CN102947251B

CN102947251B - Process and apparatus for the reduction of gasoline benzene content by alkylation with dilute ethylene

Info

Publication number: CN102947251B
Application number: CN201180027533.3A
Authority: CN
Inventors: C·P·尼古拉斯; A·巴塔查里亚
Original assignee: Universal Oil Products Co
Current assignee: Honeywell UOP LLC; Universal Oil Products Co
Priority date: 2010-06-11
Filing date: 2011-06-01
Publication date: 2015-04-08
Anticipated expiration: 2031-06-01
Also published as: WO2011156182A2; RU2505515C1; WO2011156182A3; BR112012030169A2; CN102947251A

Abstract

The process and apparatus converts ethylene in a dilute ethylene stream and dilute benzene in an aromatic containing stream via alkylation to heavier hydrocarbons. The catalyst may be a zeolite such as UZM-8. The catalyst is resistant to feed impurities such as hydrogen sulfide, carbon oxides, and hydrogen and selectively converts benzene. At least 40 wt-% of the ethylene in the dilute ethylene stream and at least 20 wt-% of the benzene in the dilute benzene stream can be converted to heavier hydrocarbons.

Description

By the method and apparatus using rare ethylene alkylation to reduce benzene content in gasoline

At the priority request of first national applications

This application claims U. S. application No.12/813,533 and U. S. application No.12/813, both 534(all on June 11st, 2010 submit to) right of priority.

Background technology

The field of the invention is use rare ethene by the method and apparatus of the benzene alkylation in petroleum naphtha stream.Motor spirit is can be used as through alkylating product.

Dry gas is the common name of the stream of working off one's feeling vent one's spleen from fluid catalytic cracking unit, and it comprises ethane boiling point and more lower boiling all gas.Compression works off one's feeling vent one's spleen stream to remove C3 and C4 gas as much as possible.Amine absorption agent is used also mostly to absorb sulphur from stream of working off one's feeling vent one's spleen in scrubber.Remaining mass flow is called as FCC dry gas.Common dry gas stream contains 5 to 50wt% ethene, 10 to 20wt% ethane, 5 to 20wt-% hydrogen, 5 to 20wt-% nitrogen, 0.05 to 5.0wt-% carbon monoxide, 0.1 to 5.0wt-% carbonic acid gas and be less than 0.01wt-% hydrogen sulfide and ammonia, and surplus is methane.

Current FCC dry gas stream is admitted to burner as fuel gas.The FCC unit in process 7,949 kilolitres (50,000 barrel)/sky will burn 181,000kg (200 tons) dry gas/sky, and described dry gas contains such as 36,000kg (40 tons) ethene as fuel.Owing to there is larger price difference between fuel gas and motor spirit product or pure ethylene, attempt to reclaim this ethene and seem economical interest.But dry gas stream contains the impurity that can make poisoning of catalyst, and it is proved wastefully by gas recovery system for rare to such an extent as to ethylene recovery.

Need to use rare ethene in refinery stream.

Catalytic reforming be established for petroleum refining industry to improve the hydroconversion process of the octane quality of hydrocarbon feed, the primary product of reformation is for starting motor benzin.In catalytic reforming, feed naphtha is mixed with the recovery stream comprising hydrogen, and in reaction zone at the temperature of about 493 ° to 510 ° C (920 ° to 950 °F) and under the middle pressure of about 1379 to 3792kPa (200 to 550psig) with catalyst exposure.The raw material being generally used for catalytic reforming is for being called petroleum naphtha and having the petroleum fractions of the initial boiling point of 46 ° of C (115 °F) and the full boiling point of 204 ° of C (400 °F).

Catalystic reforming method is specially adapted to process straight-run spirit, and described straight-run spirit is made up of the naphthenic hydrocarbon of relatively large content and the paraffinic hydrocarbons of basic straight chain, and it stands aromizing by dehydrogenation and/or cyclization.Catalyzer is by except dehydrogenation with reset molecular structure and " reformation " is contained in the molecular structure of the hydrocarbon in raw material petroleum naphtha to improve the octane value of petroleum naphtha.But the increase of octane value also reduces the liquid volume of petroleum naphtha, because proportion adds.Due to the multiplicity of compound in raw material petroleum naphtha, the real reaction occurred in catalytic reforming is a lot.But some in many products therefroms are aryl or aromatic substance, and it all demonstrates high-octane rating.The aryl compound produced depends on starting material, and described starting material are controlled by the boiling range of the petroleum naphtha used and crude oil origin in refinery." through what reform " product from catforming process is commonly referred to reformate, and be usually divided into two kinds of cuts by conventional distil-lation, the heavy reformate product of boiling range to be the lightweight reformate of 46 ° to 121 ° C (115 ° to 250 °F) and boiling range be 121 ° to 204 ° C (250 ° to 400 °F).Therefore aryl compound in often kind of cut depends on its boiling point.Comparatively lower boiling or comparatively lightweight aryl compound, such as benzene, toluene and dimethylbenzene are contained in lightweight reformate, and higher aryl compound is contained in heavy reformate product.

Benzene concentration in gasoline is specified by United States Government now.Average benzene level in the gasoline that Mobil Source Air Toxicsregulation (MSAT II) requires purifier to produce be in the gasoline produced in arbitrary refinery lower than 0.62vol-%, be up to 1.3vol-%.By reforming method and FCC method, benzene produces with the level higher than above-mentioned level usually.Due to two that from the reformate of FCC unit and petroleum naphtha stream are gasoline in refinery maximum sources, the strategy reducing benzene therefore must be used.

Usual saturation unit of being delivered to by benzene is to be reduced to hexanaphthene by benzene at present.But the method uses the hydrogen of at least three moles to every mole of benzene transformed, and exist and benzene be converted into the relevant loss of octane of hexanaphthene.Reduce the benzene in gasoline and do not lose octane or use the method for hydrogen to be necessary.

The benzene stream using concentrated ethylene stream alkylation concentrated is known.Alkylation is usually directed to use clean ethylene stream, because alkylation catalyst is to feed impurities sensitivity.Accordingly, rare ethene is seldom used as oligomerization raw material, because it has much lower reactivity relative to more senior alkene.For the aromatic substance of more heavy by the consideration of favors alkylation, the benzene stream being fed to alkylation reactor is also concentrated, thus requires to use ethene excessive greatly before reducing benzene concentration and producing not required polyalkylated benzene.

Definition

Following definitions is suitable in this document in the whole text.

It is that operation allows that term " connection " means described flow of material between the assembly enumerated.

What term " communicating downstream " meant the material of the main body flow in communicating downstream can operate its target be communicated with it of outflow at least partly.

Term " upstream connection " mean flow out upstream be communicated with in main body material can operate the target flowing to it and be communicated with it at least partly.

Term " tower " means for being separated one or more distillation towers with different volatile one or more components based on boiling point difference.Tower can have reboiler and have condenser at its tower top bottom it.Except as otherwise noted, the condenser that each tower is included in the tower top of tower is with condensation and feed back stream part top stream gets back to the top of tower, and the reboiler of bottom being included in tower is to evaporate and to carry a part of tower bottoms stream to get back to the bottom of tower.Charging to tower can be through preheating.Top pressure is the pressure of the exit overhead vapours at tower.Bottom temp is liquid bottom temperature out.Tower top pipeline and bottom pipe refer to backflow or boil to the mesh duct out from tower downstream of tower again.

Term used herein " component-Fu stream " means, and the described rich stream of flow container has this component of greater concn compared with the charging of container.

Term used herein " component-lean stream " means, and the described lean stream of flow container has this component of lower concentration compared with the charging of container.

Term " Cx " is interpreted as the molecule that finger has the carbonatoms represented by subscript " x ".Similarly, term " Cx-" refers to containing being less than or equal to x and the molecule of preferred x and less carbon atom.Term " Cx+ " refers to have and is more than or equal to x and the hydrocarbon of preferred x and Geng Duo carbon atom.

Invention summary

We have found that, be used in the ethene in rare ethylene stream (as FCC dry gas stream) through zeolite catalyst, can by the rare benzene alkylation in the stream (as reformate or FCC light naphtha) containing aromatic substance.Can be separated and fusion enters gasoline and diesel pool compared with heavy hydrocarbon.We have found that, be applicable to use light olefin by most of zeolite catalyst of benzene alkylation in rare ethylene stream by quick inactivating.Be the dilution character of ethene or the impurity of existence not materially affect comprise the catalyzer of UZM-8.In addition, by using ethene that the transformation efficiency of benzene alkylation and toluene is equally high and higher than the aromatic substance of more heavy using UZM-8 catalyzer.Therefore, rare ethene in FCC dry gas stream can be used in by the rare benzene alkylation in petroleum naphtha stream (as reformate), reduce to provide benzene concentration and the liquid fuel product be separated in easily unconverted gas stream.Unconverted gas can be used as fuel gas burning, but wherein more valuable ethene is recovered as the hydrocarbon of gasoline-range.

Advantageously, present method and device can make it possible to rare ethene of using under the existence of the raw material impurity that can be catalyzer poison in stream.

Advantageously, even if under the existence compared with heavy aromatic hydrocarbons, present method and device can make it possible to the concentration of the rare benzene be reduced in petroleum naphtha stream and not use hydrogen or reduce the octane value of liquid volume or petroleum naphtha stream.

In one embodiment, the present invention includes the method using ethene to carry out alkylated benzenes, described method comprises the rare ethylene stream of providing package containing the ethene between 5 to 50wt-%.There is provided benzene stream, described benzene stream comprises the toluene of at least 3wt-% and the paraffinic hydrocarbons of at least 20wt-%; Rare ethylene stream contacts with the alkylation catalyst comprising UZM-8 with benzene stream.Finally, by feed steam at least 20% benzene be converted into alkylbenzene.

In another embodiment, the present invention includes the method using ethene to carry out alkylated benzenes, described method comprises and makes catalyst for cracking contact by the hydrocarbon pyrolysis to be the product hydrocarbon through cracking with lower molecular weight with hydrocarbon feed steam, and on the cracking catalyst deposit coke to provide the catalyst for cracking of close-burning.From the catalyst for cracking of the product separation close-burning through cracking.Oxygen is added the catalyst for cracking of close-burning, and on the catalyst for cracking of close-burning close-burning, described close-burning catalyst for cracking oxygen burning to regenerate catalyst for cracking.Be separated through the product of cracking to obtain the rare ethylene stream comprising the ethene between 5 to 50wt-%.There is provided benzene stream, described benzene stream comprises the toluene of at least 3wt-% and the paraffinic hydrocarbons of at least 20wt-%.Rare ethylene stream contacts with the alkylation catalyst comprising UZM-8 with benzene stream.Finally, by feed steam at least 20% benzene be converted into alkylbenzene.

In another embodiment, the present invention includes the method using ethene to carry out alkylated benzenes, described method comprises the rare ethylene stream of providing package containing the ethene between 5 to 50wt-%.Contacted with reforming catalyst by petroleum naphtha stream to provide reformate benzene stream, described reformate benzene stream comprises the toluene of at least 3wt-% and the paraffinic hydrocarbons of at least 20wt-%.Rare ethylene stream contacts with the alkylation catalyst comprising UZM-8 with benzene stream.By in feed steam at least 20% benzene be converted into alkylbenzene.

In one embodiment, the present invention includes the device using ethene to carry out alkylated benzenes, described device comprises fluid catalytic cracking reactor, it is provided for catalyst for cracking and contacts hydrocarbon charging to be cracked into the product through cracking with lower molecular weight with hydrocarbon feed steam, and on the cracking catalyst deposit coke to provide the catalyst for cracking of close-burning.Described device also comprises regeneratory furnace and separator, and described regeneratory furnace is used for by contacting combustion of coke from the catalyst for cracking of close-burning with oxygen, and described separator is communicated with fluid catalytic cracking reactor, with by C ₃hydro carbons and C ₂separation of hydrocarbons is to provide rare ethylene stream.Described device also comprises and is provided for petroleum naphtha stream and contacts reforming reactor to produce reformate stream with reforming catalyst.Finally, described device comprises the alkylation reactor be communicated with described reforming reactor with described separator, it is for the fixed bed by alkylation catalyst, uses the ethene in described rare ethylene stream to be comparatively heavy alkylbenzene hydrocarbons class by the benzene alkylation in described reformate stream.Separation column is not had to be communicated with between described reforming reactor with described alkylation reactor.In alternative embodiment, separation column is not had to be communicated with between described separator with described alkylation reactor.In another embodiment, the resorber be communicated with the product exit of FCC reactor provides implication stream, described stream of working off one's feeling vent one's spleen comprises rare ethylene stream, and do not have separation column to be communicated with between described reforming reactor with described alkylation reactor, and be communicated with between described resorber with described alkylation reactor.

By specification, drawings and the claims of the present invention provided herein, other features and advantages of the present invention will be apparent.

Accompanying drawing is sketched

Fig. 1 is the schematic diagram of FCC unit, reformer unit and alkylation.

Fig. 2 is that transformation efficiency and temperature are schemed over time.

Fig. 3 is that transformation efficiency is schemed over time.

Detailed Description Of The Invention

The present invention can be used for any hydrocarbon flow, and described any hydrocarbon flow comprises the ethene of ethene and preferred Dilution ratio.Suitable rare ethylene stream can comprise the ethene between 5 to 50wt-% usually.FCC dry gas stream is suitable rare ethylene stream.Other rare ethylene stream also can be used for the present invention, as coker dry gas stream.Because the present invention is specially adapted to FCC dry gas, target application describes about the ethene used from FCC dry gas stream.

The present invention can be used for any hydrocarbon flow, and described any hydrocarbon flow comprises the benzene of benzene and preferred Dilution ratio.Suitable benzene stream can comprise the benzene between 1 to 50wt-% usually, at least the toluene of 3wt-% and the paraffinic hydrocarbons of at least 20wt-%.Reformate stream is suitable benzene stream.Other benzene streams also can be used for the present invention, as FCC aromatic petroleum naphtha stream.Because the present invention is specially adapted to reformate stream, target application describes about the benzene used from reformate stream.

Referring now to Fig. 1, the element that wherein identical numeral is identical, Fig. 1 represents refining integrated equipment 6, and it generally includes the FCC unit 10 with product recovery section 90, reformer unit 200 and alkylation 300.

FCC unit 10 comprises reactor 12 and regeneration furnace for catalyst 14.Process variable generally includes 400 ° of scission reaction temperature to 600 ° of C and 500 ° of catalyst regeneration temperature to 900 ° of C.Cracking and regeneration are both carried out under the following absolute pressure of 506kPa (72.5psia).

Fig. 1 illustrates typical FCC reactor 12, and wherein heavy hydrocarbon charge or crude oil stream 16 flow out from divider and contact with the catalyst for cracking through regenerating, and the described catalyst for cracking through regeneration enters from the catalyst standpipe 18 through regeneration.This contact can extend upwardly to generation in the narrow upcast 20 bottom reactor vessel 22.The contact origin self-fluidized type pipe 24 of charging and catalyzer gas fluidized.In one embodiment, the heat from catalyzer makes hydrocarbon charging or oil evaporation, and then when both are upwards transported into reactor vessel 22 along upcast 20, hydrocarbon charging is cracked into the hydrocarbon product of lower molecular weight in the presence of a catalyst.Inevitable side reaction occurs in upcast 20, causes sedimentation of coke to reduce catalyst activity on a catalyst.Then, use cyclonic separator to be separated the Light hydrocarbon products through cracking from the catalyst for cracking of close-burning, described cyclonic separator can be included in initial separator 26 in reactor vessel 22 and one or two rotary wind section 28.Gaseous state through cracking product autoreactor container 22 out, by product exit 31 to pipeline 32 to be transported to downstream product recovery district 90.With catalyst requirement regeneration that is useless or close-burning to use further.After separating from gaseous product hydrocarbon, the catalyst for cracking of close-burning falls into stripping zone 34, and steam is injected by nozzle wherein, to remove hydrocarbon vapour residual arbitrarily.After the stripping operation, by with useless catalyst standpipe 36 by the catalyst strips of close-burning to regeneration furnace for catalyst 14.

Fig. 1 describes regeneratory furnace 14, is called combustion chamber.But the regeneratory furnace of other types is also suitable.In regeneration furnace for catalyst 14, by the stream 30(of oxygen-containing gas as air) introduce by air distributor 38 catalyzer contacting close-burning.From the catalyzer of close-burning combustion of coke with provide through regeneration catalyzer and stack gas.Catalyst regeneration process applies a large amount of heat to catalyzer, provides energy to offset the scission reaction of the heat absorption occurred in reactor upcast 20.Catalyzer upwards flows along the combustion chamber upcast 40 being positioned at regeneration furnace for catalyst 14 together with air, and, after regeneration, be first separated by discharging via disconnector 42.Other recovery of the catalyzer through regeneration and stack gas that leave disconnector 42 are by using first and second grades of separator cyclonic separators 44 respectively in regeneration furnace for catalyst 14, and 46 reach.From the isolated catalyzer of stack gas from cyclonic separator 44,46 are distributed by dipleg (dipleg), the hot flue gases of relative lightweight is from cyclonic separator 44 in the catalyst simultaneously, and 46 orders are discharged and the flue gas outlet 47 passed through in flue gas line 48 is discharged from regeneratory furnace container 14.By the catalyst standpipe 18 through regeneration, the catalyst strips through regeneration is back to upcast 20.As the result of coke burning, the stack gas steam of discharging from the top of regeneration furnace for catalyst 14 in pipeline 48 contains CO, CO ₂, N ₂and H ₂o and other a small amount of kinds.

Product recovery section 90 and product exit 31 communicating downstream.In product recovery section 90, the gaseous state fcc product in pipeline 32 delivers to the lower district of FCC main fractionating tower 92.King-tower 92 and product exit 31 communicating downstream.Separable and take away the multiple cut of fcc product from king-tower, be included in the heavy slurries oil flow from bottom in pipeline 93, heavy recycle oil flow in pipeline 94, from the light recycle oil flow pipeline 95 that outlet 95a takes away, and from the heavy naphtha stream pipeline 96 that outlet 96a takes away.In pipeline 93-96 can be cooled arbitrarily or all and pumped back king-tower 92 to cool the king-tower usually in higher position.Gasoline and gaseous state light hydrocarbon remove from king-tower 92 in overhead line 97, and are condensed before entering king-tower collector 99.King-tower collector 99 and product exit 31 communicating downstream, king-tower 92 is communicated with king-tower collector 99 upstream.

Aqueous stream is removed from the receptor (boot) collector 99.In addition, the light naphtha stream of condensation removes in pipeline 101, and overhead materials stream removes in pipeline 102 simultaneously.Overhead materials stream in pipeline 102 contains gaseous light hydrocarbon, and it can comprise rare ethylene stream.In pipeline 105, a part for the light naphtha stream of the condensation in pipeline 101 can be got back to main fractionating tower 92, leave the light naphtha stream of clean condensation in pipeline 103.Stream in pipeline 101 and 102 can enter the vapor recovery district 120 of product recovery section 90.

Display vapor recovery district 120 is the system based on absorbing, but any vapor recovery system can be used to comprise cold casket (cold box) system.For obtaining the abundant separation of light gas components, the gaseous stream in pipeline 102 is compressed into compressor 104.More than one compressor stage can be used, usually use two stage compression the gaseous stream in pipeline 102 to be compressed between 1.2MPa to 2.1MPa (gauge pressure) (180 to 300psig).Three stage compression can be favourable, to provide at least up to the additional pressure of 3.4MPa (gauge pressure) (500psig).

C3+ hydrocarbon liquid stream in primary absorber bottom line 107 and the C2-hydrocarbon flow in stripper overhead pipeline 108 are added in the compressed light hydrocarbon stream in pipeline 106, chilling is also delivered to high voltage collector 110.Aqueous stream from collector 110 can be passed to king-tower collector 99.The gaseous state first fcc product stream in pipeline 112 comprising rare ethylene stream is passed to the unit of the separation caused between C3+ and C2 – hydrocarbon, is primary absorber 114 in the present embodiment.In primary absorber 114, rare ethene, the first fcc product stream contact to cause being separated between C3+ and C2 – hydrocarbon with the second fcc product stream, and described second fcc product stream comprises the gasoline of the non-stabilization in pipeline 103 from king-tower collector 99.For by C ₃hydro carbons and C ₂the separator of separation of hydrocarbons, it can be primary absorber 114, with king-tower collector 99 communicating downstream.Pipeline 106 got back to by liquid C3+ stream in pipeline 107 before chilling.Remove to comprise rare ethylene stream in the primary exit gas stream of the overhead materials comprising the primary absorber 114 of the dry gas being mainly C2 – hydrocarbon and hydrogen sulfide, ammonia, oxycarbide and hydrogen in pipeline 116.But in order to further concentrating ethylene stream and reclaim comparatively heavy component, pipeline 116 optionally points to second unit, and described second unit causes the separation between C3+ and C2 – hydrocarbon, is secondary resorber 118 in the present embodiment.In secondary resorber, the recycle stream departing from the light cycle in pipeline 121 of pipeline 95 is absorbed in the residual C5+ of major part in primary exit gas stream and some C3-C4 materials.Secondary resorber 118 and primary absorber 114 communicating downstream.What the pump pump around circuit via pipeline 95 made more to be rich in C3+ material is back to king-tower 92 from the light cycle of secondary absorber bottom in pipeline 119.Remove to comprise rare ethylene stream in the secondary outlet gas stream of the overhead materials comprising the secondary resorber 118 of the dry gas being mainly C2 – hydrocarbon and hydrogen sulfide, ammonia, oxycarbide and hydrogen in pipeline 122.Absorber column 114 and 118 neither has condenser or reboiler, but can use pump pump around circuit cooling loop.

The liquid from high voltage collector 110 in pipeline 124 is delivered to stripping tower 126.Major part C2 – is removed and is back to pipeline 106 via overhead line 108 in the overhead materials of stripping tower 126.Stripping tower 126 does not have condenser but is received in the liquid feeding through cooling in pipeline 124.Via pipeline 128, the liquid column bottoms streams from stripping tower 126 is delivered to debutanizing tower 130.From going the overhead materials stream in pipeline 132 of dealkylation tower to comprise C3-C4 olefinic product, and the bottoms stream in pipeline 134 comprising the gasoline of stabilization can be further processed and deliver to gasoline storage.In one embodiment, the bottoms stream in pipeline 134 can be sent to naphtha splitter tower 140.Light naphtha can reclaim from naphtha splitter tower 140 in overhead line 142, and wherein heavy naphtha stream reclaims in bottom line 144.The aromatic petroleum naphtha comprising benzene in pipeline 146 can be used as middle runnings, and in this case, naphtha splitter tower 140 can be partition tower.One in pipeline 142 and 144 in light naphtha and heavy naphtha stream or its both can be taken to gasoline distribution system 148.The heavy naphtha stream illustrating in only pipeline 144 enters the gasoline distribution system 148 in Fig. 1, because the light naphtha stream in pipeline 142 can be used for the processing separated with heavy naphtha.

Rare ethylene stream of the present invention can comprise FCC dry gas stream, and described FCC dry gas stream is included between 5 and 50wt-%, the preferably ethene of 10 to 30wt-%.The main ingredient that methane will typically be in rare ethylene stream, concentration is between 25 and 55wt-%, and ethane exists with the amount typically be between 5 and 45wt-% substantially.Between 1 and 25wt-%, typically the hydrogen of 5 to 20wt-% and nitrogen can be present in rare ethylene stream separately.The water of saturated level also can be present in rare ethylene stream.Rare ethylene stream in overhead line 116 can have and is no more than 3wt-%, is no more than the propylene of 1wt-% suitably, and is usually no more than 25wt-%, be no more than the C3+ material of 15wt-% suitably.If use secondary resorber 118, the rare ethylene stream in overhead line 122 can have the C3+ being no more than 5wt-%, is usually less than the propylene of 0.5wt-%.Except hydrogen, other impurity such as hydrogen sulfide, ammonia, oxycarbide and acetylene also can be present in rare ethylene stream.

Impurity in dry gas ethylene stream can poison alkylation catalyst.Carbonic acid gas and ammonia can attack the sour site on catalyzer.Known hydrogen sulfide is deactivation zeolite catalyst sometimes.Acetylene polymerizable also forms blocking on catalyzer or equipment.

Comprise the primary exit gas stream in pipeline 116 of rare ethylene stream or the secondary outlet gas stream in pipeline 122 can be introduced into optional amine absorber unit 150 to remove hydrogen sulfide to lower concentration.Water-based amine aqueous solution (as comprising the water-based amine aqueous solution of monoethanolamine or diethanolamine) introduced resorber 150 by pipeline 152 and contacts with absorbing hydrogen sulphide with the stream of working off one's feeling vent one's spleen of flowing, and by pipeline 154 hydrogen sulfide containing for richness water-based amine absorbent solution removed from uptake zone 150 and reclaim and may process further.

Can by the optional poor hydrogen sulfide in pipeline 156, rare ethylene stream of amine process introduces the residual amine that optional washing unit 160 brings from amine resorber 150 with removing, and the ammonia reduced in the rare ethylene stream in pipeline 156 and gas concentration lwevel.By the washing in water introduction pipe line 162.Water in pipeline 162 usually slightly by acidifying to improve alkali molecules catching as amine.The aqueous stream in pipeline 164 being rich in amine and potential ammonia and carbonic acid gas is left washing unit 160 and can be further processed.

Optionally amine process in pipeline 166, then rare ethylene stream of optionally washing can process to remove one or more impurity if carbon monoxide, hydrogen sulfide and ammonia are to low concentration in optional protection bed 170.Protection bed 170 can comprise sorbent material may poison the impurity of alkylation catalyst as ammonia with absorption.Protection bed 170 can comprise multiple sorbent material with absorption more than a kind of impurity.Typical sorbent material for adsorption of hydrogen sulfide is ADS-12, and the typical sorbent material for sorbing carbon monoxide is ADS-106, and the typical sorbent material for adsorb ammonia is UOP MOLSIV 3A, all from UOP, LLC.Sorbent material can mix and maybe can be arranged in successive bed in single bed.

Optionally amine process in pipeline 172, optionally wash and the stream of optionally adsorption treatment can be dry with except anhydrating to 500wppm water in moisture eliminator 174.Water can disadvantageous effect alkylation catalyst.

Optionally amine process, optionally wash, optionally adsorption treatment and the optionally dry rare ethylene stream in pipeline 176 there is at least one following impurity concentration usually: the carbon monoxide of 0.05wt-% to 5.0wt% and/or the carbonic acid gas of 0.1wt-% to 5.0wt%, and/or at least 1wppm to 500wppm hydrogen sulfide and/or at least 1 to 500wppm ammonia, and/or at least 5 to 20wt-% hydrogen.The dopant type existed and concentration thereof depend on processing and rare ethylene stream source and changing.

If must be forced into alkylation reactor pressure, then rare ethylene stream is brought to compressor 180 by pipeline 176.Compressor 180 and king-tower 92, product recovery section 90 and product exit 31 communicating downstream.Compressor 180 can comprise one or more levels with interstage cooling.Well heater can be needed so that compressed stream is brought to temperature of reaction.In pipeline 182, compressed rare ethylene gas stream is brought to alkylation 300.Rare ethylene stream is fed to alkylation reactor unit 300 by pipeline 182.Alkylation reactor unit 300 can with compressor 180 and/or for by C ₃hydro carbons and C ₂first or second separator downstream of separation of hydrocarbons is communicated with, and it can be respectively elementary or secondary resorber 114 and 118.In one embodiment, fractionation unit is not had for by C ₃hydro carbons and C ₂first separator of separation of hydrocarbons or be communicated with between the second separator with alkylation reactor 320.Therefore, in one embodiment, fractionation unit is not had to be communicated with in primary absorber 114 or between secondary resorber 118 with alkylation reactor 320.In this embodiment, rare ethylene stream can stand the separation based on absorption or absorption, but do not carry out the fractionation based on boiling point difference to rare ethylene stream, this rare ethylene stream can be included in primary absorber 114 and/or the elementary or secondary outlet gas between secondary resorber 118 and alkylation reactor 320.This embodiment is contrary with traditional concept, and traditional concept is thought, before the alkylated reaction that ethene can bear with benzene, rare ethene dry gas stream needs fractionation (as fractionation in demethanizing tower) to remove comparatively light constituent.The elimination of demethanizing tower causes the saving of a large amount of operation and capital.

Go to reformer unit 200, the feed naphtha stream in pipeline 202 mixes with the stream comprising hydrogen from pipeline 204, in reforming reactor 210 heating and with catalyst exposure to produce reformate.Desirably, reforming reactor 210 is flowing bed reactor, and its rare gas element by fluidisation is accepted the catalyzer through regeneration by pipeline 220 and discharged with useless catalyzer to breeding blanket 230 by pipeline 222.Catalyzer flows to bottom from the top of stack type reactor 210, first by reduction zone 224, the gas being rich in hydrogen wherein from pipeline 226 contacts and the granules of catalyst reduced through being oxidized.From this place, catalyst stream through multiple reaction zone, wherein naphtha feed contact catalyst particle.Reforming reactor 210 can comprise stack type reactor array, and it can comprise multiple reaction zone.Each reaction zone have catalyst bed in stack type reactor 210 with allow granules of catalyst from reaction zone, top 212 respectively by second and the 3rd reaction zone 214 and 216 to final district 218 continuously or intermittent flow.Can be drawn out of from the first reaction zone by the effluent of the 3rd reaction zone 212-216, heat and make it to be back to subsequent reaction zone 214-218 respectively.Catalyst bed more or less can be used.Reformate product stream can by from end reaction district 218 suction pipeline 232.Lower reservation room 234 bottom stack type reactor 210 accepts with useless catalyzer.The washing fluid preferably comprising hydrogen enters lower reservation room 234 with the speed of being cleaned lower reservation room 234 from granules of catalyst by hydrocarbon from pipeline 236.

The raw material being generally used for catalytic reforming is for being called petroleum naphtha and having the petroleum fractions of the initial boiling point of 46 ° of C (115 °F) and the full boiling point of 204 ° of C (400 °F).Catalystic reforming method is specially adapted to process virgin naphtha, and described virgin naphtha is made up of the naphthenic hydrocarbon of relatively large concentration and the paraffinic hydrocarbons of basic straight chain, and it stands aromizing by dehydrogenation and/or cyclization.In reformation, hexanaphthene, the dehydrogenation-isomerization of dehydrogenation and alkyl cyclopentane obtains aromatic substance, the dehydrogenation of paraffinic hydrocarbons obtains alkene, the dehydrocyclization of paraffinic hydrocarbons and alkene obtains aromatic substance, the isomerization of n-paraffin and alkyl naphthene obtains hexanaphthene, the aromatic substance of replacement be isomerized and paraffinic hydrocarbons by hydrocracking.

Catalytic reforming usually granules of catalyst exist under carry out, described granules of catalyst by one or more group VIII noble metals as platinum, iridium, rhodium, palladium and halogen form in conjunction with porous support (as refractory inorganic oxide).Halogen is generally chlorine.Aluminum oxide is conventional carrier.Preferred alumina material is γ, η and θ aluminum oxide, and wherein γ and η aluminum oxide obtains optimum.The critical nature relevant with catalyst performance is the surface-area of carrier.Preferred vector has 100 to 500m ²the surface-area of/g.Particle is generally spherical and has the diameter of 1/16th to 1/8th inch (1.5-3.1mm), although it can be as big as 1/4th inch (6.35mm).In the process of reforming reaction, as the result of some mechanism (as the mechanism of sedimentation of coke on particle), granules of catalyst becomes inactivation; That is, after used a period of time, the ability of granules of catalyst promotion reforming reaction is reduced to the level that catalyzer is die on.It can again for reforming process in before, catalyzer must be repaired or regenerate.

Breeding blanket 230 regenerated catalyst is also recycled to pipeline 220.The granules of catalyst that use containing deposits of coke is given up is from the separation vessel 240 flowed breeding blanket 230 by riser duct 222 in the lower reservation room 234 of stack type reactor 210.Separation vessel 240 can comprise Liang Ge district.In upper district 242, elutriation fluid to be broken or the speed of cracked granules of catalyst and catalyst fines enters upper district 242 to be separated from the whole granules of catalyst of the bottom leaving separation vessel 240.Catalyst debris and particulate and elutriation fluid flow out from upper district 242, and described elutriation fluid can be filtered and be recycled to district 242.In inferior segment 244, the catalyzer through elutriation contacts to adsorb chlorine and hydrogenchloride on a catalyst with the stack gas through cooling from pipeline 246.By the stack gas in pipeline 246 and the stack gas heat exchange from dechlorination in the pipeline 248 of inferior segment 244, adsorption conditions can be entered to make it cool before being fed to inferior segment 244.Catalyzer enters regeneration furnace for catalyst 250 by pipeline 252 from inferior segment 244.

Regeneration furnace for catalyst 250 comprises combustion zone 254 and regulatory region 256.In combustion zone, catalyzer declines in inner annular chamber 258, and described inner annular chamber 258 can comprise catalyzer by impermeable concentric screens.By with the stack gas heat exchange in pipeline 246, the stack gas of dechlorination reclaimed in pipeline 248 is heated and is fed to outer annular room 260.Stack gas through reclaiming enters inner annular chamber 258 with heatable catalyst wherein from outer annular room 260 by outer screen.What comprise the oxygen that rises from regulatory region and chlorine also enters inner annular chamber 258 with from catalyst combustion deposits of coke for the gas in regulatory region 256.Hot combustion gas leaves inner concentric screen cloth and enters internal pipeline 245 and leave the combustion zone 254 in pipeline 246.Catalyzer through burning declines and enters surge chamber 256 and enter central zone 262 in ring-type traverse baffle.Can oxygen be rich in and the air feed mixed with chlorine enters the lower annular chamber 266 outside pipeline 264 to ring-type traverse baffle, and pass into central zone 262 with catalyst exposure to disperse metal on a catalyst.Through the catalyzer of regeneration leave regulatory region 256 and be lifted in pipeline 220 gas of fluidisation auxiliary under get back to reforming reactor 210.

Reformate splitter tower 270 can with reforming reactor 210 communicating downstream, and to be communicated with between alkylation reactor at reforming reactor 210 by pipeline 232.In this embodiment, the control valve on pipeline 278 is closed at least partly, and the control valve on pipeline 272 is opened at least partly, makes pipeline 272 can from pipeline 232 feed reformer product product stream to reformate splitter tower 270.Fractionation produces lightweight reformate stream in overhead line 274, and then it enter pipeline 304 and alkylation reactor 320 by the control valve benzene feed stream that it is opened.Lightweight reformate benzene stream can have the benzene of 20 to 50wt-%, and the toluene of at least paraffinic hydrocarbons of 20wt-% and surplus at least 3wt-%.In one embodiment, lightweight reformate benzene stream has the paraffinic hydrocarbons of concentration larger than benzene.Benzene stream preferably comprises the benzene of at least 4.0wt-%.The bottoms stream leaving the heavy reformate product in the pipeline 276 at the end half of reformate splitter tower 270 can bypass alkylation reactor 320 and is passed to gasoline distribution system 148 and is not communicated with alkylation reactor 320.

Alternatively, the whole reformate streams in pipeline 232 can bypass reformate splitter 270 or reformer unit 200 can omit reformate splitter tower 270 completely.In this embodiment, control valve on pipeline 272 and 274 is closed, and the control valve on pipeline 278 is opened at least partly, thus pipeline 232 can the whole reformate product stream of charging to pipeline 304 and alkylation reactor 320.In this embodiment, whole reformate stream can deliver to alkylation 300 in pipeline 278.Can whole omission reformate splitter.In this embodiment, separation column is not had to be communicated with between described reforming reactor 210 with described alkylation reactor 320.In this embodiment, whole reformate stream can stand the separation based on absorption or absorption, but does not carry out the fractionation based on boiling point difference to the reformate stream between reforming reactor 210 and alkylation reactor 320.This embodiment is contrary with traditional view, and traditional view is thought, whole reformate stream needs fractionation (as in reformate splitter tower) to remove heavy aromatic compounds can bear the alkylated reaction with alkene at benzene before.The elimination of reformate splitter tower causes the saving of a large amount of operation and capital.

Whole reformate stream will comprise the benzene of 1 to 10wt-%, and the toluene of 3 to 30wt-% and surplus be the paraffinic hydrocarbons of 20wt-% and heavy aromatic compounds at least.Whole reformate stream comprises the aromatic compounds substrate concentration of molecular weight higher compared with the concentration of benzene higher than benzene.Especially, whole reformate stream can have the aromatic substance with 8 carbon atoms of greater concn compared with benzene concentration.In addition, whole reformate stream can have the paraffinic hydrocarbons of greater concn compared with benzene.

Benzene stream is fed to alkylation 300 by pipeline 304.Alkylation 300 can with reformate splitter tower 270 communicating downstream.Alkylation reactor 320 preferably also can contain multiple catalyst bed 342-46 containing fixing catalyst bed 342.Catalyzer is preferably the UZM-8 zeolite bound with aluminum oxide.

In one embodiment, diene in the rare ethylene stream of gaseous state in pipeline 182 in bottoms stream is optionally transferred into and first reacts with the selective hydrogenation catalyst in selec-tive hydrogenation district 310, not exclusively makes it saturated for paraffinic hydrocarbons optionally to make diene saturated.The conditions suitable of operation selec-tive hydrogenation process comprises with the conveying of the mol ratio of 0.5 to 5 moles of hydrogen/mole diene in the rare ethylene stream of gas phase in pipeline 302 with pass through catalyzer from the hydrogen of pipeline 308, described catalyzer comprises the metal that at least one is selected from nickel, palladium and platinum, be deposited on carrier as on aluminum oxide, temperature is 20 ° to 200 ° C (68 ° to 392 °F), pressure is 689 to 3447kPa (g) (100 to 500psig), and air speed is 0.5 to 10hr ^-1.Two or more reaction zones can be used, although only show one.The recovery (not shown) of reactor effluent to reactor inlet can be carried out in each reaction zone, and wherein reclaiming with the ratio of ethylene feed stream is 0 to 20.The diene content that this process remains can be 1 to 100wppm, depends on the stringency of operation.

Rare ethylene stream of the selective hydrogenation reaction device 310 in the future in comfortable pipeline 312 is injected into alkylation reactor 320.On the one hand, the moisture eliminator (not shown) on pipeline 312 can be used with except anhydrating to lower concentration, and it may affect alkylation catalyst.Also estimate that other protection beds are to remove catalyzer poison as being low to moderate 1 to 500wppm except deammoniation or amine.One in catalyst bed can be used as protection bed with except anhydrating and catalyzer poison.If moisture eliminator or protection bed are used for the ethylene feed side of alkylation 300, then one in moisture eliminator 176 and adsorbent bed 170, part or both can omit from product recovery section 90.Rare ethylene stream in pipeline 312 with in pipeline 114 or 122, there is substantially identical composition, except the impurity be removed.Optionally amine process, optionally wash, optionally adsorption treatment and the optionally dry rare ethylene stream in pipeline 312 usually can have the following impurity concentration of at least one: 0.05wt-% is also up to the carbon monoxide of 5.0wt% and/or 0.1wt-% and is up to the carbonic acid gas of 5.0wt%, and/or at least 1wppm be up to the hydrogen sulfide and/or at least 1 and be up to ammonia and the amine of 500wppm of 500wppm, and/or at least 5 and be up to the hydrogen of 20wt-%.

Although transalkylation reaction can occur in alkylation reactor 320, alkylated reaction is main.Alkylation reactor is shown as flow reactor, but downflow reactor also can be suitable.Before entering catalyst bed 342,344 and 346 respectively, the stream of rare ethene in pipeline 312 is injected in multiple pipeline 322,324 and 326 alkylation reactor 320 and enters preparation bed space 332,334 and 336.Catalyst bed 342,344 and 346 containing alkylation catalyst with by ethylene alkylation to benzene to produce ethylbenzene, and by ethylene alkylation to toluene to produce ethyltoluene.There are other alkylated reactions to produce alkylbenzene and Alkylaromatics.Liquid benzene stream in pipeline 304 is fed to alkylation reactor 320, makes it first absorb rare ethylene stream from the pipeline 326 preparation bed space 336 and enter catalyst bed 346 together wherein.Before entering alkylation reactor 320, the aromatics reformate feed steam in pipeline 304 also can accept the FCC aromatic streams from pipeline 146.Alternatively, if naphtha splitter only provides two streams, then one of them can use aromatic petroleum naphtha feeding line 304, and aromatic petroleum naphtha is preferably the light naphtha stream in pipeline 142.Gaseous ethylene be dissolved into liquid reformate stream with aromatic ring alkylation.

Effluent from catalyst bed 346 is mixed with fresh dry gas, and described fresh dry gas comprises the rare ethene from the pipeline 324 in preparation bed space 334, and enters catalyst bed 344 together.Effluent from catalyst bed 344 is mixed with fresh dry gas, and described fresh dry gas comprises the rare ethene from the pipeline 322 in preparation bed space 332, and enters catalyst bed 342 together.Described process is repeated to the multiple beds in alkylation reactor 300.Although demonstrate three catalyst beds in alkylation reactor 300, it is suitable that more or less bed and other reactors can be.The alkylate stream effluent of self-alkylation reaction device 320 is conveyed into effluent pipeline 352 in the future.Heat exchanger 354 can cool effluent in pipeline 352 to required temperature.By making alkylation reactor effluent stream reduce pressure through pressure controlled valve, or by making the supercharging of alkylation reactor effluent stream through pump, both all do not show.

Preferred alkylation catalyst of the present invention is as described below.Preferred alkylation catalyst comprises UZM-8 zeolite.One in the component of the support of the catalyst used in the present invention is aluminum oxide.Alumina source can be any number of Alpha-alumina monohydrate as boehmite or plan-boehmite structure in multiple hydrated aluminum oxide or alumina gel, the Alpha-alumina trihydrate of gibbsite structure, beta-alumina trihydrate of bayerite structure etc.Particularly preferred aluminum oxide can trade mark Catapal purchased from Sasol North America Alumina Product Group.This material is the Alpha-alumina monohydrate (plan-boehmite) of extreme high purity, shows it after high-temperature calcination, obtains highly purified gama-alumina.The zeolites component of catalyzer for being described in US 6,756, the UZM-8 in 030.

Suitable alkylation catalyst is prepared to reach required zeolite-ratio-alumina ration by the UZM-8 and aluminum oxide being mixed into the volume of ratio.In one embodiment, 70wt-%UZM-8 and 30wt-% alumina powder will provide suitable carrier.In one embodiment, to be that weight ratio that 70-is more different than-30 can be than aluminum oxide suitable from UZM-8, and scope is from 90wt-%UZM-8 content to 20wt-%UZM-8 content, and surplus is aluminum oxide.

Can by monoprotic acid as nitric acid or formic acid add mixture in aqueous solution with peptization aluminum oxide in a binder.Other water can be added mixture and think that composition has enough denseness doughs and provides enough humidity to be extruded or spraying dry.

This paste or dough can make the form of shaped particles, and preferred method is that the die orifice of opening by wherein having desired size and shape extrudes dough, and squeezed effluent is broken for the extrudate of desired length and dried afterwards.The intensity that further calcining increases to give extrudate can be carried out.Usually, calcine and carry out in dry air stream at 260 ° of C (500 °F) to 815 ° of C (1500 °F) temperature.

The particle extruded can have the shape of cross section of any appropriate, that is, symmetrical or asymmetric, but the most usually has symmetric cross-sectional shape, preferably spherical, cylindrical or leafy (polylobal) shape.The cross-sectional diameter of particle can be little of 40 μm; But, it typically is 0.635mm (0.25 inch) to 12.7mm (0.5 inch), preferred 0.79mm (1/32 inch) to 6.35mm (0.25 inch), most preferably 0.06mm (1/24 inch) to 4.23mm (1/6 inch).Trefoil cross section is similar to, as at US 4, shown in Fig. 8 and 8A of 028,227 in preferred catalyst configuration.Preferred cloverleaf pattern particle is make each " blade " of cross section by 270 ° of arc definition of the circle of diameter between 0.51mm (0.02 inch) and 1.27mm (0.05 inch).Other preferred particles are have those of four leaf shape of cross sections, comprise asymmetric shape and symmetrical shape, as US 4, and 028, the Figure 10 in 227.

Because reaction is carried out under at least partial liquid phase conditions, adjustable reaction pressure is to maintain ethene at least in part in the liquid phase.Ethene is also suitable in the gas phase.Pressure can change in the wide region of 101 to 13172kPa (gauge pressure) (1 to 1900psig).In fact, in the scope of pressure usually between 1379 and 6985kPa (gauge pressure) (200 to 1000psig), but in scope usually between 2069 and 4137kPa (gauge pressure) (300 and 600psig).Be applicable to using ethene to be between 100 ° and 300 ° of C by the temperature range of benzene alkylation.Aromatic substance than ethene ratio should 1:10 and up to 10:1 between, the preferably ratio of 0.5 to 1.0.

Rare ethylene feed can be fed at temperature between 100 ° and 300 ° of C the alkylation reactor 320 in gas phase.Reaction mainly counts WHSV 0.01 to 10hr-with ethene in the liquid phase ¹lower generation.Gaseous ethylene Absorbable rod enters in liquid benzene stream there is alkylation.We have found that, make us uncannily, poison catalyzer although exist in charging and dilute the impurity of the ethene in charging, in feed steam at least 40wt-% to as high as the ethene of 75wt-% and aromatic ring alkylation to be converted into comparatively heavy alkylaromatic hydrocarbons.

Rare benzene charging can be fed at temperature between 100 ° and 300 ° of C the alkylation reactor 320 in liquid phase.Reaction mainly counts WHSV 0.1 to 40hr-with benzene in the liquid phase ¹lower generation.We have found that, make us uncannily, although the comparatively heavy aromatic compounds of benzene existed in charging in dilution charging and paraffinic hydrocarbons, at least 20wt-% in feed steam, at least 50wt-% and the benzene up to 100wt-% are converted into comparatively heavy alkylbenzene suitably.In addition, the transformation efficiency of benzene is at least 80% of toluene conversion, preferably at least 90%, most preferably at least 95%.Even if rare benzene charging can have the aromatic substance with 8 carbon atoms of greater concn compared with benzene concentration, but compared with having the aromatic substance of 8 carbon atoms, benzene stands higher transformation efficiency.Benzene can be between 0.2 and 4.0 than the ratio of alkene.

Even if be impure charging, catalyzer is still stablized, but it can be reproduced when inactivation.Suitable regeneration condition comprises catalyzer is stood, (such as, original position), the warm air of 500 ° of C 3 hours.Activity and selectivity through the catalyzer of regeneration can be suitable with live catalyst.

The alkylate stream from alkylation reactor in pipeline 352 can be transferred into alkylate separation column 360, and it can be simple flash drum, but is preferably separation column with from liquid stream separating gaseous stream.Alkylate separation column 360 and alkylation reactor 320 communicating downstream.Gaseous product stream in overhead line 362 can be transferred into fuel element 370 to produce steam in pipeline 372, and described gaseous product stream comprises light gas as hydrogen, methane, ethane, unreacted alkene and light impurities.Alternatively, the gaseous product in overhead line 362 can be burned to light well heater (not shown) and/or to provide flue gas sources to generate electricity to make internal combustion turbine (not shown).Overhead line 362 is communicated with fuel element 370 upstream.Can make from comprising in the pipeline 364 of alkylate separation column 360 descendingly compared with the liquid column bottoms streams of heavy hydrocarbon being recycled to product separation district 90 by valve via LCO pump pump around circuit 95.Therefore, king-tower 92 is communicated with upstream with alkylation reactor 320 communicating downstream.Preferably the materials at bottom of tower stream in pipeline 364 is recycled to king-tower 92, described king-tower 92 is between heavy naphtha outlet 96a and light recycle oil export 95a.The bottom communicating downstream of recovery line 364 and alkylate separation column 360.Alternatively, recovery line 364 charging light recycle oil pump pump around circuit pipeline 95 or heavy naphtha pump pump around circuit pipeline 96.Recovery line 364 and alkylation reactor 320 communicating downstream, be communicated with king-tower 92 upstream.Alternatively, the alkylate in pipeline 364 can be transported to gasoline distribution system 148 and not be recycled to product separation district 90.

The naphtha range alkylbenzene stream with the more benzene of small concentration compared with (its can from sideing stream in outlet line 366) in pipeline 304 can be recovered and be sent to gasoline distribution system 148.Gasoline distribution system 148 can comprise to outlet, extremely for filling the divider of the tank for carrying or the pipe arrangement to petrol storage tanks.Gasoline distribution system 148 and alkylation reactor 320 communicating downstream.In one embodiment, compared with the bottoms stream (it can be only viscosity stream) in pipeline 364, the stream that sides stream in pipeline 366 will have larger flow velocity.

Embodiment

Application of the present invention will be shown by following embodiment.

Embodiment 1

Be 12 by combination UZM-8 powder with Si/Al ratio, and with plan-boehmite that Catapal trade mark provides, synthesize the UZM-8 catalyzer through extruding.Before mixing with unbodied silica-alumina, use nitric acid peptization plan-boehmite.Catalyzer dough extruded by the 1.59mm opening in column-form and under 550 ° of C calcining before in flakes cracked.Final catalyzer is made up of 70wt-%UZM-8 and 30wt-% aluminum oxide and has 368m ²the surface-area of/g.

Embodiment 2

The catalyzer of testing example 1 in fixed bed operation on 10mL catalyzer 205 ° of C, 3447kPa (500psig), 0.4OWHSV (olefin feed weight space time velocity) and liquid feeding WHSV is the benzene alkylation under 4.9.Gas feed is by 23mol-%C ₂h ₄and 77mol-%CH ₄composition.Liquid feeding is by 2.6wt-% amylene, 6.4wt-%C ₆h ₆, 30wt-%n-heptane, 25wt-% toluene, 18wt-% have aromatic substance (C9 aromatic substance) composition that the aromatic substance (C8 aromatic substance) of 8 carbon atoms and 19wt-% have 9 carbon atoms.

For ethene, 83% is converted, and the benzene of 51% is converted.Toluene conversion is 49%, and C8 and C9 aromatic compound conversion rate is less than 20%.Be 5% to the selectivity of ethylbenzene, be 25% to the selectivity of ethyltoluene, the selectivity of p-diethylbenzene is 6%, is 37% to the selectivity of other gasoline-range compounds, is 27% to boiling point higher than the selectivity of the compound of 225 ° of C.

After 13 hours, temperature is raised to 236 ° of C.At 26 hour-symbols, liquid feeding WHSV is increased to 12.7.Under these conditions, conversion of ethylene is 83%, and benzene transformation efficiency is 32%, and toluene conversion is 27%, C ₈and C ₉aromatic conversion rate is for being less than 15%.Be 4% to the selectivity of ethylbenzene, be 17% to the selectivity of ethyltoluene, the selectivity of p-diethylbenzene is 2.5%, is 53.5% to the selectivity of other gasoline-range compounds, is 23% to boiling point higher than the selectivity of the compound of 225 ° of C.

At 46 hours on stream, gas feed is converted into the adulterant representing FCC dry gas composition, and FCC dry gas composition contains 34mol-%CH ₄, 23mol-%C ₂h ₄, 14mol-%C ₂h ₆, 13mol%H ₂, 13mol-%N ₂, 2mol-%CO ₂, 1mol-%CO and 1ppmH ₂s.Transformation efficiency and selectivity do not change.Test shown in Figure 2.

Embodiment 3

The catalyzer of testing example 1 in fixed bed operation on 12mL catalyzer 205 ° of C, 3447kPa (500psig), 0.8OWHSV and liquid feeding WHSV is the benzene alkylation under 7.The similar dry gas charging of gas feed is by 34mol-%CH ₄, 23mol-%C ₂h ₄, 14mol-%C ₂h ₆, 13mol-%H ₂, 13mol-%N ₂, 2mol-%CO ₂, 1mol-%CO and 1ppm H ₂s forms.Liquid feeding is made up of 39wt-% benzene, 49wt-% normal heptane and 12wt-% toluene.Ethene is 77% to 58% through 50 hours transformation efficiencys on stream, and benzene transformation efficiency is constant 44%.Toluene conversion is 47%.Be 50-53% to the selectivity of ethylbenzene, be 14-16% to the selectivity of ethyltoluene, the selectivity of p-diethylbenzene is 17-19%, is 11-14% to the selectivity of other gasoline-range compounds, is 3% to boiling point higher than the selectivity of the compound of 225 ° of C.Test shown in Figure 3.

Though do not elaborate further, believe that those skilled in the art can use above-mentioned explanation, utilize the present invention to ultimate attainment.Therefore aforementioned preferred specific embodiments is appreciated that as only exemplary, and limits rest part of the present disclosure never in any form.

In the preceding article, all temperature are degree Celsius, all numbers and percentage ratio by weight, unless otherwise specified.

According to aforementioned explanation, those skilled in the art can easily determine inner characteristic of the present invention, and can carry out multiple changes and improvements of the present invention when without departing from the spirit and scope of the present invention, adapt to multiple use and condition to make it.

Claims

1. use ethene to carry out a method for alkylated benzenes, described method comprises:

Providing package contains rare ethylene stream of 5 to 50wt-% ethene and the methane between 25 and 55wt-%;

Providing package is containing the benzene stream of at least 3wt-% toluene and at least 20wt-% paraffinic hydrocarbons, and this benzene stream is liquid benzene stream;

Make to comprise further at least 1wppm hydrogen sulfide to contact with the alkylation catalyst comprising UZM-8 with liquid benzene stream with rare ethylene stream of at least 1wppm ammonia; And

By in liquid benzene stream at least 20% benzene be converted into alkylbenzene, wherein the transformation efficiency of benzene is at least 90% of toluene conversion.

2. the method for claim 1, wherein benzene stream has the aromatic substance of molecular weight higher than benzene of greater concn compared with the concentration of benzene.

3. the method for claim 1, wherein benzene stream comprises the aromatic substance with 8 carbon atoms of greater concn compared with benzene, but compared with having the aromatic substance of 8 carbon atoms, benzene stands higher transformation efficiency.

4. the method for claim 1, wherein said benzene stream has the paraffinic hydrocarbons of greater concn compared with benzene.

5. the method for claim 1, wherein said contact procedure is carried out in the fixed bed of described catalyzer.

6. the method for claim 1, wherein said rare ethylene stream comprises at least one impurity, and described impurity is selected from the group be made up of the carbonic acid gas of the hydrogen of at least carbon monoxide, at least 5wt-% of 0.05wt-% and at least 0.1wt-%.

7. the method for claim 1, wherein said benzene stream provides from reforming reactor as reformate stream.

8. method as claimed in claim 7, wherein not reformate stream described in fractionation between described reforming reactor and described alkylation reactor.

9. use ethene to carry out a device for alkylated benzenes, described device comprises:

Fluid catalytic cracking reactor, it is provided for catalyst for cracking and contacts hydrocarbon charging to be cracked into the product through cracking with lower molecular weight with hydrocarbon feed steam, and on the cracking catalyst deposit coke to provide the catalyst for cracking of close-burning;

Regeneratory furnace, it is for the catalyst for cracking combustion of coke by contacting with oxygen from described close-burning;

The separator be communicated with described fluid catalytic cracking reactor, it is for by C ₃hydro carbons and C ₂separation of hydrocarbons is to provide rare ethylene stream;

Reforming reactor, it is provided for petroleum naphtha stream and contacts to produce reformate stream with reforming catalyst; And

The alkylation reactor be communicated with described reforming reactor with described separator, it is for the fixed bed at alkylation catalyst, use the ethene in described rare ethylene stream to be comparatively heavy alkylbenzene hydrocarbons class by the benzene alkylation in described reformate stream, wherein do not have separation column to be communicated with between described separator with described alkylation reactor;

With the alkylate separation column of described alkylation reactor communicating downstream;

With the bottom communicating downstream of alkylate separation column and the pipeline that is communicated with FCC main fractionating tower or gasoline distribution system upstream.