CN101600496A - Be used for the combined unit that aromatic hydrocarbons is produced - Google Patents

Be used for the combined unit that aromatic hydrocarbons is produced Download PDF

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CN101600496A
CN101600496A CNA200780050595XA CN200780050595A CN101600496A CN 101600496 A CN101600496 A CN 101600496A CN A200780050595X A CNA200780050595X A CN A200780050595XA CN 200780050595 A CN200780050595 A CN 200780050595A CN 101600496 A CN101600496 A CN 101600496A
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stream
benzene
rich
tower
dimethylbenzene
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L·E·萨利文
G·马赫
D·A·哈姆
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Honeywell UOP LLC
Universal Oil Products Co
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UOP LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/04—Benzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2724—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals

Abstract

Allow transalkylation to handle C 10The toluene of alkylaromatic hydrocarbon and not extraction can be realized following improvement.Because no longer extracting toluene can slightly be removed the reformate knockout tower.Extraction cells (27) can be moved to the cat head of benzene tower and integrate to reduce cost with transalkylation (36).Owing to no longer require C 9And C 10Strictness between the alkylaromatic hydrocarbon separates, and can slightly remove the heavy aromatics tower.This transalkylation requires to stablize transalkylation catalyst by introducing metal function.Therefore these improvement have been saved the internal cell limit curve cost of Aromatic Hydrocarbon United Plant and have been improved investment in this class combined unit again.

Description

Be used for the combined unit that aromatic hydrocarbons is produced
Background of invention
The present invention relates to aromatics complex flow scheme, it is to use the combination in device district of technique unit that can be used for naphtha is changed into the basic petrochemical industry intermediate of benzene, toluene and dimethylbenzene.Based on the toluene of handling not extraction and more the metal catalytic alkyl transfering process and the olefin saturation process of heavy aromatics, this improved flow process is removed equipment item and the processing step as reformate knockout tower and heavy aromatics tower and so on, thereby obtains remarkable economic benefits when making xylene isomer.
Most new aromatics complexes are designed to make benzene and the maximization of paraxylene yield.Benzene is by used versatile petrochemical construction unit in its many different products that derive (comprising ethylo benzene, cumene and cyclohexane).Paraxylene also is important construction unit, and it almost is exclusively used in polyester fiber, resin and film that manufacturing forms via terephthalic acid (TPA) or dimethyl terephthalate intermediates.Correspondingly, can be according to required product, can get raw material and Ke De risk capital with many different modes structure Aromatic Hydrocarbon United Plant.Multiple option allows to change flexibly the product composition balance of benzene and paraxylene to meet the downstream processing request.
Meyers is at H ANDBOOK OFP ETROLEUMR EFININGP ROCESSES, second edition, 1997, a kind of aromatics complex flow scheme of prior art is disclosed among the McGraw-Hill.
The US 3,590,092 that authorizes people such as Uitti discloses the method that benzene is extracted in the combination of using extractive distillation, the rectifying of aromatic hydrocarbons side-draw and fractionation.
The US 3,996,305 that authorizes Berger discloses and has related generally to toluene and C 9The transalkylation of alkylaromatic hydrocarbon is to make the fractionation scheme of benzene and dimethylbenzene.This alkyl transfering process also with the aromatic hydrocarbons extraction process integration.This fractionation scheme comprises single tower, two flow to into and three streams leave this tower, thereby obtain overall economic efficiency.
The US 4,053,388 that authorizes Bailey discloses the method that is prepared aromatic hydrocarbons by naphtha, and it is by with the integrated yield that improves realized in catalytic reforming unit and hot hydrocracking unit.In combined process flow, use extraction and fractionation, transalkylation, paraxylene to separate and dimethylbenzene isomerization processes recovery aromatic hydrocarbons.The rerun tower of heavy aromatics is also disclosed.
The US 4,341,914 that authorizes Berger discloses a kind of transalkylation, wherein C 10Alkylaromatic hydrocarbon recirculation is to improve the dimethylbenzene yield of this method.This transalkylation is also preferred integrated with paraxylene Disengagement zone and dimethylbenzene isomerization zone (it moves as the successive loops that receives the mixed xylenes raw material and be discharged in the fractionation zone from the transalkylation reaction zone raw material).
The US 4,642,406 that authorizes Schmidt discloses the high intensity method that is used to make dimethylbenzene, serves as the transalkylation reaction zone of isomerization zone when it uses on non-metallic catalyst.Make high-quality benzene with xylene mixture, it can separate by absorbability isolates paraxylene from this mixture, and sends this fluid that removes isomers back to transalkylation reaction zone.
Authorize people's such as Boitiaux US 5,417,844 disclose the method that is used in the presence of Raney nickel the olefine selective dehydrogenation of steam cracking oil, it is characterized in that, before using catalyst, the organic compound of sulfur-bearing is mixed in the catalyst outside reactor before use.
The US 5,658,453 that authorizes people such as Russ discloses comprehensive reformation and alkene saturation.This olefin saturation is used mixed vapour phase, wherein to preferably contain the reformate liquid that the refractory inorganic oxide of platinum group metal with optional metals modifier contact in add hydrogen.
The US 5,763,720 that authorizes people such as Bucha nan discloses by make C on the catalyst that comprises zeolite (as ZSM-12) and hydrogenation noble metal (as platinum) 9 +Alkylaromatic hydrocarbon contacts the transalkylation of making benzene and dimethylbenzene with benzene and/or toluene.Use sulphur or this catalyst of steam treatment.
The US 5,847,256 that authorizes people such as Ichioka discloses by the catalyst that contains zeolite (it is preferably modenite) and containing metal (it is preferably rhenium) by containing C 9The raw material of alkylaromatic hydrocarbon is made the method for dimethylbenzene.
Summary of the invention
Aromatics complex flow scheme with effective alkyl transfering process requires to stablize transalkylation catalyst by introducing metal function.Allow alkyl transfering process to handle C 10The toluene of alkylaromatic hydrocarbon and not extraction can be realized following flow scheme improvements.By use toluene under the situation of earlier toluene not being sent into extraction cells, this flow process has been omitted the reformate knockout tower.Less capacity extraction unit together moves to the cat head of benzene tower.By benzene extraction only, use simple extractive distillation, because have only heavier pollutant just to require more expensive associating liquid-liquid extraction method.By effectively using C simultaneously in the transalkylation 9And C 10Alkylaromatic hydrocarbon, this flow process has further been omitted the heavy aromatics tower.
Another embodiment of the present invention comprises the device based on these processing steps, and it changes into paraxylene with naphtha effectively.Can use the transalkylation tower slightly to remove independent benzene tower.Can use and have the heavy aromatics tower that side is heated up in a steamer or the replacement of the benzenol hydrorefining of side-draw conduit is independent.
Can from as detailed below of the present invention, obtain other target of the present invention, embodiment and details.
The accompanying drawing summary
Fig. 1 has shown aromatics complex flow scheme figure of the present invention, the saturated and metal stabilized of its alkene.
Fig. 2 has shown another embodiment of the present invention, and it comprises the flow chart based on the transalkylation stripper column that has stabilizer section.
Detailed Description Of The Invention
The charging of this combined unit can be a naphtha, but also can be drippolene (pygas), import mixed xylenes or import toluene.The naphtha of sending into Aromatic Hydrocarbon United Plant at first hydrotreatment is less than 0.5wt-ppm so that before the naphtha that will handle turns to reformer unit 13 sulphur and nitrogen compound be removed to.Under the petroleum naphtha hydrogenation treatment conditions, contact and carry out the petroleum naphtha hydrogenation processing by making naphtha in the pipeline 10 in unit 11, handle catalyst with petroleum naphtha hydrogenation.Point out, therefore term " unit " is used to represent various treatment regions at this specification in the whole text, and this class " zone " can be understood to include following process equipment and device part: as reactor, heater, separator, interchanger, pipeline, pump, compressor, controller with carry out each technology necessary (non-limiting) and be interpreted as any and all miscellaneous equipments and the machinery of the part in this class unit or zone by each technology field those of ordinary skill.
Petroleum naphtha hydrogenation is handled catalyst and is made of first component of cobalt oxide or nickel oxide and second component and the 3rd component inorganic oxide carrier (it is high purity aluminium oxide normally) of molybdenum oxide or tungsten oxide usually.Usually be that 1 to 5 weight % and molybdenum oxide component realize good result when being 6 to 25 weight % in cobalt oxide or nickel oxide component.Alumina (or aluminium oxide) is set to supplies this petroleum naphtha hydrogenation and handle the composition of catalyst so that all components adds up to 100 weight %.A kind of hydrotreating catalyst used among the present invention is disclosed in US 5,723, and in 710, its instruction is incorporated herein by this reference.Typical hydroprocessing condition comprises 1.0 to 5.0hr -1Liquid hourly space velocity (LHSV) (LHSV), 50 to 135Nm 3/ m 3Hydrogen/hydrocarbon (or feed naphtha) ratio and 10 to 35kg/cm 2Pressure.
In reformer unit 13, alkane and cycloalkane are changed into aromatic hydrocarbons.This is an actual only element of making aromatic ring in this combined unit.Other unit in this combined unit is separated into various aromatic component stand-alone product and various aromatics classes is changed into the more product of high value.This reformer unit 13 is designed to be equivalent to make operation under the very high strength of 100 to 106 research octane number (RON) (RON) reformats so that aromatic hydrocarbons production maximization usually.The C of this reformate is also eliminated in this high strength operation 8 +Nearly all non-aromatic impurities in the cut has also been eliminated extraction C 8And C 9The needs of aromatic hydrocarbons.
In this reformer unit 13, contact under the condition of reorganization with reforming catalyst from the naphtha of the hydrotreatment of pipeline 12.This reforming catalyst is made of the first component platinum group metal, the second component modification agent metal and the 3rd component inorganic oxide carrier (it is high purity aluminium oxide normally) usually.Usually be that 0.01 to 2.0 weight % and modifier metal component realize good result when being 0.01 to 5 weight % in the platinum group metal.Aluminium oxide is set to supplies this petroleum naphtha hydrogenation and handle the composition of catalyst so that all components adds up to 100 weight %.This platinum group metal is selected from platinum, palladium, rhodium, ruthenium, osmium and iridium.Preferred platinum group metal component is a platinum.Metal modifiers can comprise rhenium, tin, germanium, lead, cobalt, nickel, indium, gallium, zinc, uranium, dysprosium, thallium and composition thereof.A kind of reforming catalyst used among the present invention is disclosed in US 5,665, and in 223, its instruction is incorporated herein by this reference.Typical the condition of reorganization comprises 1.0 to 5.0hr -1The hydrogen/hydrocarbon ratio and 2.5 of liquid hourly space velocity (LHSV), hydrocarbon charging 1 to 10 moles of hydrogen that every mole enters reformer section to 35kg/cm 2Pressure.The hydrogen of making in reformer unit 13 leaves in pipeline 14.
Reformate from reformer unit 13 is sent to debutanizer zone 53 in pipeline 15, it is usually included in the debutanizing tower 20 that stripping in the pipeline 21 goes out light fraction hydrocarbon (butane and lighter).This debutanizer zone 53 also can comprise at least one olefin saturation zone 16, and it can be positioned at the upstream or the downstream of debutanizing tower 20.Fig. 1 has shown upstream option, and Fig. 2 has shown downstream option.In addition, the fluid from other unit in this Aromatic Hydrocarbon United Plant also can be sent to debutanizing tower 20 so that stripping via pipeline 19.These other unit comprise transalkylation reaction zone (it carries the transalkylation stripper column overhead streams in pipeline 17) and isomerization zone (it carries the deheptanizer overhead streams in pipeline 18).These two unit are more detailed description hereinafter all.
Olefin saturation zone 16 can be made of to handle residual olefin contaminants known clay treatment device or other device.The clay treatment device comprises that the optional hydrogen that uses is as olefin saturation catalyst means.Correspondingly, this olefin saturation zone 16 is included in the olefins hydrogenation of work under the alkene saturation conditions.
Suitable olefins hydrogenation contains preferred negative and is loaded in elemental nickel or platinum-group component on the inorganic oxide carrier (it is aluminium oxide normally) among the present invention.Under the situation that has elemental nickel on the carrier, nickel preferably exists with the amount of 2 to 40 weight % of total catalyst weight.A kind of catalyst used among the present invention is disclosed in US 5,658, and in 453, its instruction is incorporated herein by this reference.Perhaps, clay itself is preferred olefins hydrogenation, optional use with hydrogen, and this class clay can be defined as having shades of colour, fine and close and frangible but common soil plasticity and adhesion when wetting when drying.Clay is the aluminium hydrosilicate that mixes with powdery feldspar, quartz, sand, iron oxide and various other mineral usually, and being decomposed to form by pelite (as the feldspar in the granite).Can adopt any suitable clay of the ability that shows the selectivity saturation of olefins in the present invention.Highly preferred clay comprises attapulgus clay and covers unsticking soil.It is believed that the ability of native iron content influence clay olefin(e) compound in the selectivity saturated aromatic raw material when preserving olefin(e) compound of many type clay.Typical alkene saturation conditions comprises that 20 to 200 ℃ temperature, 5 is to 70kg/cm 2Pressure and the stoichiometric proportion of 0.1: 1 to 15: 1 hydrogen (if existence) and alkene.
The debutanization reformate that comprises aromatic hydrocarbons in the pipeline 22 and the transalkylation stripper column in the pipeline 24-tower bottom flow is merged and be sent to benzene-toluene (BT) fractionation zone 54 via pipeline 23.This BT fractionation zone 54 comprises at least one tower usually, and comprises benzene tower 25 and toluene tower 31 usually.But,, can slightly remove benzene tower 25 owing to have the transalkylation stripper column 52 of the stabilizer section that is enough to make suitable benzene stream as shown in Figure 2.This BT fractionation zone 54 produces the rich dimethylbenzene+stream in benzene stream and the pipeline 33 of being the richest in rich benzene stream in pipelines 26, the pipeline 32.Usually, the rich benzene stream in the pipeline 26 flows out deposits yields by the cat head of benzene tower 25, and the bottom stream of benzene tower 25 is sent into toluene tower 31 via pipeline 30.The benzene stream of being the richest in the pipeline 32 is flowed out deposits yields and is sent to transalkylation 36 by the cat head of toluene tower 31, and the bottom stream of toluene tower 31 produces the rich dimethylbenzene+stream in the pipeline 33.To be sent to the dimethylbenzene recovery section 55 of following Aromatic Hydrocarbon United Plant from the rich dimethylbenzene+stream in pipeline 33 of toluene tower 31 bottoms.
Rich benzene stream in the pipeline 26 is sent to extractive distillationzone 27, and it produces the high pure benzene product stream in the pipeline 29 and discharge the accessory substance raffinate stream in pipeline 28.This raffinate stream can be mixed in the gasoline, is used as the raw material of ethylene unit, or changes into extra benzene in the reformer unit 13 by being recycled to.Liquid-liquid extraction/extractive distillation technology that extractive distillation replaces liquid-liquid extraction to use or unite produces improvement economically.Extractive distillationzone 27 comprises at least one tower that is known as main destilling tower usually, and can comprise second tower that is known as recovery tower.This second tower also can obtain from the benzene tower of another fractionation part (as BT fractionation zone 54) of Aromatic Hydrocarbon United Plant by being used to again.
Extractive distillation is to separate the technology of mixture have almost equal volatility and to have the component of boiling point much at one.The component that is difficult to separate this class mixture by traditional fractionating process.In extractive distillation, above the entrance of the fluid mixture of the hydrocarbonaceous that will separate, solvent is introduced main extraction distillation column.This solvent makes the volatility of the fluid components of the hydrocarbonaceous that seethes with excitement under higher temperature be different from the fluid components of the hydrocarbonaceous of boiling at a lower temperature, thereby be enough to promote fluid components, and this kind solvent leaves with tower bottom distillate by the various hydrocarbonaceous of separated.Suitable solvent comprises thiophane 1,1-dioxide (or sulfolane), NFM (positive formyl-morpholine), NMP (positive methyl pyrrolidone), diethylene glycol, triethylene glycol, TEG, methoxyl group triethylene glycol and composition thereof.Other glycol ether also can be united as suitable solvent separately or with above-listed those.The raffinate stream that comprises non-aromatic compound in the pipeline 28 is left extractive distillationzone 27 in main extractive distillation column overhead, and the tower bottom distillate that contains solvent and benzene simultaneously leaves below main extraction distillation column.The tower bottom flow of in the future autonomous extraction distillation column is sent to solvent recovery tower, at this recovered overhead benzene in pipeline 29, and reclaims solvent and sends main extraction distillation column back at the bottom of tower.The rate of recovery from the high pure benzene in pipeline 29 of extractive distillationzone 27 surpasses 99 weight % usually.
Extractive distillation section of the present invention is freely processed rich benzene stream usually and is simplified in several modes.For example, when main processing benzene charging, can slightly remove in solvent recovery tower the stripping apparatus of the common necessary costliness of aromatics separation from solvent.In other words, the operation under the situation that does not have stripping and relevant device substantially is a feature of the present invention, and does not exist substantially and be meant not exist from the heavy arene mixture that comprises toluene and reclaim solvent required quantity of steam usually.Benzene also can replace steam to use with the required any solvent in this unit of regenerating.Point out in arbitrary figure, all there is not to show specially the optional benzene tower of main extraction distillation column, solvent recovery tower and extractive distillationzone 27.
In a simplified flow chart of the present invention, solvent recovery tower is simplified to benzene tower 25.Therefore, transalkylation stripper column 52 shown in Fig. 2 still produces rich benzene stream 26, but independent benzene tower serves as the recovery tower of extractive distillation unit now, the main extraction distillation column product stream (not shown) that thus can fractionation contains solvent and benzene to be producing the high pure benzene product at cat head, and can reclaim solvent at the bottom of tower.Perhaps and except above-mentioned flow chart, the benzene tower also can with the benzene rate of recovery of solvent recovery tower coupling two recovery towers effectively to be provided and to realize improving, obtain the extra benzene product that reclaims and the solvent streams of purifying.
In the pipeline 32 be the richest in benzene circulation normal with pipeline 41 in the C that is rich in by benzenol hydrorefining 39 generations 9And C 10The fluid fusion of alkylaromatic hydrocarbon is also packed transalkylation 36 into to make extra dimethylbenzene and benzene via pipeline 34.In transalkylation 36, this charging is contacted under transalkylation conditions with transalkylation catalyst.Preferred catalyst is a metal stabilized.This class catalyst comprises solid acid component, metal component and inorganic oxide component.This solid acid component is the pentasil zeolite normally, and it comprises MFI, MEL, MTW, MTT and FER structure (IUPAC Commission on Zeolite Nomenclature), β zeolite or modenite.It is modenite preferably.Other suitable solid acid component comprises mazzite, NES type zeolite, EU-1, MAPO-36, MAPSO-31, SAPO-5, SAPO-11, SAPO-41.Preferred mazzite comprises Zeolite Omega.At US 4,241, the synthetic of Zeolite Omega described in 036.European patent application EP 0 378 916 A1 have described NES type zeolite and have prepared the method for NU-87.At US 4,537, EUO structure type EU-1 zeolite has been described in 754.At US 4,567, MAPO-36 has been described in 029.At US 5,296, MAPSO-31 has been described in 208, and at US 4,440, typical SAPO composition has been described in 871, comprise SAPO-5, SAPO-11, SAPO-41.
This metal component is noble metal or base metal normally.Noble metal is the platinum group metal, is selected from platinum, palladium, rhodium, ruthenium, osmium and iridium.Base metal is selected from rhenium, tin, germanium, lead, cobalt, nickel, indium, gallium, zinc, uranium, dysprosium, thallium and composition thereof.Base metal can make up with another base metal or with noble metal.This metal component preferably comprises rhenium.Suitable amount of metal is 0.01 to 10 weight % in this transalkylation catalyst, and the scope of 0.1 to 3 weight % is preferred, and the scope height of 0.1 to 1 weight % is preferred.Suitable amount of zeolite is 1 to 99 weight % in this catalyst, preferred 10 to 90 weight %, more preferably 25 to 75 weight %.The remainder of this catalyst is used to promote the catalyst manufacturing by choosing wantonly, provides the fire resistant adhesive or the matrix of intensity and reduction manufacturing cost to constitute.This adhesive should be fire-resistant relatively under even aspect the composition and used in the method condition.Suitable bonding comprises inorganic oxide, as in aluminium oxide, magnesia, zirconia, chromium oxide, titanium dioxide, boron oxide, thorium oxide, phosphate, zinc oxide and the silica one or more.Aluminium oxide is a preferred adhesive.Used in the present invention a kind of transalkylation catalyst is disclosed in US 5,847, and in 256, its instruction is incorporated herein by this reference.
Used condition generally includes 200 to 540 ℃ temperature in the transalkylation reaction zone.This transalkylation reaction zone 1 to 60kg/cm 2Appropriate elevated pressure under move.Can realize transalkylation reaction in wide air speed scope, higher space velocity is that cost realizes higher paraxylene ratio with the conversion ratio.Liquid hourly space velocity (LHSV) is generally 0.1 to 20hr -1This raw material is transalkylation in gas phase and in the presence of the hydrogen of supplying via pipeline 35 preferably.If transalkylation in liquid phase, then the existence of hydrogen is chosen wantonly.If there is free hydrogen, it associates with the amount of 10 moles of 0.1 mole to every mole alkylaromatic hydrocarbons of every mole of alkylaromatic hydrocarbon and the hydrocarbon of this raw material and recirculation.Hydrogen also is known as hydrogen/hydrocarbon ratio with this ratio of alkylaromatic hydrocarbon.
To be sent to transalkylation stripper column 52 from the effluent of transalkylation 36 to remove light fraction, be sent to BT fractionation zone 54 by pipeline 24 and 23 then.Reclaim the benzene product, fractionate out the diformazan benzo and be sent to dimethylbenzene recovery area 55 via the rich dimethylbenzene+stream in the pipeline 33.Overhead material from transalkylation stripper column 52 is recycled to the reformer unit debutanizing tower to reclaim residual benzene via pipeline 17 usually.Perhaps, on the transalkylation stripper column 52 or after stabilizer section or tower are set.This transalkylation stabilizer section can produce the rich benzene stream that is fit to extractive distillation, and eliminates the needs to independent benzene tower in the BT fractionation zone as shown in Figure 2, and Fig. 2 is at tower 52 top display blocks 25.Therefore, perhaps, when slightly removing independent benzene tower 25, be included in the definition of BT fractionation zone 54 from this stabilizer or the stripper of transalkylation reaction zone.Transalkylation stripper column 52 also can receive from olefin saturation zone or from the product of the processing of alkylaromatic isomerization deheptanizer cat head, it recycles back reformer unit debutanizing tower 20 usually.
As mentioned above, will be sent to the dimethylbenzene recovery section 55 of Aromatic Hydrocarbon United Plant from the rich dimethylbenzene+stream in pipeline 33 of toluene tower 31 bottoms.This section of Aromatic Hydrocarbon United Plant comprises at least one benzenol hydrorefining 39 and further comprises the technique unit that is used for separating at least one xylene isomer (its normally from the paraxylene product of Aromatic Hydrocarbon United Plant, but also can be inclined to one side xylene isomer) usually.With the paraxylene isomers separation of Xylene Isomer district is described below.Preferably, this paraxylene Disengagement zone 43 be used for that the balance that contains paraxylene or isomerization unit 51 cooperations of nearly equilibrium mixture are returned in residual alkyl aromatic compound isomerization, this mixture can be again with circuit type recirculation with further recovery.Correspondingly, with the rich dimethylbenzene+stream in the pipeline 33 (its can with recirculation flow fusion in the pipeline 38 to form the fluid in the pipeline 37) benzenol hydrorefining 39 of packing into.This benzenol hydrorefining 39 is designed to the to the utmost point low C of the incoming flow redistillation of sending into paraxylene Disengagement zone 43 in the pipeline 40 9Alkylaromatic hydrocarbon (A 9) concentration.A 9Compound may accumulate in the strippant closed circuit in the paraxylene Disengagement zone 43, and it is more effective therefore removing this material in benzenol hydrorefining 39 upstreams.Will be from the cat head incoming flow in pipeline 40 of the benzenol hydrorefining 39 paraxylene Disengagement zone 43 of directly packing into.
C is rich in material conduct from benzenol hydrorefining 39 bottoms 9And C 10The fluid of alkylaromatic hydrocarbon extracts via pipeline 41, and it is sent to transalkylation reaction zone 36 subsequently to make extra dimethylbenzene and benzene.Going up the fluid in pipeline 41 that extracts as side-draw stream at benzenol hydrorefining (it has eliminated the heavy aromatics tower) is activated by metal stabilized easily.This metal stabilized no longer needs to carry out strict the separation, because can not handled them under the situation because of the remarkable inactivation of coking so that coke precursors (as methyl indan or naphthalene) does not enter the independent tower of this fluid.Discharge any residual C via pipeline 42 from benzenol hydrorefining 39 bottoms 11 +Material.Another embodiment is only with whole benzenol hydrorefining tower bottom flow but not side-draw stream is sent to transalkylation.
Perhaps, if make ortho-xylene in this combined unit, then this benzenol hydrorefining is designed to separate partially and ortho-xylene and the ortho-xylene of aim parameter is dropped down onto at the bottom of the tower.Then this benzenol hydrorefining bottoms is sent to the ortho-xylene column (not shown), at this from the high-purity ortho-xylene product of recovered overhead.C is rich in material conduct from the ortho-xylene column bottom 9And C 10The fluid extraction of alkylaromatic hydrocarbon is sent to transalkylation then.Discharge any residual C from the ortho-xylene tower bottom 11 +Material.
This paraxylene Disengagement zone 43 can be based on fractional crystallization or adsorption method of separation, and the both is as known in the art, and is preferably based on adsorption method of separation.This adsorption method of separation can reclaim above the pure paraxylene of 99 weight % with high every flow process rate of recovery in pipeline 44.Extract any residual toluene in the charging that enters separative element with paraxylene, fractionate out in the treating column in this unit, and the optional subsequently transalkylation stripper column 52 that is recycled to.Therefore, the raffinate from paraxylene Disengagement zone 43 almost completely removes paraxylene to common content less than 1 weight %.This raffinate is sent to alkylaromatic isomerization unit 51 via pipeline 45,, makes extra paraxylene in this balance or nearly balanced distribution by rebuilding xylene isomer.According to the type of used heterogeneous catalyst, any ethylo benzene in the paraxylene separative element raffinate is converted to additional xylenes or changes into benzene by taking off alkyl.
In alkylaromatic isomerization unit 51, the raffinate stream in the pipeline 54 is contacted under isomerization conditions with heterogeneous catalyst.This heterogeneous catalyst is made of molecular sieve component, metal component and inorganic oxide component usually.The selection of molecular sieve component can be controlled catalyst performance according to the total demand of benzene is taken off at ethylbenzene isomerization and ethylo benzene between the alkyl.Usually, this molecular sieve can be zeolite aluminosilicate or non-zeolite molecular sieve.Zeolite aluminosilicate (or zeolite) component is the pentasil zeolite normally, and it comprises MFI, MEL, MTW, MTT and FER structure (IUPACCommission on Zeolite Nomenclature), β zeolite or modenite.According to " Atlas of Zeolite Structure Types " (Butterworth-Heineman, Boston, Mass., the 3rd edition 1992), non-zeolite molecular sieve is one or more in the AEL framework types normally, especially one or more in SAPO-11, or the ATO framework types, especially MAPSO-31.This metal component is noble metal component normally, and except that noble metal or replace noble metal, can comprise optional base metal modifier components.Noble metal is the platinum group metal, is selected from platinum, palladium, rhodium, ruthenium, osmium and iridium.Base metal is selected from rhenium, tin, germanium, lead, cobalt, nickel, indium, gallium, zinc, uranium, dysprosium, thallium and composition thereof.Base metal can make up with another base metal or with noble metal.Suitable total amount of metal is 0.01 to 10 weight % in this heterogeneous catalyst, and the scope of 0.1 to 3 weight % is preferred.Suitable amount of zeolite is 1 to 99 weight % in this catalyst, preferred 10 to 90 weight %, more preferably 25 to 75 weight %.The remainder of catalyst is by inorganic oxide adhesive, and aluminium oxide constitutes usually.A kind of heterogeneous catalyst used among the present invention is disclosed in US 4,899, and in 012, its instruction is incorporated herein by this reference.
Typical isomerization conditions comprises that 0 to 600 ℃ temperature and atmospheric pressure are to 50kg/cm 3Pressure.With respect to the volume of catalyst, the hydrocarbon liquid hourly space velocity (LHSV) of raw material is 0.1 to 30hr -1Hydrocarbon with pipeline 46 in the hydrogeneous stream of gaseous state with 0.5: 1 to 15: 1 or bigger hydrogen/hydrocarbon mol ratio, this catalyst of contact under the situation that preferred 0.5 to 10 ratio mixes.If liquid-phase condition is used for isomery, then in this unit, do not add hydrogen.
To be sent to deheptanizer 48 via pipeline 47 from the effluent of isomerization unit 51.If necessary, in alkene saturation unit 50, handle the tower bottom flow in pipeline 49 from deheptanizer 48 to remove alkene with above-mentioned alkene saturation.Alkene saturation unit 50 perhaps is set after isomerization unit 51 and uses deheptanizer 48 to remove remaining hydrogen.If used catalyst is an ethylbenzene dealkylation type in the isomerization unit 51, do not require fully that then alkene is saturated.
Then the deheptanizer tower bottom flow in pipeline 49 after the olefin treated is recycled back benzenol hydrorefining 39 via pipeline 38.Thus, all C 8Aromatic hydrocarbons recycles continuously in the dimethylbenzene recovery area of this combined unit and leaves Aromatic Hydrocarbon United Plant until them as paraxylene, benzene or optional ortho-xylene.Overhead streams from deheptanizer 48 recycles back reformer unit debutanizing tower 20 to reclaim residual benzene via pipeline 18 usually.Perhaps, overhead liquid is recycled back transalkylation stripper column 52.
Correspondingly, Aromatic Hydrocarbon United Plant of the present invention shows excellent economic benefit.Therefore these improvement have been saved the internal cell limit curve cost of Aromatic Hydrocarbon United Plant and have been improved investment in this class combined unit again.

Claims (10)

1. make the combined unit of benzene and xylene isomer by rich aromatic hydrocarbons stream:
(a) comprise the extractive distillationzone (27) of main destilling tower and benzene tower, the benzene product stream (29) that produces raffinate stream (28) and reclaim at this rich benzene stream (26) as the product of described device;
(b) comprise the fractionation zone (54) of toluene tower (31), at this rich aromatic hydrocarbons is flowed (22) and separates with at least a portion transalkylated product stream (24) and be the richest in benzene with generation and flow (32) and rich dimethylbenzene+stream (33);
(c) comprise the transalkylation reaction zone of reactor (36) and transalkylation stripper column (52), make at this to be the richest in benzene stream (32) and to be rich in C 9And C 10The benzenol hydrorefining stream (41) and the metal stabilized of alkylaromatic hydrocarbon contacts the rich benzene stream (26) with transalkylated product stream (24) that produces step (b) and step (a) under transalkylation conditions; With
(d) comprise the dimethylbenzene recovery section (55) in dimethylbenzene fractionating column (39) and separation of Xylene Isomer district, wherein the rich dimethylbenzene of dimethylbenzene fractionating column separating step (b)+stream (33) is to provide the C that is rich in of step (c) 9And C 10The benzenol hydrorefining stream (41) of alkylaromatic hydrocarbon and cat head dimethylbenzene stream (40), and wherein the separation of Xylene Isomer district is condensed into the product stream (44) that is rich in xylene isomer with cat head dimethylbenzene stream (40), and its product as described device flows back to receipts.
2. the device of claim 1, wherein dimethylbenzene recovery section (55) further comprises alkylaromatic isomerization district (51), has deheptanizer fractionation zone and optional at least one olefin saturation zone (50) of at least one deheptanizer (48).
3. the device of claim 1, wherein the feature of benzene tower further is, moves under the situation that does not have the essence stripping apparatus.
4. the device of claim 1, wherein the feature of benzenol hydrorefining (39) further is, has to extract as sideing stream to be rich in C 9And C 10The device of the fluid of alkylaromatic hydrocarbon (41).
5. the device of claim 1, wherein dimethylbenzene recovery section (55) further comprises ortho-xylene column.
6. the device of claim 1, wherein the benzene tower leave main destilling tower main distillation stream to produce solvent streams, send it back to main destilling tower.
7. the device of claim 8 further comprises recovery tower, and it receives at least a portion solvent streams and produces benzene stream of reclaiming and the solvent streams of purifying, and the solvent streams of this purifying is sent to main destilling tower.
8. make the integrated processes of benzene and xylene isomer by rich aromatic hydrocarbons stream, comprising:
(a) at least a portion transalkylated product stream and rich aromatic hydrocarbons stream are fed to the fractionation zone that comprises transalkylation stripper column and toluene tower, wherein this fractionation zone produces rich benzene stream, is the richest in benzene stream and rich dimethylbenzene+stream;
(b) make and be the richest in benzene stream and be rich in C 9And C 10The benzenol hydrorefining stream of alkylaromatic hydrocarbon contacts under transalkylation conditions in containing the reactor of metal stabilized to produce the transalkylated product stream of step (a);
(c) rich benzene stream is fed to the benzene product of extractive distillationzone that comprises main destilling tower and recovery tower to produce raffinate stream and from described method, to reclaim as product stream;
(d) in the dimethylbenzene fractionating column the rich dimethylbenzene+stream of separating step (a) to produce the C that is rich in of step (b) 9And C 10The benzenol hydrorefining stream of alkylaromatic hydrocarbon and cat head dimethylbenzene stream; With
(e) cat head dimethylbenzene stream is sent to the separation of Xylene Isomer district, the product stream of xylene isomer is rich in its generation, and its product as described method flows back to receipts.
9. the method for claim 8, wherein transalkylation catalyst comprises solid acid component and is selected from the metal component of platinum, palladium, rhodium, ruthenium, osmium and iridium, rhenium, tin, germanium, lead, cobalt, nickel, indium, gallium, zinc, uranium, dysprosium, thallium and composition thereof; Wherein transalkylation conditions comprises that 200 to 540 ℃ temperature, 1 is to 60kg/cm 2Pressure and 0.1 to 20hr -1Liquid hourly space velocity (LHSV); And wherein rich aromatic hydrocarbons stream comprises the aromatic component that is selected from catalytic reforming product, drippolene, import mixed xylenes, import toluene and composition thereof.
10. the method for claim 8, wherein main destilling tower produce and mainly distillate stream, and it is sent to recovery tower, and this recovery tower produces solvent streams, sends this solvent streams back to main destilling tower.
CNA200780050595XA 2007-01-29 2007-01-29 Be used for the combined unit that aromatic hydrocarbons is produced Pending CN101600496A (en)

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