dilution, and also the pressure drop at relevant control valve two ends can be reduced.Fixed bed This non-hydrogen dilution of reactor feed and then can reduce the power run required for compressor, this returns Because of in the hydrogen freight volume reduced.

As it has been described above, embodiment disclosed herein can provide the production for high end point gasoline, than As reclaimed by one or more flow lines 94,84 and 82, there is being less than by weight 50,20 or the total sulfur content of even 10ppm.

After processing according to method described herein, the C5/C6 side reclaimed via flow line 16 The sulfur content of fraction product can be less than about 50ppm in some embodiments；Other embodiment party Less than 40ppm in case；In other embodiments less than 30ppm；The least In 20ppm；In other embodiments less than 10ppm；In other embodiments less than 5ppm； And less than 1ppm in yet other embodiments, above-mentioned each of which is based on weight meter.

After processing according to method disclosed herein, via the sulfur of the hydrocarbon-fraction that flow line 82 reclaims Content can be less than about 50ppm in some embodiments；In other embodiments less than 40 ppm；In other embodiments less than 30ppm；In other embodiments less than 20ppm； In other embodiments less than 10ppm；In other embodiments less than 5ppm；And Less than 1ppm in yet other embodiments, above-mentioned each of which is based on weight meter.

After processing according to method disclosed herein, the intermediate hydrocarbons fraction reclaimed via flow line 94 Sulfur content can be less than about 50ppm in some embodiments；The least In 40ppm；In other embodiments less than 30ppm；In other embodiments less than 20 ppm；In other embodiments less than 10ppm；In other embodiments less than 5ppm；With And less than 1ppm in yet other embodiments, above-mentioned each of which is based on weight meter.

After processing according to method disclosed herein, the heavy hydrocarbon fractions reclaimed via flow line 82 Sulfur content can be less than about 50ppm in some embodiments；The least In 40ppm；In other embodiments less than 30ppm；In other embodiments less than 20 ppm；In other embodiments less than 10ppm；In other embodiments less than 5ppm；And And less than 1ppm in yet other embodiments, above-mentioned each of which is based on weight meter.

Relative to typical hydrodesulfurization, typical hydrodesulfurization generally uses the behaviour of harshness Make condition, cause the heavy losses of alkene, and by the product of desulfurization produced by processes disclosed herein The alkene of signal portion can be kept, cause the product of the terminal (end) of much higher value.Implement at some In scheme, method disclosed herein the total concentration of olefin of the product that produces can be in 5 to 55 weight % In the range of；In other embodiments in the range of about 10 to about 50 weight %；And In other embodiment in the range of about 20 to about 45 weight %.Compared to initial hydrocarbon charging (flow line 8), the total product stream reclaimed from embodiment disclosed herein (includes for corresponding real The suitable flow line of scheme of executing 16,94,82 and 84) alkene in initial hydrocarbon charging can be kept At least 25%；At least 30% of alkene during initial hydrocarbon can be kept in other embodiments to feed； At least 35% of alkene during initial hydrocarbon can be kept in other embodiments to feed；Real at other Execute at least the 40% of the alkene that can keep in scheme in initial hydrocarbon charging；In other embodiments At least 45% of alkene during initial hydrocarbon can be kept to feed；Can keep in other embodiments At least 50% of alkene in initial hydrocarbon charging；And can keep initial in other embodiments At least 60% of alkene in hydrocarbon charging.

Advantageously, embodiment disclosed herein can provide from ASTM D-86 terminal be at least The hydrocarbon feed of 350 °F, and even from high terminal hydrocarbon feed (such as, have higher than 450 °F, 470 °F, 500 °F, 525 °F or the terminal of 550 °F and containing being obstructed sulphur compound) produce the vapour of low sulfur content Oil distillate (have the most by weight 10ppm S).Additionally, due to not With the process under stringency and selected operating condition, including using heavy hydrocarbon dilution or suitable catalyst Using, it is one or more that embodiment disclosed herein can provide in the following: high alkene The recombinant mercaptans that is saturated and that reduce that selects of reservation, alkene and/or aromatic compounds is formed.According to The further benefit of the technique of embodiment disclosed herein is to control gasoline in the middle of produced to evaporate The ability of the terminal divided.

Although the present invention is described already in connection with the embodiment of limited quantity, but benefit from this Disclosed in it will be appreciated by persons skilled in the art that and can design the model without departing substantially from invention disclosed herein Other embodiment enclosed.Therefore, the scope of the present invention should only be limited by appended claims.

Claims

1. for the method that makes full boiling range cat cracked naphtha desulfurization, described method include as Lower step:

A complete to (1) boiling range naphtha stream and (2) hydrogen are fed to the first distillation column reactor, described (1) by () Full boiling range naphtha stream comprises alkene, alkadienes, mercaptan and other organosulfur compound and has at least The ASTM D86 final boiling point of 350 °F；

B () simultaneously carries out following (i) and (ii) in described first distillation column reactor,

I () alkadienes in described full boiling range naphtha stream and mercaptan are at group VIII metal catalytic Contact in the rectifying section of described first distillation column reactor in the presence of agent, thus occur Following reaction:

(A) part for described mercaptan is reacted to form sulfur with a part for described alkadienes Ether, and/or

(B) part for described alkadienes is reacted to form alkene with a part for described hydrogen； And

(c) using described first heavy naphtha as first the bottomsstream from described first distillation column reaction Device reclaims；

D described first the bottomsstream and hydrogen are fed in after-fractionating tower reactor by ()；

E () carries out following (i) and (ii) in described after-fractionating tower reactor simultaneously,

I () makes at least some of of the organosulfur compound in described first the bottomsstream and hydrogen In the presence of Hydrobon catalyst in the rectifying section of described after-fractionating tower reactor Reaction, so that a part for other organosulfur compound is converted into hydrogen sulfide, and

(ii) the first heavy naphtha is separated into the second heavy naphtha and ASTM D86 terminal exists The first medium naphtha in the range of 270 °F to 400 °F；

F described first medium naphtha, unreacted hydrogen, and hydrogen sulfide are evaporated by () as the second tower top Go out thing to reclaim from described after-fractionating tower reactor；

(g) using containing be obstructed organosulfur compound the second heavy naphtha as second the bottomsstream from Described after-fractionating tower reactor reclaims；

H second the bottomsstream and hydrogen are fed to accommodate the first of Hydrobon catalyst and fix by () In bed reactor；

(i) will be obstructed organosulfur compound and hydrogen anti-in described first fixed bed with Hydrobon catalyst Answer in device and contact, so that the described organosulfur compound that is obstructed changed into hydrogen sulfide at least partially；

J () reclaims the effluent from described first fixed bed reactors；

K diesel hydrocarbon fraction, before described contact procedure (i), is mixed by () with described second the bottomsstream Close, with by least some of of the organosulfur compound that is obstructed in described second heavy naphtha fraction and institute State diesel oil distillate and be converted into hydrogen sulfide.

2. the method described in claim 1, described method also include in the following at least one :

L () separates unreacted hydrogen and sulfuration from the effluent from described first fixed bed reactors Hydrogen；

M () separates unreacted hydrogen and hydrogen sulfide from described second overhead；

N effluent (l) that () will separate, a part for the second tower top effluent, it is fed in fractionating column To separate unreacted hydrogen and hydrogen sulfide, thus reclaim the bottomsstream hydrocarbon-fraction；

O the bottomsstream hydrocarbon-fraction and hydrogen are fed to accommodate Hydrobon catalyst by () second solid In fixed bed reactor, with changing into the sulphur compound in the bottomsstream hydrocarbon-fraction at least partially Hydrogen sulfide；With

P () separates at least some of sulfuration from the effluent from described second fixed bed reactors Hydrogen, to form the naphtha cut of the sulfur content with reduction.

3. for the method that makes full boiling range cat cracked naphtha desulfurization, described method include as Lower step:

B () is simultaneously carried out in described first distillation column reactor,

I () makes the alkadienes in described full boiling range naphtha stream and mercaptan urge at group VIII metal Contact in the rectifying section of described first distillation column reactor in the presence of agent, thus send out Raw following reaction:

(A) part for described mercaptan forms thioether with the part reaction of described alkadienes, And/or

(B) part for described alkadienes forms alkene with the part reaction of described hydrogen；With And

(ii) described full boiling range cracked naphtha fractional distillation is the product of distillation containing C5 hydrocarbon and contains First heavy naphtha of sulphur compound；

D described first the bottomsstream and hydrogen are fed to after-fractionating tower reactor by ()；

E () is carried out in after-fractionating tower reactor simultaneously,

I () makes at least some of of the organosulfur compound in described first the bottomsstream and hydrogen In the presence of Hydrobon catalyst in the rectifying section of described after-fractionating tower reactor Reaction, changes into hydrogen sulfide with the part by other organosulfur compound described, and

H described second the bottomsstream and hydrogen are fed to accommodate the first of Hydrobon catalyst by () Fixed bed reactors；

(i) by described be obstructed organosulfur compound and hydrogen with described Hydrobon catalyst described first Fixed bed reactors contact, so that the described organosulfur compound that is obstructed changed into sulfur at least partially Change hydrogen；

J effluent from the first fixed bed reactors is reclaimed by ()；

K () forms diesel hydrocarbon from described at least partially from the effluent of the first fixed bed reactors Fraction；

L described diesel hydrocarbon fraction, before described contact procedure (i), is distillated at the bottom of described second tower by () Thing mixes, so that the described organosulfur compound that is obstructed is changed into hydrogen sulfide at least partially.

4. the method described in claim 3, described method also includes at least one in the following:

M () separates unreacted hydrogen and sulfur from described from the effluent of the first fixed bed reactors Change hydrogen；

N () separates unreacted hydrogen and hydrogen sulfide from described second overhead；

O effluent (m) that () will separate, a part for the second tower top effluent, it is fed in fractionating column To separate unreacted hydrogen and hydrogen sulfide, thus reclaim the bottomsstream hydrocarbon-fraction；

P the bottomsstream hydrocarbon-fraction and hydrogen are fed to accommodate Hydrobon catalyst by () second solid In fixed bed reactor, with changing into the sulphur compound in the bottomsstream hydrocarbon-fraction at least partially Hydrogen sulfide；With

Q () separates at least some of sulfuration from the effluent from described second fixed bed reactors Hydrogen, to form the naphtha cut of the sulfur content with reduction.

5. the method described in claim 3, described method also includes:

Reclaim the first fixed bed reactors effluent from step (i), described first fixed bed reactors Effluent comprises hydrogen, hydrogen sulfide and has the hydrocarbon of sulfur content of reduction；And

Described first fixed bed reactors effluent is fed to knock-out drum, at least partially with from institute State and hydrocarbon-fraction separates hydrogen and hydrogen sulfide.

6. the method described in claim 3, described method also includes:

At least some of of described first fixed bed reactors effluent and ASTM D86 terminal are existed The first medium naphtha mixing in the range of 270 °F to 400 °F, produces the medium naphtha merged Fraction；And

The medium naphtha fraction of described merging is fed to cold drum, with from the middle stone of described merging Naphtha fraction additionally separates hydrogen and hydrogen sulfide.