CN106103663B - Method for oil plant heavy hydrocarbon to be modified to petroleum chemicals - Google Patents

Abstract

The present invention relates to a kind of methods for oil plant heavy hydrocarbon to be modified to petroleum chemicals, the described method comprises the following steps：(a) hydrocarbon raw material is fed to ring-opening reaction area；(b) effluent from (a) is fed to separative element, is used to prepare the gas stream comprising lightweight boiling hydrocarbon, the liquid flow comprising naphtha boiling-range hydrocarbon and the liquid flow for including diesel boiling range hydrocarbon；(c) liquid flow comprising naphtha boiling-range hydrocarbon is fed to Hydrocracking unit.

Description

Method for oil plant heavy hydrocarbon to be modified to petroleum chemicals

The present invention relates to a kind of methods for oil plant heavy hydrocarbon to be modified to petroleum chemicals.

EP 1 779 929 is related to a kind of form for being converted into the hydrocarbon raw material of sulfur-bearing suitable for automotive diesel Method.

U.S. Patent Application No. 2012/000819 is related to a kind of method for producing the alkylbenzene of tool high added value, with And the catalyst for this method, wherein the method is by causing hydrocracking reaction appropriate without causing unnecessary ring In the case of hydrogenation (nuclear hydrogenation) allow that minimum cycloalkanes ring-opening reaction occurs.

U.S. Patent number 4,943,366 is related to the cut fraction hydrogenation of the high-aromaticity by will be obtained from catalytic cracking operation Cracking prepares high-knock rating gasoline, wherein gas oil (gas oil) and residue are fed the cracking in FCC unit, and will split Change product to be fractionated in cracker fractionator and in a distillation column.Hydrotreater, hydrotreater shape will be then sent to compared with low boiler cut At the first stage of Hydrocracking unit.Then the recycle oil of hydrogen will be added to be passed through another hydrocracker, the hydrocracker The second stage of unit is formed, the saturation of wherein aromatic compounds continues, and open loop and ring crack occurs, and forms hydrogen and splits The product of change.In the separator after hydrogen separation, hydrocracker effluent is fractionated in a distillation column, formation includes dry gas, vapour Oily, midbarrel and bottom sediment fraction product.

WO2007/055488 is related to the method for preparing aromatic hydrocarbons and liquefied petroleum gas (LPG) by hydrocarbon mixture, and this method includes Following steps：(a) hydrocarbon material mixture and hydrogen are introduced at least one reaction zone；(b) in the reaction zone, in catalyst In the presence of, the hydrocarbon material mixture (i) is converted to non-aromatic hydrocarbon compound by being hydrocracked, and (ii) passes through de- alkyl Change/transalkylation is converted to the aromatic compound rich in benzene, toluene and dimethylbenzene (BTX)；(c) pass through gas-liquid separation And distillation, recycling LPG and aromatic compound in the reaction product obtained respectively from step (b).

WO99/22577 is related to low pressure hydrocracking, and this approach includes the following steps：(a) liquid feedstock and hydrogen are mixed It closes, (b) splits the hydrogenation mixture in the mixed bed hydrocracker of the bed at least two catalyst filling particles Change, prepare light fraction and heavy end, a part for heavy end (c) is passed through into the elimination that includes the following steps (extinction) process recycling：(1) material to be recycled is led into hydrocracker, and (2) by the weight of effluent Matter fraction recycles.

U.S. Patent Application No. 2012/205285 is related to the method for hydrotreating hydrocarbon charging, and the method includes (a) The charging is set to be contacted with (i) diluent and (ii) hydrogen, to prepare liquid feedstock；(b) liquid feedstock is made to be urged with first Agent contacts in the first treatment region, to generate the first product effluent；(c) first product effluent and second is made to be catalyzed Agent contacts in second processing area, to generate the second product effluent；And (d) by a part for second product effluent It is recycled in the diluent in step (a) as recycle product stream, wherein first treatment region includes extremely In few two stages, wherein first catalyst is hydrotreating catalyst, and second catalyst is ring opening catalyst, First treatment region and second processing area are full liquid reaction zone.

U.S. Patent Application No. 2012/083639 is related to a kind of for making high value aromatics using the proposition of stabilized crude benzol The maximized method of production of chemicals, this approach includes the following steps：Aromatics comprising C 5 fraction and C6 to C10 fractions is reacted Device effluent is separated into benzene-enriched stream and at least one liquid flow and at least one gas stream (poor benzene), and one in poor benzene liquid flow Kind includes the C6 fractions of poor benzene；And from benzene-enriched stream remove C 5 fraction at least part.

U.S. Patent Application No. 2006/287561 is related to the method for the generation for increasing C2-C4 light olefins, will use In the technique for generating aromatics hydrocarbon mixture and liquefied petroleum gas (LPG) by hydrocarbon mixture previous technique is can be used as with for generating In the technique of hydrocarbon raw material of raw material be combined together.

U.S. Patent Application No. 2007/062848 is related to a kind of for being hydrocracked charging to produce comprising no less than 35 weights Measure % C2-4 paraffins mixtures product stream method, the charging include no less than 20 weight % more than one include extremely The aromatic compounds of few two thick aromatic rings, the compound are unsubstituted or are replaced by most two C1-4 alkyl.According to U.S. State's number of patent application 2007/062848, by the bitumen feed from oil-sand to conventional distillation unit, and it is single to come from distillation The naphtha stream of member is fed to naphtha hydrotreater unit.Gaseous overhead stream is light gas/light paraffinic hydrocarbon stream, and And it is fed to the hydrocarbon cracker.Diesel stream from distillation unit is fed to diesel hydrotreater unit, and will be come from The gas oil stream of distillation unit is fed to vacuum distillation unit, wherein by the vacuum gas oil (VGO) logistics from vacuum distillation unit It feeds to gas oil hydrotreater.Light gas logistics from gas oil hydrotreater is fed to the hydrocarbon cracker.Decompression will be come from Gas oil hydrotreater plus hydrogen vacuum gas oil (VGO) is fed to catalytic cracker unit.Tower base stream from vacuum distillation unit It is vacuum (weight) Residual oil and is sent to delay coking device, to produce multiple logistics, as sent to naphtha hydrotreater unit Naphtha stream, diesel stream is sent to diesel hydrotreater unit to produce the diesel oil for adding hydrogen, and gas oil stream is sent to decompression watt This oily hydrotreater unit, generates the gas oil stream for adding hydrogen, the gas oil object of hydrogen should be added to be streamed to catalytic cracking unit.

U.S. Patent number 4,137,147 is related to a kind of for from containing with the distillation point below about 360 DEG C and at least Per molecule has the method just with charging the manufacture ethylene and propylene of isoparaffin of at least four carbon atom, wherein：In hydrogenolysis area Hydrogenolysis is carried out to the charging under the effect of the catalyst, (b) is fed the effluent from hydrogenolysis to Disengagement zone, from institute It states Disengagement zone (i) to be discharged from top, methane and may have hydrogen, (ii) is substantially had the hydrocarbon group of 2 and 3 carbon atoms by per molecule At fraction and (iii) be discharged from bottom, substantially there is the fraction that forms of hydrocarbon of at least four carbon atom by per molecule, (c) Only the fraction that substantially by per molecule there is the hydrocarbon of 2 and 3 carbon atoms to form is fed to steaming in the presence of steam Per molecule there is at least part of the hydrocarbon of 2 and 3 carbon atoms to be transformed into monoolefine by the vapour zone of cracking；It will be from the separation The fraction that substantially by per molecule there is the hydrocarbon of at least four carbon atom to form that the bottom in area obtains is supplied to the second hydrogenolysis Area is herein under the effect of the catalyst handled it, the effluent from the second hydrogenolysis area is supplied to Disengagement zone, with discharge On the one hand the per molecule for being at least partly recycled to second hydrogenolysis area has the hydrocarbon of at least four carbon atom, on the other hand base There is the fraction that the mixture of the saturated hydrocarbons of 2 and 3 carbon atoms forms by hydrogen, methane and per molecule in sheet；From the mixture Detach hydrogen logistics and methane stream, and by the hydrocarbon of the mixture with 2 and 3 carbon atoms with after the first hydrogenolysis area Disengagement zone recycling substantially by per molecule have the fraction that forms of hydrocarbon of 2 and 3 carbon atoms feed together to The steam cracking area.Exit in steam cracking area, obtain in addition to methane and hydrogen logistics and per molecule have 2 Hes Except the logistics of the alkane of 3 carbon atoms, also alkene and per molecule of the per molecule with 2 and 3 carbon atoms is at least 4 The product of a carbon atom.

EP 0 219 195 is related to a kind of for that will be converted to relatively low boiling, higher octane comprising the charging of hydrocarbon compound It is worth the method for hydrocarbon, by the presence of the hydrogen contacting the charging on a catalyst, selectively to hydrogenate and hydrogen is added to split Change condensed bicyclic hydrogenated aromatic hydrocarbon compound, to prepare the product of lower molecular weight, higher octane.

WO2012/071137 is related to a kind of method being used to prepare gas conveter raw material, and the method includes containing The charging of one or more alkanes for including 4 to 12 carbon atoms is with catalyst in the presence of the hydrogen in raised temperature and liter It is contacted under high pressure, and by least 40 weights of the total weight based on the alkane comprising 4 to 12 carbon atoms in charging The paraffin conversion comprising 4 to 12 carbon atoms of % is measured into ethane and/or propane, includes ethane and/or propane to obtain It is hydrocracked gas cracker raw material.

U.S. Patent number 6,187,984 is related to a kind of method for normal butane to be dehydrogenated to butylene, the method includes Contact the raw material containing normal butane in the presence of a catalyst in the case where being suitable for normal butane being converted to the reaction condition of butylene.

U.S. Patent Application No. 2003/232720 be related to by can dehydrogenation hydrocarbon dehydrogenation method, the method includes can The hydrocarbon of dehydrogenation is contacted with dehydrogenation catalyst complex, to provide the hydrocarbon of dehydrogenation.

Routinely, crude oil is treated as many fractions such as naphtha, gas oil and Residual oil by distillation.In these fractions Each with many potential purposes, such as generating transport fuel such as gasoline, diesel oil and kerosene, or as some stones The charging of oily chemical products and other processing units.

Light crude oil fraction such as naphtha and some gas oils can be used for generating lightweight by the technique of such as steam cracking Steam dilution is evaporated and used to hydrocarbon charging logistics in steam cracking and later in short stop by alkene and monocyclic aromatics It is exposed to very high temperature (750 DEG C to 900 DEG C) in time (＜ 1 second) stove (reactor) pipe.It, will be in such technique Hydrocarbon molecule in charging is converted into molecule shorter when compared with feed molecules (on average) and with lower hydrogen-carbon ratio Molecule (such as alkene).The technique also generates the by-product such as methane of the lesser value of the hydrogen and significant quantity as useful by-product With C9+ aromatic compounds and condensed aromatic compounds species (containing more aromatic rings with common edge).

Typically, it is further processed the aromatic compounds species of heavier (or higher) in crude oil refineries, such as Residual oil, So that the yield of the product of relatively light (retortable) from crude oil maximizes.This processing can be by being such as hydrocracked (wherein Hydrocracker charging is fractured into shorter hydrocarbon point in the case where causing some fractions of feed molecules that hydrogen is added at the same time Suitable catalyst is exposed under conditions of son) technique carry out.Heavy refinery stream is hydrocracked typically in high pressure With progress under high temperature and therefore with high fund cost.

Heavier crude oil fractions are opposite to be rich in the aromatic compounds species replaced and is especially enriched in substituted fused aromatic chemical combination Species (contain more than two aromatic rings with common edge), and under the conditions of steam cracking, these substances obtain real mass Heavy byproduct such as C9+ aromatic compounds and fused aromatic compounds.Therefore, crude distillation and steam cracking routinely combine The result is that preferably without the crude oil fractions for handling real mass by steam cracker, reason is it is believed that having from heavier fraction The cracking yield of valuable product is not high enough to compared with alternative refinery fuel is worth.

Techniques discussed above is on the other hand, even if ought light crude oil fraction only be handled (such as by steam cracking Naphtha) when, also by the fraction of the significant quantity of feed stream be converted into low value heavy byproduct such as C9+ aromatic compounds and Fused aromatic compounds.For typical naphtha and gas oil, these heavy byproducts can account for the 2 of overall product yield To 25% (Lyle F.Albright et al., pyrolysis：Theoretical and industrial practice (Pyrolysis：Theory and Industrial Practice), page 295, Table VI, Academic Press, 1983).Although this expression is split in conventional steam Change the apparent finance of expensive naphtha and/or gas oil in lesser value substance in the scale of device to degrade, these heavy by-products The yield of object is usually typically without proving these substances upgrading (such as by being hydrocracked) to be that can prepare significant quantity The reasonability of capital input needed for the logistics of the chemicals of higher-value.This is partly due to being hydrocracked equipment has high provide Golden cost, and as most of petroleum chemicals techniques, the fund costs of these units typically with the 0.6 of yield or 0.7 power is proportional.It is, therefore, usually considered that the fund cost of small-scale Hydrocracking unit is too high, so that it cannot proof pair Handle the reasonability of the investment of steam cracker heavy byproduct.

The conventional hydrocracking of heavy refinery stream such as Residual oil is that these are typically being chosen so as on the other hand It is carried out under the trade-off conditions of transformation in planta rate needed for realizing.Because feed stream contains the species for being easy to cracking in a certain range Mixture, this so that some fractions for being hydrocracked the retortable product to be formed by the species being relatively easily hydrocracked exist Be more difficult to the species being hydrocracked be hydrocracked needed under conditions of further convert.Which increase with the relevant hydrogen of the technique Consumption and heat management difficulty, and the yield of lighter molecules such as methane is also increased using more valuable species as cost.

It is that the steam cracking of crude distillation and lighter distillation fraction combines in this way as a result, steam cracker furnace is often unsuitable for In the fraction of material of the processing containing a large amount of boiling points for having and being more than~350 DEG C, because it is difficult to ensure in the hydrocarbon and steaming that will be mixed Steam flow is exposed to the evaporating completely for promoting these fractions before the high temperature needed for thermal cracking.If existed in the hot arc of cracking tube The drop of liquid hydrocarbon, then coke be deposited in pipe surface rapidly, it reduce heat exchange and increase pressure drop, and finally carry The preceding operation for terminating cracking tube, it is necessary to make stove shut down, to allow to devoke.Due to this difficulty, quite a few original crude oil Light olefin and aromatic compounds species cannot be processed into via steam cracking.

US2009/173665 is related to a kind of for increasing single aromatic content of the hydrocarbon raw material comprising polynuclear aromatic Catalyst And Method, wherein undesired compound can be reduced by the increase of gasoline/diesel yield and simultaneously, to reach list The increase of aromatic compounds, to provide a kind of route that the hydrocarbon for that will include a large amount of polynuclear aromatics modifies.

LCO Unicracking or the LCO-X processes of the UOP disclosed in WO2009/008878 are added using Partial Conversion Hydrogen cracking, to prepare high-quality gasoline and diesel oil material with simple one way flow scheme.By raw material by pretreated Catalyst is processed, and is then hydrocracked in same stage.It then will production in the case where not needing liquid recycle Product detach.LCO Unicracking processes can be designed as being used for lower pressure operation, it is meant that pressure requirements will be more harsh than high Property add hydrogen higher, but significantly lower than regular section conversion and completely conversion Hydrocracking unit design.The midbarrel of modification Product causes suitable ultra-low-sulphur diesel (ULSD) blend components.Low pressure hydrocracking naphtha products tool from LCO-X There are super-low sulfur and high-octane rating, and can directly be blended into the pond super low-sulfur oil (ULSG).

US 7,513,988 is related to a kind of compound of the processing comprising more than two thick aromatic rings to be saturated at least one ring, so Obtained saturated rings are split to generate the side of C2-4 alkane streams and aromatic compounds logistics from the aromatic portion of the compound afterwards Method.Such method can combine with hydrocarbon (such as ethylene) (steam) cracker so that the hydrogen from cracker can be used to It is saturated and splits and include the compound of more than two aromatic rings and the C2-4 alkane streams can be fed to the hydrocarbon cracker, or It can be combined with the hydrocarbon cracker (for example, steam cracker) and ethylbenzene unit, processing is from processing oil-sand, Tar sands, shale The heavy still bottoms of the oil of oils or any condensed ring aromatic compound with high-content is suitable for petroleum chemicals production to prepare Logistics.

US2005/0101814 is related to a kind of for improving into the paraffinicity in the raw material of steam cracking unit Method, including：Charging comprising C5 to C9 hydrocarbon (including C5 to C9 normal alkanes) is passed in ring-opening reaction device, the ring-opening reaction Device is included in is converted under conditions of cycloalkane the catalyst of operation and in the item by cycloalkanes at alkane by aromatic hydrocarbon The catalyst of operation under part, and prepare the second feeding flow；And at least part of the second feeding flow is passed into steam cracking Unit.

US 7,067,448 is related to a kind of be used for from the mineral containing cycloalkane, alkene, cycloolefin and/or aromatic compounds Oil distillate and the method for coming self-heating or the fraction preparation w-alkane of catalyzed conversion factory.More specifically, the disclosure refers to one kind Method for processing the mineral oil fractions for being rich in aromatic compounds, wherein by what is obtained after the hydrogenation of aromatic compounds For cycloalkanes at w-alkane, chain length is as small as possible in the carbon being filled with.

LCO methods discussed above are related to complete conversions of the LCO to naphtha and are hydrocracked, and wherein LCO is containing mono- virtue The logistics of compounds of group and two-aromatic compounds.Completely conversion be hydrocracked as a result, obtaining high cycloalkanes, low octane rating stone Cerebrol, such naphtha must be reformed, and required octane is blended to prepare product.

WO2006/122275 is related to a kind of method, this method be used for the modification of heavy hydrocarbon crude oil material as compared with low-density or Oil that is lighter, containing less sulphur than original heavy hydrocarbon crude oil material, while manufacturing the value of such as alkene and aromatic compounds Higher material, this approach includes the following steps：A part of heavy hydrocarbon crude oil is mixed with oil-soluble catalyst to be formed Reaction mixture makes pretreated raw material be reacted under relatively low hydrogen pressure to form product stream, wherein the first of product stream Part includes light oil, and the second part of product stream includes heavy crude oil residue, and the Part III of product stream includes lightweight Appropriate hydrocarbon gas, and a part of light hydrocarbon gas stream is injected into Cracking Unit to generate the stream of hydrogeneous and at least one alkene.

WO2011005476 is related to a kind of method for the processing using catalytic hydrogenation treatment preprocessing process heavy oil, institute It includes that crude oil, decompression residuum, Tar sands, pitch and vacuum gas oil (VGO) specifically sequentially use hydrodemetallization to state heavy oil (HDM) and hydrodesulfurization (HDS) catalyst, to improve the efficiency of follow-up coke-oven plant (coker refinery).

US2008/194900 is related to a kind of for a kind of olefine side of the naphtha containing aromatic compounds of steam cracking Method, the method includes：The gasoline stream that alkene and pyrolysis are recycled from steam cracker furnace effluent, by the gasoline stream of pyrolysis Hydrogenate and therefrom recycling C6-C8 logistics, by the naphtha stream hydrotreating containing aromatic compounds, with obtain naphtha into Material, by C6-C8 logistics naphtha feed stream dearomatization in general aromatic compounds extraction unit, to obtain raffinate Stream；And raffinate stream is fed to steam cracker furnace.

WO2008/092232 be related to for from raw material (such as oil, natural gas condensate or petrochemical material, such as whole process (full Range) feed naphtha) extraction chemical constituent method, the described method comprises the following steps：Whole feed naphtha is carried out Sweetening process, from the whole feed naphtha of desulfurization detach C6 to C11 hydrocarbon-fractions, in aromatic compounds extraction unit from C6 to C11 hydrocarbon-fractions recycle aromatic fraction, aromatic compounds precursor fraction and raffinate fraction, by aromatic compounds precursor fraction In aromatic compounds precursor be converted to aromatic compounds, and the step from aromatic compounds extraction unit recycles aromatics Compound.

It is an object of the present invention to provide one kind for heavy hydrocarbon feedstocks to be modified to aromatic compounds (BTXE) and LPG Method.

It is a further object to provide one kind for preparing light olefin and aromatic compounds from heavy hydrocarbon feedstocks Method, wherein high aromatic compounds yield can be obtained.

It is a further object to provide a kind of for being modified to crude oil material with high carbon efficiencies and hydrogen The method for integrating the petroleum chemicals of (a high carbon efficiency and hydrogen integration).

Present invention is accordingly directed to a kind of method for oil plant heavy hydrocarbon to be modified to petroleum chemicals, the methods Include the following steps：

(a) hydrocarbon raw material is fed to ring-opening reaction area；

(b) effluent from (a) is fed to separative element, is used to prepare the gas stream comprising lightweight boiling hydrocarbon, packet The liquid flow of the hydrocarbon containing naphtha boiling-range and the liquid flow for including diesel boiling range hydrocarbon；

(c) liquid flow comprising naphtha boiling-range hydrocarbon is fed to Hydrocracking unit,

(d) reaction product of the Hydrocracking unit of step (c) is separated into the tower overhead gas for including lightweight boiling hydrocarbon Stream and the tower base stream for including the BTX mixture of toluene and dimethylbenzene (benzene),

(e) by the overhead gas stream from the Hydrocracking unit of step (d) and described point from step (b) The gas stream from unit is fed to steam cracking unit at least one or more in the group being made of the following terms Unit：Dehydrogenating propane unit, butane dehydrogenation and the propane-butane of combination dehydrogenation unit preferably contain from air-flow separation After hydrogen logistics.

The present inventor is it is assumed that by by ring opening process and Hydrocracking unit (i.e. so-called gasoline hydrogenation cracking Unit/charging Hydrocracking unit (" GHC/FHC ")) it combines, total process no longer generates the combustion other than LPG and BTXE Material, and only generate LPG and BTXE.The latter is also used as when all azeotropic mixtures (co-boiler) of BTXE are all cracked into The logistics of purifying directly obtains.LPG can be used in steam cracking and/or PDH/BDH.The hydrogen of there output can be used for this A little hydrogen processing (hydro processing) step chargings.It, can be according to catalyst/technique if necessary to hydrodesulfurization (HDS) It is required that implementing hydrodenitrogeneration (HDN).Herein, term " being hydrocracked " is used with the meaning that it usually receives, and therefore may be used To be defined as the catalytic cracking process assisted by the presence of raised hydrogen partial pressure；See such as Alfke (2007).This process Product is the hydrocarbon of saturation, also, depends on reaction condition such as temperature, pressure and air speed and catalyst activity, is the virtue for including BTX Race's hydrocarbon.

Term " LPG " as used in this article refers to the initial accepted extensively for term " liquefied petroleum gas " Abbreviation.LPG is usually by the blend of C3-C4 hydrocarbon, i.e. the mixture composition of C3 and C4 hydrocarbon.

One of petrochemicals produced in the method for the invention is BTX.Term as used in this article " BTX " is related to the mixture of benzene, toluene and dimethylbenzene.Preferably, the product produced in the method for the invention further includes Useful aromatic hydrocarbon such as ethylbenzene.Therefore, present invention preferably provides the mixtures for generating benzene,toluene,xylene and ethylbenzene The method of (" BTXE ").The product produced can be the physical mixture of different aromatic hydrocarbons or can directly carry out further (such as passing through distillation) is detached to provide different purified product logistics.Such purified product logistics may include benzene product object Stream, toluene products logistics, xylene products logistics and/or ethylbenzene product logistics.Term " cycloalkane (naphthenic Hydrocarbon) " or " cycloalkanes (naphthene) " or " cycloalkane (cycloalkane) " is contained with what it had been established herein Justice uses and is therefore related to the alkane type in the chemical constitution of its molecule with one or more carboatomic rings.

By from ring opening process liquid efflunent or even total reactor effluent (preferably will only contain it is polycyclic After the heavier recirculation stream of component is separated) it feeds to Hydrocracking unit (" GHC/FHC ").Which greatly simplifies Ring opening process and the redundancy for reducing required separative element.It note that in another embodiment, liquid efflunent existed Into the front evaporator of Hydrocracking unit.Therefore, can be liquid phase, gas phase or mixing into the charging of Hydrocracking unit Gas and liquid phase.Hydrogen circuit can surround two units, that is, ring-opening reaction area and Hydrocracking unit (" GHC/FHC ") is implemented, and use The addition of multiple hydrogen and decanting point.According to another embodiment, only naphtha stream or part of it are sent anti-to FHC/GHC Section is answered, and may be by all heavier Recycle of material further to convert, therefore simplifies flow chart.

This method further includes that the reaction product of the Hydrocracking unit of step (c) is separated into comprising lightweight boiling hydrocarbon Overhead gas stream and tower base stream containing BTX.Hydrogen-containing gas stream can be isolated from the overhead gas stream comprising lightweight boiling hydrocarbon.

This method further preferably includes：By the overhead gas stream of the Hydrocracking unit from step (d) and come from The gas stream of the separative element of step (b) feeds to another separative element and feeds the logistics so detached To the steam cracking unit and one or more dehydrogenation units.

According to the present invention, certain embodiments are catalytic process and Steam cracking processes are thermal cracking processes.

According to a preferred embodiment, the method further includes：By from Hydrocracking unit overhead stream and Gas stream from separative element feeds one or more to steam cracking unit and in the group being made of the following terms A unit：The propane-butane dehydrogenation unit of dehydrogenating propane unit, butane dehydrogenation and combination, preferably detached from air-flow it is hydrogeneous It is carried out after logistics.

By increasing open loop, heavier charging can be processed, these heavier chargings will be sent directly to FHC/GHC Unit.In addition, adding separative element before ring opening process so that FHC/GHC units will boil in naphtha range into Any cycloalkanes in material stream is all converted to aromatic compounds/BTX.When compared with only open loop, this mode can obtain more High BTX yields because these cycloalkanes otherwise can the cracking in ring opening process, generate LPG rather than BTX.

According to a preferred embodiment, this method further includes that the hydrocarbon raw material is pre-processed in separation equipment unit, From the separation equipment unit by naphtha boiling-range hydrocarbon be fed directly to Hydrocracking unit and by its heavier fraction into Expect to ring-opening reaction area.

This method, which is further preferably included in aromatic compounds extraction unit, pre-processes the hydrocarbon raw material, from the aromatic compounds Its rich aromatic compounds is flowed into material to the reaction zone for open loop, wherein the aromatic compounds carries by object extraction unit Unit is taken to be selected from following various types：Distillation unit type, molecular sieve type and solvent extraction unit type.

In addition to separation equipment as described above, can also " precracked " will be fed by using hydrocracking technology and come into one Step improves the yield of BTX.Based on the type that can be subject to processing the feed material to prepare maximum BTX in FHC/GHC sections, Such preferred method can prepare high cycloalkanes and aromatics naphtha range material because again, when with directly into Material is compared to ring opening process, and even more cycloalkanes is converted to BTX.

Purity, cascade (cascading), stress level can will be optimized for the hydrogen circuit of three conversion zones.It can In the Recycle of material of the heavy unconverted in the exit of ring-opening reaction device to ring opening process or first plus hydrogen will be recycled to Hydrocracking step.

Therefore, this method further includes that the hydrocarbon raw material is preferably pre-processed in pre- Hydrocracking unit, from the pre-add hydrogen Gas stream comprising LPG is fed to steam cracking unit to be selected from at least one or more and is made of the following terms by Cracking Unit Group in unit：The propane-butane dehydrogenation unit of dehydrogenating propane unit, butane dehydrogenation unit and combination, by its heavy hydrocarbon Fraction, which feeds to the ring-opening reaction area and is fed directly to the logistics comprising naphtha boiling-range hydrocarbon, described is hydrocracked list Member.

It was found by the inventors of the present invention that in another embodiment, can be replaced with hydrodealkylation/reforming process First pre- hydrocracking step, so as to cause high-purity BTXE logistics.As a result, because in the first reactor of reformation type " active " additional aromatic compounds prepare, so with the embodiment of pre- hydrocracking step compared with or even can prepare more More BTX are, which means that not only make cycloalkanes aromatisation, but also some additional cyclization occur certainly.

Therefore, the method for the present invention, which is further preferably included in hydrodealkylation/weight integer unit, pre-processes the hydrocarbon raw material, From the hydrodealkylation/weight integer unit, BTXE logistics is obtained, the gas stream comprising LPG is fed to one or more Unit in the group being made of the following terms：Steam cracking unit, dehydrogenating propane unit, butane dehydrogenation unit and combination Propane-butane dehydrogenation unit, and its heavier hydrocarbon-fraction is fed to ring-opening reaction area.

The method of the present invention further includes preferably by tower base stream (such as rich BTX logistics of Hydrocracking unit) charging to alkyl Buanch unit.

In addition, the method for the present invention further include preferably by the liquid flow comprising diesel boiling range hydrocarbon from separative element feed to Aromatic compounds saturation unit.

This method further include preferably by from separative element gas stream, from hydrodealkylation/weight integer unit The charging of at least one of gas stream and gas stream from pre- Hydrocracking unit is to Hydrocracking unit.According to another reality Apply scheme, by the logistics from hydrodealkylation/weight integer unit and the logistics from pre- Hydrocracking unit at least It is a kind of to send to the reaction zone for open loop.Such logistics can be gas stream.

Can by the tower top stream from the Hydrocracking unit, the gas stream from the separative element and it is possible come It is separated into individual logistics from the gas stream of the pre- Hydrocracking unit and the hydrodealkylation/weight integer unit, often A logistics includes mainly respectively C2 alkanes, C3 alkanes and C4 alkanes, and each independent logistics is fed to steam and is split Change the special stove section of device unit, wherein sending hydrogeneous logistics to one or more hydrogen consumption processing units, is such as hydrocracked Unit and reaction zone for open loop.

According to a preferred embodiment, the gas stream part to steam cracker unit will be sent to send to dehydrogenation unit, Wherein it is preferred that only C3-C4 fractions are sent to dehydrogenation unit, especially as separation C3 and C4 logistics, more preferably as combination C3+C4 logistics.

Therefore, this method includes steam cracker unit and selected from least one of the group being made of the following terms unit Combination：Butane dehydrogenation unit, dehydrogenating propane unit, the propane-butane dehydrogenation unit of combination or the combination of its unit, with system Standby mix products stream.This combination of unit provides the high yield of desired product Ji Xi race and aromatics petroleum chemicals, Conversion is wherein significantly increased to the part of the crude oil of LPG.

According to a preferred embodiment, by gas stream (such as the tower overhead gas of the Hydrocracking unit from step (d) The gas stream of stream and separative element from step (b)) it is separated into one or more logistics, wherein it is preferable to use include hydrogen Logistics as the hydrogen source for being hydrocracked purpose, it is preferable to use the logistics comprising methane as fuels sources, it is preferable to use comprising The logistics of ethane as steam cracking unit charging, it is preferable to use the logistics comprising propane as dehydrogenating propane unit into Material, it is preferable to use the logistics comprising butane as butane dehydrogenation unit charging, it is preferable to use including C1-'s or less (minus) Logistics as fuels sources and/or as hydrogen source, it is preferable to use include charging of the C3- logistics below as dehydrogenating propane unit, But according to another embodiment, also as the charging of steam cracking unit, it is preferable to use the logistics comprising C2-C3 is as third The charging of alkane dehydrogenation unit, but according to another embodiment, also as the charging of steam cracking unit, it is preferable to use comprising Charging of the logistics of C1-C3 as dehydrogenating propane unit, but according to another embodiment, also as steam cracking unit Charging, it is preferable to use the logistics comprising C1-C4 butane as butane dehydrogenation unit charging, it is preferable to use including C2-C4 butane Logistics as butane dehydrogenation unit charging, it is preferable to use include charging of the C2- logistics below as steam cracking unit, It is preferable to use the logistics comprising C3-C4 as propane or butane dehydrogenation unit or combination propane and butane dehydrogenation unit into Material is, it is preferable to use include charging of the C4- logistics below as butane dehydrogenation unit.

The method of the present invention further includes from one or more selected from by steam cracking unit, dehydrogenating propane unit, butane dehydrogenation The reaction product of unit in the group of unit and the propane-butane dehydrogenation unit of combination composition recycles hydrogen, and will recycle in this way Hydrogen feed the reaction zone to Hydrocracking unit and for open loop, especially further include from dehydrogenation unit recycle hydrogen, and will The hydrogen recycled in this way is fed to any hydrogen consumption unit, the reaction zone such as Hydrocracking unit and for open loop.

It is preferably included for the technological condition in the reaction zone of open loop：100 DEG C to 500 DEG C of temperature and 2 to The raw material of the pressure of 10MPa and every 1,000kg use 50 to 300kg hydrogen, and use aromatic hydrogenation catalyst, and Ring crack solution unit is led into the logistics of gained, the ring crack solution unit is in 200 DEG C to 600 DEG C of temperature and 1 to 12MPa pressure The logistics of the gained of power and every 1,000kg uses 50 to 200kg hydrogen, and uses ring catalyst for cracking.

Term " (aromatics) ring open loop unit " refers to the refinery unit for carrying out hydrocracking process, is suitable for compare Charging relatively rich in the aromatic hydrocarbon with the boiling point in kerosene and gas oil boiling spread is converted to prepare LPG, and is depended on In process conditions, light fraction (gasoline for being originated from ARO) is prepared.Such aromatic ring ring-opening process (ARO techniques) is for example described in US 7,513,988.Therefore, ARO techniques may include the temperature at 300-500 DEG C, the pressure and 10-30 weight % of 2-10MPa Hydrogen (related with hydrocarbon raw material), the aromatic ring saturation carried out in the presence of aromatic hydrogenation catalyst, and in 200-600 DEG C of temperature Degree, the pressure of 1-12MPa and the hydrogen (related with hydrocarbon raw material) of 5-20 weight % carry out in the presence of ring is broken catalyst Ring is broken, wherein the aromatic ring saturation and ring fracture can be carried out in a reactor or in two flow reactors. Aromatic hydrogenation catalyst can be conventional hydroprocessed/hydrotreating catalyst as being included on refractory support (typically, aluminium oxide) Ni, W and Mo mixture catalyst.It includes metal component and carrier that ring, which is broken catalyst, is preferably selected from by the following One or more metals of the group of composition：Pd, Rh, Ru, Ir, Os, Cu, Co, Ni, Pt, Fe, Zn, Ga, In, Mo, W and V.Pass through Residence time under aromatic ring saturation conditions is adjusted, which can be guided to the fully saturated of all rings and subsequent disconnected (the long residence time under aromatic ring saturation conditions) or guiding are split to one aromatic ring unsaturation of holding and then remove one The fracture (the shorter residence time under aromatic ring saturation conditions) of all rings outside ring.In the later case, ARO techniques generate It is opposite that rich in tool, there are one the lightweight distillates (" ARO- gasoline ") of the hydrocarbon compound of aromatic ring.

Technological condition in separative element preferably includes：149 DEG C to 288 DEG C of temperature and 1MPa to 17.3MPa Pressure.

Technological condition in Hydrocracking unit preferably includes：300-580 DEG C, preferably 450-580 DEG C, more preferably 470-550 DEG C of reaction temperature, the pressure of 0.3-5MPa gauge pressures, the preferably pressure of 0.6-3MPa gauge pressures, particularly preferred 1000- The pressure of 2000kPa gauge pressures, the most preferably pressure of 1-2MPa gauge pressures, the most preferably pressure of 1.2-1.6MPa gauge pressures, 0.1-10h- 1, the weight hourly space velocity (WHSV) of preferably 0.2-6h-1, more preferable 0.4-2h-1.

Technological condition in steam cracking unit preferably includes：About 750-900 DEG C of reaction temperature, 50-1000 The residence time of millisecond, and it is depressed into selected from air the pressure of 175kPa gauge pressures.

A kind of very versatile method for converting alkanes to alkene includes " steam cracking ".As used herein , term " steam cracking " is related to a kind of petrochemical processing, wherein by the hydrocarbon pyrolysis of saturation at smaller, often undersaturated Hydrocarbon, such as ethylene and propylene.In steam cracking, with steam is by gaseous state hydrocarbon charging such as ethane, propane and butane or theirs is mixed It closes object (gas cracking) or liquid hydrocarbon feed such as naphtha or gas oil (cracked liquid) to dilute, and there is no the stoves of oxygen In of short duration heating.Typically, reaction temperature is very high, at about 850 DEG C, but reaction is only allowed briefly to occur very much, usually Residence time is 50-500 milliseconds.Preferably, hydrocarbon compound ethane, propane and butane are split respectively in the stove of corresponding specialization Change, to ensure cracking at optimum conditions.It is using quench oil that gas is rapid sudden cold to stop after having reached cracking temperature The only reaction in transfer line heat exchanger or inside sudden cold head.Steam cracking causes the coke of carbon form to be slowly deposited on reactor On wall.Decoking needs to detach stove with the technique and the stream of steam or Steam/air mixture is passed through stone or metal plate for standing a stove on as a precaution against fire later Pipe.This converts strong carbon-coating to carbon monoxide and carbon dioxide.Once the reaction is completed, i.e., stove is returned and used.Pass through steaming When the product that vapour cracking generates depends on the composition fed, the ratio of hydrocarbon and steam and is stopped depending on cracking temperature and stove Between.Light hydrocarbon feed such as ethane, propane, butane or light naphtha generate the alkene rich in relatively lightweight polymer grade, including Ethylene, propylene and butadiene.Heavier hydrocarbon (whole and heavy naphtha and gas oil fraction) also generates the production rich in aromatic hydrocarbon Object.

For the different hydrocarbon compound separation that will be prepared by steam cracking, the gas of cracking is made to pass through fractionation unit. Such fractionation unit is well known in the art, and can include usually said gasoline fractionator, wherein by heavy distillat (" carbon black oil ") and middle fraction (" fraction of cracking ") are detached with light fraction and gas.In subsequent chilling tower, it can will lead to The most of of the light fraction (" pyrolysis gasoline " or " pygas ") of steam cracking preparation is crossed by condensing light fraction to divide from gas From.Then, multiple compression stages can be carried out to gas, wherein can between compression stage by the remainder of light fraction with Gas detaches.Sour gas (CO2 and H2S) can also be removed between compression stage.In below the step of, it can will pass through Pyrogenically prepared gas is by multiple stages of cascade refrigerating system and partial condensation is to only about residual hydrogen in the gas phase Situation.Then different hydrocarbon compounds can be detached by simple distillation, wherein ethylene, propylene and C4 alkene are to pass through steam Most important high value chemicals prepared by cracking.The methane prepared by steam cracking is typically used as fuel gas, can incite somebody to action Hydrogen detaches and is recycled to the process of consumption hydrogen, such as hydrocracking process.It is preferred that will be selected by acetylene made from steam cracking It is hydrogenated to ethylene to property.The alkane for including in the gas of cracking can be recycled to the mistake for converting alkanes to alkene Journey.

Term " dehydrogenating propane unit " as used in this article, which is related to wherein converting propane feed logistics to, includes The petrochemical processing unit of the product of propylene and hydrogen.Therefore, term " butane dehydrogenation unit " is related to for turning butane feed stream Turn to the technique unit of C4 alkene.In short, by lower alkyl is described as the technique of the dehydrogenation of lower paraffin hydrocarbon such as propane and butane Hydrocarbon dehydrogenating technology.The technique of dehydrogenation for lower paraffin hydrocarbon is as known in the art and includes oxidation hydrogenation process and non-oxygen Fluidized dehydrogenation technique.In oxidative dehydrogenation process, work is provided by the partial oxidation of one or more lower paraffin hydrocarbons in charging Skill heat.In the context of the present invention in preferred Non-oxidative dehydrogenation technique, such as obtained by fuel gas by external heat source To hot flue gases or steam process heat for dehydrogenation reaction of absorbing heat is provided.For example, containing the platinum being carried on aluminium oxide Catalyst in the presence of, in moving-burden bed reactor, UOP Oleflex techniques allow dehydrogenating propane to form propylene and (different) fourth Or mixtures thereof alkane dehydrogenation formation (different) butylene ()；See, for example, US 4,827,072.On being carried on zinc-alumina spinel Co-catalysis platinum catalyst in the presence of, Uhde STAR techniques allow dehydrogenating propane to form propylene or butane dehydrogenation to form fourth Alkene；See, for example, US 4,926,005.STAR techniques have been improved by the principle of application oxidative dehydrogenation recently.In reactor In two level adiabatic region in, by a part of hydrogen from intermediate product using addition oxygen selective convert to form water.This Thermodynamical equilibrium is moved to higher conversion and realizes higher yield.In addition, being converted by part by exothermic hydrogen Outside heat needed for ground supply heat absorption dehydrogenation reaction.Lummus Catofin techniques use many consolidating based on circular flow Fixed bed reactor.Catalyst is the activated alumina for being impregnated with 18-20 weight % chromium；See, for example, 0 192 059 A1 of EP and GB 2 162 082 A.Catofin techniques are it is reported that being firm and can handle the impurity that will make Pt catalyst poisoning. The property of butane charging and used butane dehydrogenation technique are depended on by the product that butane dehydrogenation technique generates.In addition, Catofin techniques allow butane dehydrogenation to form butylene；See, for example, US 7,622,623.

The hydrocarbon raw material of step (a) is selected from the group of the following terms composition：Shale oil, crude oil, kerosene, diesel oil, AGO (atmospheric gas oil) (AGO), gas condensate (gas condensates), wax, contaminated crude naphtha, vacuum gas oil (VGO) (VGO), decompression Residual oil, reduced crude, naphtha and pretreated naphtha or combination thereof.Other preferred charge raw materials are light recycles Oil/heavy recycle stock (LCO/HCO), coking naphtha (coker naphtha) and diesel oil, FCC naphtha and diesel oil, and very To be what slurry oil.

The present invention is more fully described below with reference to attached drawing, wherein same or similar element is by being identically numbered table Show, and wherein：

Fig. 1 is the schematic illustration of an embodiment of the method for the present invention.

Fig. 2 is another embodiment of the method for the present invention.

Fig. 3 is another embodiment of the method for the present invention.

Fig. 4 is another embodiment of the method for the present invention.

Fig. 5 is another embodiment of the method for the present invention.

Fig. 6 is another embodiment of the method for the present invention.

Referring now to the method and apparatus of schematic depiction in Fig. 1, which show for modifying oil plant heavy hydrocarbon At the method 101 of petroleum chemicals.Hydrocarbon raw material 5 is sent to ring-opening reaction area 1, and its effluent 17 is sent to separative element 2, prepare gas stream 4, the liquid flow 18 comprising naphtha boiling-range hydrocarbon and the liquid flow 15 comprising diesel boiling range hydrocarbon for including LPG. It is preferred that the entrance that ring-opening reaction area 1 will be recycled to comprising the logistics 15 of diesel boiling range hydrocarbon.The object of naphtha boiling-range hydrocarbon will be included Stream 18 is sent to Hydrocracking unit 3, is prepared the overhead gas stream 9 comprising LPG and is included the tower base stream 11 of aromatic hydrocarbon such as BTX.It will Logistics 4 and logistics 9 are combined into logistics 10, and further in steam cracker unit and in the group being made of the following terms It is processed in dehydrogenation unit：The propane/butane dehydrogenation unit of dehydrogenating propane unit, butane dehydrogenation unit and combination.Embodiment party herein In case, gas stream 10 is separated into individual logistics 24,25,26 in separative element 20 first.However, the quantity of logistics not by Limitation.Light fractions 24 are sent to gas steam cracker unit 22, and its effluent is sent to other segregation section 23, The segregation section 23 can include multiple separative elements.Logistics 25,26 is handled in dehydrogenation section 21, which can include multiple Dehydrogenation unit, such as the propane/butane dehydrogenation unit of dehydrogenating propane unit, butane dehydrogenation unit and combination.By the effluent of dehydrogenation 28 send to separative element 23, and are separated into individual logistics 29,30, such as the logistics comprising alkene.However, the quantity of logistics is not It is restricted.According to another embodiment, logistics 4 can (partly) be sent to Hydrocracking unit 3, prepared comprising LPG Overhead gas stream 9 and the tower base stream 11 for including aromatic hydrocarbon such as BTX.

According to process 201 (see Fig. 2), hydrocarbon raw material 5 is pre-processed in separation equipment unit 5, prepares and boiled comprising naphtha The logistics 16 of journey hydrocarbon.Logistics 16 is fed directly to Hydrocracking unit 3.By the outflow of the separation equipment unit 5 comprising heavy hydrocarbon Object is sent to ring-opening reaction area 1.Ring-opening reaction area 1 prepares effluent logistics 17, logistics 17 is sent to separative element 2, preparation includes The gas stream 4 of LPG, the liquid flow 18 comprising naphtha boiling-range hydrocarbon and the logistics 15 comprising diesel boiling range hydrocarbon.It is preferred that will include bavin The logistics 15 of oily boiling range hydrocarbon is recycled to the entrance in ring-opening reaction area 1.Logistics 18 is further turned in Hydrocracking unit 3 Change, prepares the overhead gas stream 9 comprising LPG and the tower base stream 11 comprising BTX.Logistics 4 and logistics 9 are combined into logistics 10, and Can be as described in the discussion of figure 1 above be further processed.It, can be by 4 (part of logistics according to another embodiment Ground) it send to Hydrocracking unit 3, it prepares the overhead gas stream 9 comprising LPG and includes the tower base stream 11 of aromatic hydrocarbon such as BTX.

In addition to the separation equipment unit 5 discussed in such as figure 2 above, the yield of BTX can be by providing pre- Hydrocracking unit 6 It further increases.Hydrocarbon raw material 5 is hydrocracked by method 301 according to fig. 3 in advance in pre- Hydrocracking unit 6, prepares gas stream 13 and the tower base stream 8 comprising naphtha.Logistics 8 is fed directly to Hydrocracking unit 3.Pre-add hydrogen Cracking Unit 6 will be come from Double distilled send to ring-opening reaction area 1.In ring-opening reaction area 1, the hydrocarbon from preheating Hydrocracking unit 6 is converted to outflow Object 17.Effluent 17 is sent to separative element 2, gas stream 4, the liquid flow 18 comprising naphtha boiling-range hydrocarbon for including LPG are prepared With the logistics 15 comprising diesel boiling range hydrocarbon.Logistics 15 comprising diesel boiling range hydrocarbon is recycled to entering for pre- Hydrocracking unit 6 Mouthful.By the charging of logistics 18 to Hydrocracking unit 3, the overhead gas stream 9 comprising LPG and the tower base stream 11 comprising BTX are prepared. Gas stream 4 and 9 is combined into logistics 10, can as above discuss in Fig. 1 like that, which is further processed.According to another Logistics 4 and logistics 13 can (partly) be sent to Hydrocracking unit 3, prepare the tower overhead gas for including LPG by one embodiment Stream 9 and the tower base stream 11 for including aromatic hydrocarbon such as BTX.Furthermore, it is possible to (partly) send logistics 13 to ring-opening reaction area 1.

According to another embodiment, the method 401 being now in Fig. 4 can use hydrodealkylation unit 7 to replace As above the first hydrocracking step discussed in figure 3, obtains BTXE logistics 12 and comprising the gas stream of LPG from the unit 7 14.Heavier fraction from unit 7 is sent to ring-opening reaction area 1, and obtains effluent 17.Ring-opening reaction area 1 will be come from Effluent 17 send to separative element 2, prepare the gas stream 4 comprising LPG, the liquid flow 18 comprising naphtha boiling-range hydrocarbon and comprising The logistics 15 of diesel boiling range hydrocarbon.The entrance of hydrodealkylation unit 7 will be recycled to comprising the logistics 15 of diesel boiling range hydrocarbon.It will Logistics 18 is sent to Hydrocracking unit 3, and the overhead gas stream 9 comprising LPG and the tower base stream 11 comprising BTX are prepared.It can will be The rich BTXE logistics prepared in unit 7 is further processed in Hydrocracking unit 3.Gas stream 14,4 and 9 is combined into logistics 10, the further processing that logistics 10 can be discussed as above in Fig. 1.It, can be by object according to another embodiment (not shown) Stream 4 and logistics 14 (partly) are sent to Hydrocracking unit 3, are prepared the overhead gas stream 9 comprising LPG and are included aromatic hydrocarbon such as BTX Tower base stream 11.Furthermore, it is possible to (partly) send logistics 14 to ring-opening reaction area 1.

In a preferred embodiment, as shown in Figure 5, according to for oil plant heavy hydrocarbon to be modified to oil The method 501 for learning product, hydrocarbon raw material 5 is sent to ring-opening reaction area 1, and its effluent 17 is sent to separative element 2, prepares packet Gas stream 4 containing LPG, the liquid flow 18 comprising naphtha boiling-range hydrocarbon and the liquid flow 15 for including diesel boiling range hydrocarbon.It can will wrap The logistics 15 of the hydrocarbon containing diesel boiling range (partly) is recycled to the entrance in ring-opening reaction area 1.Fig. 5 is also shown, will include that diesel oil boils The logistics 15 of journey hydrocarbon is sent as logistics 49 to aromatic compounds saturation unit 50, and effluent stream 51 is prepared.Remaining technique unit and Logistics is similar to and those of is referred in figure 1 above.According to another embodiment, logistics 4 can (partly) be sent to adding hydrogen Cracking Unit 3 prepares the overhead gas stream 9 comprising LPG and includes the tower base stream 11 of aromatic hydrocarbon such as BTX.

According to another preferred embodiment, by least part and 9 and 10 carbon number aromatics of benzene and toluene Compound is introduced in transalkylation reaction zone.According to this embodiment shown in Figure 6 as method 601, logistics 11 is introduced to In transalkylation reaction zone 60, to enhance the preparation of xylene compounds, logistics 62 is generated.Also the hydrogen-rich gas stream of one way 61 is introduced Into transalkylation reaction zone 60.This gas stream 61 can be obtained by other hydrogen preparation units, such as from steam cracking unit and dehydrogenation list The hydrogen of the reaction product recycling of member.It is preferred that the operating condition used in transalkylation reaction zone include 177 DEG C to 525 DEG C temperature and Liquid hourly space velocity (LHSV) within the scope of 0.2 to 10hr.Any suitable transalkylation catalyst can be used in transalkylation reaction zone.It is excellent The transalkylation catalyst of choosing contains the weak metal of non-frame (the reduced non-of molecular sieve, refractory inorganic oxide and reduction framework weak metal).Preferred molecular sieve is zeolite aluminosilicate, such as MFI type zeolite, can have to be more than 10 silica: any one of those of alumina ratio and 5-8 angstroms of aperture zeolite.According to another embodiment party Case can (partly) send logistics 4 to Hydrocracking unit 3, overhead gas stream 9 of the preparation comprising LPG and comprising aromatic hydrocarbon such as The tower base stream 11 of BTX.

Embodiment

Technological process used herein is according to technological process shown in Fig. 1.By the charging of hydrocarbon raw material 5 to for open loop Reaction zone 1, and the reactant 17 that it is generated in reaction zone is separated into overhead stream 4, side logistics 18 and bottom of tower by unit 2 Logistics 15.Side logistics 18 is fed to gasoline hydrogenation cracker (GHC) unit 3, wherein the reaction product of GHC units 3 is detached At the overhead gas stream 9 for including light components such as C2-C4 alkanes, hydrogen and methane, and it is main comprising compound aromatic hydrocarbon and non-aromatic The logistics 11 of race's hydrocarbon compound.The overhead gas stream 9 of gasoline hydrogenation cracker (GHC) unit 3 and the logistics for being originated from unit 2 will be come from 4 combinations.

According to circumstances 1 (according to an embodiment of the invention) will be sent as the kerosene of raw material to the reaction zone for open loop, and By its side, logistics is sent to gasoline hydrogenation cracker (GHC) unit, and LPG fractions are detached from the overhead materials of unit 2.

According to circumstances 2 (according to an embodiment of the invention), by as the lightweight vacuum gas oil (VGO) (LVGO) of raw material send to It is sent to gasoline hydrogenation cracker (GHC) unit, overhead materials of the LPG fractions from unit 2 in the reaction zone of open loop, and by its side logistics Middle separation.

The characteristic of kerosene and LVGO can be found in table 1.Table 2 shows single aromatic compounds in charging and has more than one The distribution of the aromatic molecules (two+aromatic compounds) of a ring.Table 3 shows that production district product constitutes (the weight % of raw material).

Table 1：The characteristic of kerosene and LVGO

Table 2：The classification of the aromatic molecules of function as the aromatic ring quantity in kerosene and LVGO

Table 3：Production district product constitutes (the weight % of raw material)

Data expression shown above, the presence of the reaction zone of open loop and gasoline hydrogenation cracking (GHC) for that will feed Polycyclic aromatic molecule is converted to more valuable monocyclic aromatics and LPG.In addition, also from cycloalkane to monocyclic aromatic The dehydrogenation for closing object obtains BTX.

Claims (27)

1. a kind of method for oil plant heavy hydrocarbon to be modified to petroleum chemicals the described method comprises the following steps：

(a) hydrocarbon raw material is fed to the reaction zone for open loop, wherein the main technique item in the reaction zone for open loop Part is：The raw material of 100 DEG C to 500 DEG C of temperature and 2 to 10MPa pressure and 50 to 300kg hydrogen/1,000kg, and make With aromatic hydrogenation catalyst, and the logistics of gained is passed into ring breakage unit in the following conditions：At 200 DEG C to 600 DEG C Temperature and 1 to 12MPa pressure and 50 hydrogen/1,000kg to 200kg described in gained logistics, and urged using ring crack solution Agent；

(b) effluent from (a) is fed to separative element, is used to prepare the gas stream comprising lightweight boiling hydrocarbon, includes stone The liquid flow of cerebrol boiling range hydrocarbon and the liquid flow for including diesel boiling range hydrocarbon；

(c) liquid flow comprising naphtha boiling-range hydrocarbon is fed to Hydrocracking unit, wherein being hydrocracked list described Technological condition in member is：300-580 DEG C of reaction temperature, the pressure of 0.3-5MPa gauge pressures and the weight of 0.1-10h-1 Space time velocity；

(d) by the reaction product of the Hydrocracking unit of step (c) be separated into the overhead gas stream comprising lightweight boiling hydrocarbon and Include the tower base stream of the mixture of benzene, toluene and dimethylbenzene,

(e) overhead gas stream of the Hydrocracking unit of step (d) and the separation list from step (b) will be come from The gas stream of member feed to steam cracking unit and at least one or more selected from by dehydrogenating propane unit, butane dehydrogenation And the unit in the group of the propane-butane dehydrogenation unit composition of combination.

2. method described in claim 1, wherein the step (e) carries out after the hydrogeneous logistics of gas flow separation.

3. method described in claim 1, the method further include：The institute of the Hydrocracking unit of step (d) will be come from The gas stream for stating overhead gas stream and the separative element from step (b) is fed to another separative element and will be as The logistics of this separation is fed to the steam cracking unit and one or more dehydrogenation units.

4. the method described in any one of claim 1-3, wherein selected from by dehydrogenating propane unit, butane dehydrogenation and combination The certain embodiments carried out at least one of group of propane-butane dehydrogenation unit composition or multiple units are catalytic process, and And the Steam cracking processes carried out in the steam cracking unit are thermal cracking processes.

5. method described in claim 1, the method further includes that the hydrocarbon original is pre-processed in aromatic compounds extraction unit Material flows into material to the reaction zone for open loop from the aromatic compounds extraction unit by its rich aromatic compounds.

6. the method described in claim 5, wherein the aromatic compounds extraction unit is selected from by distillation unit type, molecular sieve The group of type and solvent extraction unit type composition.

7. method described in claim 5 or 6 further includes pre-processing the hydrocarbon raw material in separation equipment unit, from described point Naphtha boiling-range hydrocarbon-fraction is fed directly to the Hydrocracking unit from unit, and its heavier fraction is fed To the ring-opening reaction area.

8. method described in claim 5 or 6 further includes pre-processing the hydrocarbon raw material in pre- Hydrocracking unit, from described Pre- Hydrocracking unit feeds heavy hydrocarbon fractions to the ring-opening reaction area, by the logistics comprising naphtha boiling-range hydrocarbon directly into Material is fed to the Hydrocracking unit, and by the gas stream comprising LPG to steam cracking unit and one or more choosings Unit in the group of free dehydrogenating propane unit, butane dehydrogenation unit and the propane-butane dehydrogenation unit of combination composition.

9. method described in claim 5 or 6 further includes pre-processing the hydrocarbon original in hydrodealkylation/weight integer unit Material, the mixture stream passes of benzene, toluene and dimethylbenzene is obtained from the hydrodealkylation/weight integer unit, by heavy hydrocarbon fractions Charging is fed to the ring-opening reaction area, and by the gas stream comprising LPG to steam cracking unit and one or more choosings From the unit of the propane-butane dehydrogenation unit of dehydrogenating propane unit, butane dehydrogenation unit and combination.

10. the method described in any one of claim 1-3, the method further include：The separation list of step (b) will be come from The gas stream of member, the gas stream from the hydrodealkylation/weight integer unit and from being hydrocracked list in advance At least one of described gas stream of member is fed to the Hydrocracking unit.

11. according to the method described in any one of claim 2-3, the method further includes that will be hydrocracked list from described The tower base stream of member is fed to transalkylation.

12. the method described in any one of claim 1-3, the method further includes that will include bavin from the separative element The liquid flow of oily boiling range hydrocarbon is fed to aromatic compounds saturation unit.

13. the method described in any one of claim 1-3, the method further include：It will be from the Hydrocracking unit The overhead gas stream, the gas stream of the separative element from step (b) and from pre- Hydrocracking unit and described The gas stream of hydrodealkylation/weight integer unit is separated into individual logistics, each logistics respectively mainly comprising C2 alkanes, C3 alkanes and C4 alkanes, and each independent logistics is fed to the special stove section of the steam cracker unit, It is middle to send hydrogeneous logistics to one or more hydrogen consumption technique units,

Further include：It will only C3-C4 fractions at least one of feed to the dehydrogenation unit.

14. the method described in claim 13 is split wherein one or more of hydrogen consumption technique units is the pre-add hydrogen Change unit and the reaction zone for open loop.

15. the method described in claim 13, wherein the C3-C4 fractions are separated C3 and C4 streams.

16. the method described in claim 13, wherein the C3-C4 fractions are the C3+C4 logistics of combination.

17. the method described in any one of claim 1-3, wherein the technological condition in the separative element is 149 DEG C to 288 DEG C of temperature and 1MPa to 17.3MPa pressure.

18. the method described in any one of claim 1-3, wherein the technological condition in the Hydrocracking unit It is：450-580 DEG C of reaction temperature, the pressure of 0.6-3MPa gauge pressures, 0.2-6h^-1Weight hourly space velocity.

19. method of claim 18, wherein the reaction temperature is 470-550 DEG C.

20. method of claim 18, wherein the pressure is the pressure of 1000-2000kPa gauge pressures.

21. method of claim 18, wherein the pressure is the pressure of 1-2MPa gauge pressures.

22. method of claim 18, wherein the pressure is the pressure of 1.2-1.6MPa gauge pressures.

23. method of claim 18, wherein the weight hourly space velocity is 0.4-2h^-1。

24. the method described in any one of claim 1-3, wherein the technological condition in the steam cracking unit It is：750-900 DEG C of reaction temperature, 50-1000 milliseconds of residence time, and it is depressed into selected from air the pressure of 175kPa gauge pressures.

25. the method described in any one of claim 1-3, the wherein hydrocarbon raw material of step (a) are selected from by the following terms group At group：Shale oil, crude oil, kerosene, diesel oil, AGO (atmospheric gas oil), condensate, wax, vacuum gas oil (VGO), decompression residuum, normal pressure slag Oil, naphtha, light cycle, heavy recycle stock, diesel oil and slurry oil or combination thereof.

26. the method described in any one of claim 1-3, the wherein hydrocarbon raw material of step (a) are selected from by the following terms group At group：Pretreated naphtha, coking naphtha, FCC naphtha or combination thereof.

27. the method described in any one of claim 1-3, the wherein hydrocarbon raw material of step (a) are selected from by the following terms group At group：Contaminated crude naphtha.