CN103764799A

CN103764799A - Upgrading hydrocarbon pyrolysis products by hydroprocessing

Info

Publication number: CN103764799A
Application number: CN201280041820.4A
Authority: CN
Inventors: S·H·布朗; S·M·戴维斯; J·S·布坎南; D·T·菲卢赫利; K·G·里德
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2011-08-31
Filing date: 2012-08-31
Publication date: 2014-04-30
Anticipated expiration: 2032-08-31
Also published as: CA2843517A1; WO2013033590A2; EP2751234A2; CN103764799B; EP2751234B1; WO2013033590A3

Abstract

The invention relates to upgraded pyrolysis products, processes for upgrading products obtained from hydrocarbon pyrolysis, equipment useful for such processes, and the use of upgraded pyrolysis products. A tar-containing stream recovered from the pyrolysis effluent is mixed with a utility fluid and subsequently hydroprocessed.

Description

By hydrotreatment upgrading hydrocarbon pyrolysis product

The cross reference of related application

The application requires to enjoy rights and interests and the right of priority of the U.S. Provisional Application 61/657299 of the U.S. Provisional Application submission on June 8th, 61/529588 and 2012 of the U.S. Provisional Application submission on August 31st, 61/529565,2011 of submitting on August 31st, 2011, and its full content is incorporated herein.

Invention field

The present invention relates to the pyrolysis product of upgrading, by the method for the product upgrading obtaining from hydro carbons pyrolysis, for the equipment of these methods, and the purposes of the pyrolysis product of upgrading.

Background of invention

Pyrolytic process, for example steam cracking can be used for transforming stable hydrocarbon be high value-added product as light olefin, for example, ethene and propylene.Except these useful products, the low value-added product of remarkable quantity may be also produced in hydrocarbon pyrolysis, for example steam cracker tar (" SCT ").

The SCT method for upgrading that relates to conventional catalytic hydroprocessing is limited to significant catalyst deactivation.The method can operate in the temperature range of 250 ℃ to 380 ℃ and in the pressure range of 5400 kPas to 20500 kPas, and this process can be used one or more the catalyzer containing in Co, Ni or Mo; But significantly catalyzer coking can be observed.Although catalyzer coking can, by the hydrogen partial pressure raising, reduce space velocity, and be reduced in the operating process in the temperature controlling range of 200 ℃ to 350 ℃; But SCT hydrotreatment is not under these conditions needed, this is because the increase of hydrogen dividing potential drop will make the inadequate economy of this process, due to the increase of hydrogen and equipment cost, and due to the hydrogen dividing potential drop increasing, the space velocity reducing, and the temperature range reducing will be conducive to unwanted hydrogenation.

Summary of the invention

In one embodiment, the present invention relates to a kind of hydroconversion process, the method comprises:

(a) provide the first mixture, the hydrocarbon that it comprises the weight >=10.0wt% based on the first mixture;

(b) pyrolysis the first mixture is to produce the C of comprise>=1.0wt% ₂unsaturates and>=the second mixture of 0.1wt% tar, the weight of this weight percentage based on the second mixture;

(c) separating tar logistics from described the second mixture, the molecule of atmospheric boiling point >=290 ℃ in comprise >=90.0wt% of wherein said tar stream the second mixture;

(d) provide effectiveness fluid, comprise >=40.0wt% of this effectiveness fluid aromatics carbon, based on the weight of effectiveness fluid;

(e) under catalytic hydroprocessing condition, under molecular hydrogen and the existence of effectiveness fluid, at least a portion tar stream is exposed to at least one hydrotreating catalyst to produce hydrotreater effluent, wherein effectiveness fluid: tar weight ratio is in 0.05 to 3.5 scope; With

(f) from hydrotreater effluent, isolate liquid phase, comprise >=90.0wt% of described liquid phase has the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on the weight of hydrotreater effluent,

Wherein said effectiveness fluid comprises the liquid phase of the separation of quantity >=90.0wt%, based on the weight of effectiveness fluid.

In another embodiment, the present invention relates to a kind of hydroconversion process, the method comprises:

(d) provide effectiveness fluid, this effectiveness fluid comprise by NMR, measure >=40.0wt% aromatics carbon, based on the weight of effectiveness fluid;

(e) under catalytic hydroprocessing condition, under molecular hydrogen and the existence of effectiveness fluid, at least a portion tar stream is exposed to at least one hydrotreating catalyst to produce hydrotreater effluent, wherein said effectiveness fluid: tar weight ratio is in 0.05 to 3.5 scope;

(f) from hydrotreater effluent, isolate liquid phase, comprise >=90.0wt% of described liquid phase has the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on the weight of hydrotreater effluent;

(g) from described liquid phase, isolate light weight fluid and heavy liquid, wherein said heavy liquid contains the molecule in the liquid phase that 90wt% has atmospheric boiling point >=300 ℃;

Wherein said effectiveness fluid comprises that quantity is >=light weight fluid of the separation of 90.0wt%, based on the weight of effectiveness fluid.

In another embodiment still, the present invention relates to a kind of hydroconversion process continuously, the method comprises:

(c) provide effectiveness fluid, this effectiveness fluid comprise by NMR, measure >=40.0wt% aromatics carbon, based on the weight of effectiveness fluid;

(d) under hour catalytic hydroprocessing condition of operation time length>=24, at effectiveness fluid and 50.0S m ³/ m ³to 890.0S m ³/ m ³under the existence of molecular hydrogen at (i) LHSV approximately 1.0 × 10 ^-1in approximately 10.0 scope, (ii) temperature is the scope of 300.0 ℃ to 500.0 ℃, (iii) pressure from 25 bar (definitely) to the scope of 100 bar (definitely), and (iv) effectiveness fluid: tar stream weight ratio is, in 0.1 to 3.5 scope, the tar of tar weight>=50.0wt% the second mixture based on the second mixture is exposed to at least one hydrotreating catalyst, to produce hydrotreater effluent; With

(e) from hydrotreater effluent, isolate liquid phase, comprise >=95.0wt% of described liquid phase has the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on the weight of hydrotreater effluent, wherein said effectiveness fluid comprises the liquid phase of the separation of quantity >=99.0wt%, based on the weight of effectiveness fluid.

In certain embodiments, the present invention relates to have the tar of the hydrotreatment that improves blending characteristic compared with tar charging, for example, the tar of this hydrotreatment can have less asphaltene precipitation containing the logistics blending of heavy hydrocarbon with other, than the burnt oil condition that adopts not hydrotreatment.Therefore the tar of this hydrotreatment be suitable as blending stock, for example, and for the relative low value heavy hydrocarbon of upgrading wide region.

Accompanying drawing explanation

Fig. 1 has schematically shown embodiment of the present invention, wherein in the downstream in hydrotreatment stage, utilizes separation level to be used as effectiveness fluid with the overall product liquid of separation and a part of reactor effluent that circulates.

Detailed Description Of The Invention

Part of the present invention is based on following discovery: catalyzer coking can be reduced by this SCT of hydrotreatment in the case of the effectiveness fluid of the monocycle that comprises remarkable quantity or polynuclear aromatic compound exists.Be different from traditional SCT hydrotreatment, this process can operate under the required temperature and pressure that adds hydrocrackingization reaction being conducive to respect to aromatic hydrocarbons hydrogenization.The liquid phase effluent that has been found that a part of hydrotreater can circulate and be used as and make effectiveness fluid.

Term " SCT " refers to that (a) has one or more aromatic kernels and optional (b) non-aromatic material and/or the hydrocarbon mixture of non-hydrocarbon molecule, this mixture comes from hydrocarbon pyrolysis and has boiling spread >=approximately 550 °F (290 ℃), for example, the SCT molecule of >=90.0wt% has atmospheric boiling point >=550 °F (290 ℃).SCT can comprise the weight based on SCT, for example,>=50.0wt%,>=75.0wt%, the hydrocarbon molecule (comprising their mixture and their aggregation) of>=90.0wt%, described hydrocarbon molecule has (i) one or more aromatic kernels and (ii)>=about C ₁₅molecular weight.

Have been found that SCT comprises the heavy tar (" TH ") of remarkable quantity.In this specification sheets and claims, term " heavy tar " refers to the pyrolysis product of hydrocarbon, this TH has atmospheric boiling point >=565 ℃ and the weight based on this product contains >=5.0% there is the molecule of multiple aromatic kernels.This TH is at 25.0 ℃ of solids and generally comprise the SCT cut (" conventional pentane extraction ") of the Skellysolve A that is insoluble to 5:1 (volume: volume) ratio at 25.0 ℃: SCT typically.This TH can comprise high molecular weight molecules (for example MW >=600), as bituminous matter and other high-molecular-weight hydrocarbons.Term " bituminous matter " is defined as heptane insolubles, and measures according to ASTM D3279.For example, the high molecular weight molecules that can comprise>=10.0wt% of this TH contains aromatic kernel, they can be by following one or more: (i) relatively low-molecular-weight alkane and/or alkene, for example, C ₁to C ₃alkane and/or alkene, (ii) C ₅and/or C ₆naphthenic ring, or (iii) thiphene ring.In general, the carbon atom of this TH of >=60.0wt% is comprised in one or more aromatic kernels, the carbon atom weight based on this TH, for example, in the scope of 68.0wt% to 78.0wt%.Although do not wish to be subject to the constraint of any theory or model, also believe that this TH forms the aggregation with relatively flat form, this is the result due to the Van der Waals'attractive force between TH molecule.The large size of this TH aggregation, it can be for example in their maximum dimension, and ten nanometers, to the scope of hundreds of nanometer (" nm "), cause low aggregation mobility and diffustivity under catalytic hydroprocessing condition.In other words, conventional TH transforms impaired in serious mass transfer limitations, and it causes TH to change into the highly selective of coke.Having been found that SCT is combined with effectiveness fluid-phase decomposes this aggregation and becomes single molecule, for example, its in their maximum dimension≤5.0nm and molecular weight be approximately within the scope of every mole 200 grams to every mole 2500 grams.This will cause more large fluidity and the diffustivity of TH of SCT, thereby under hydroprocessing condition, causes catalyzer duration of contact and the less conversion to coke shortened.Result is, SCT transforms can be at lower pressure, for example, moves 500psig to 1500psig (34.5-103.4 cling to gauge pressure) is lower, and this will significantly reduce cost and complicacy, with respect to the more hydrotreatment of high pressure.The present invention be advantageous in that this SCT is not the light hydrocarbon that produces in certain embodiments of making of overcracking, for example, C ₄or lighter material, being less than about 5.0wt%, it causes the independent composition of polynuclear compound, and has further reduced the consumption of hydrogen in hydrotreatment process.

In certain embodiments, the present invention relates to a kind of hydrotreatment tar as the steam-cracked tar of hydrotreatment, it has improved viscosity and blending characteristic.In these embodiments, the tar of hydrotreatment can be by obtaining tar charging being carried out to catalytic hydroprocessing under catalytic hydroprocessing condition under the existence at effectiveness fluid, this catalytic hydroprocessing condition is included in temperature 375 ℃ to 425 ℃ scopes, for example 385 ℃ to 415 ℃ scopes; Pressure at 45 bar (definitely) to the scope of 135 bar (definitely), if 60 bar (definitely) are to 90 bar (definitely); Molecular hydrogen treatment rate (based on tar charging) is at 150S m ³/ m ³to 1200S m ³/ m ³in the scope of (840SCF/B to 6700SCF/B), as at 180S m ³/ m ³to 450S m ³/ m ³in the scope of (1000SCF/B to 2500SCF/B); In 0.1 to 2.0 scope, for example 0.25 to 0.50 LHSV is based on combined feed total feed (tar+effectiveness fluid) with LHSV.This effectiveness fluid can circulate from hydrotreater effluent (optionally after separating the tarry cut of hydrotreatment), or obtains from external source.This catalyzer can be, for example, and the cobalt-molybdenum catalyzer of the alumina load of conventional sulfuration.The tar of having observed production hydrotreatment under these conditions can cause less undesirable byproduct, and it has molecular weight and is less than or equal to C4 (C _4-byproduct).

SCT parent material is different from other relatively hydrocarbon mixtures of high molecular, as former oil residue (" residual oil "), comprises that long residuum and vacuum residuum and other are common, for example, and the logistics running in oil and petroleum chemistry processing.Pass through C ¹³the aromatics carbon content of the SCT that NMR measures is obviously greater than the aromatics carbon content of Residual oil.For example, in SCT, aromatics carbon content is typically greater than 70.0wt% and aromatics carbon content in residual oil is less than 40.0wt% conventionally.In order to study some differences of knowing between residual oil and SCT, two kinds of representative SCT samples and three kinds have the performance of selection of table property residual oil sample as shown in table 1 below.The bitum signal portion of SCT has atmospheric boiling point and is less than 565 ℃.For example, in SCT1, only the bituminous matter of 32.5wt% has atmospheric boiling point and is greater than 565 ℃.This is not the situation with vacuum residuum, wherein 100% bitum atmospheric boiling point >=565 ℃ substantially.Even if solvent extraction is faulty technological process, result shows the bituminous matter in vacuum residuum, great majority be have atmospheric boiling point be greater than 565 ℃ compared with weight molecule.When with those roughly the same conditions for vacuum residuum under while experiencing heptane solvent extraction, the bituminous matter obtaining from SCT contains larger per-cent (take weight as benchmark) and has the molecule of atmospheric boiling point <565 ℃, than the situation for vacuum residuum.The metal just existing and the relative quantity of nitrogenous compound, SCT is also different from residual oil.In SCT, the total amount of metal is≤1000.0ppmw (1,000,000/portion, weight), based on the weight of SCT, for example ,≤100.0ppmw, as≤10.0ppmw.The total nitrogen existing in SCT is generally less than the nitrogen content existing in crude oil vacuum residuum.

Two kinds of representative SCT samples and three kinds have the performance of selection of table property residual oil sample as shown in the table.

Table 1

* N.M.=is unmeasured

Compared with residual oil in SCT aliphatic carbons quantity and the carbon number amount that exists in long-chain substantially lower.Although only similar to residual oil aspect slightly lower and oxygen level (weight basis) at the total carbon of SCT, the metal in SCT, hydrogen, and nitrogen content (weight basis) scope is quite low.At be generally at the 50 ℃ >=100cSt of kinematic viscosity of SCT, or >=1000cSt, though relative populations have >=and the SCT of the atmospheric boiling point of 565 ℃ is much smaller than slag oil condition.

SCT normally obtains by the product of hydrocarbon pyrolysis.This method for pyrolysis comprises, for example, pyrolysis, for example, utilize the hot pyrolytic process of water.Such pyrolytic process, steam cracking, will below illustrate in greater detail.The present invention is not limited to steam cracking, and this description do not mean that get rid of in more broad range of the present invention, use other pyrolytic processs.

By pyrolysis, obtain SCT

The pyrolysis oven that conventional steam cracking utilizes has two main sections: convection zone and radiation section.Raw material (the first mixture) enters the convection zone of this stove, wherein by the hydrocarbon component in the first mixture by with indirect contact from radiation section hot flue gases and by heating and vaporize with direct contact of steam component in the first mixture.Then the hydrocarbon mixture of steam-vaporization is introduced into radiation section and cracking reaction occurs therein.From pyrolysis oven, the second mixture is guided, the second mixture comprises any unreacted component the product that obtains from the pyrolysis of the first mixture and the first mixture.At least one separation phase is usually located at the downstream of pyrolysis oven, and this separation phase is used to separate following one or more from the second mixture: light olefin, SCN, SCGO, SCT, unreacted hydrocarbon component etc. in water and the first mixture.This separation phase can comprise, for example, and main fractionating tower.Conventionally, cooling stages, typically direct quenching or indirect heat exchange are between pyrolysis oven and separation phase.

In one or more embodiments, SCT is as in one or more pyrolysis ovens, and for example, in one or more steam cracker furnace, the product of pyrolysis obtains.Except SCT, this stove produces (i) gas-phase product conventionally, as acetylene, and ethene, propylene, one or more in butylene, and (ii) liquid product, it comprises one or more C ₅₊molecule with and composition thereof.Liquid product enters into separation phase conventionally in the lump, for example, main fractionator, for separating of following one or more: (a) comprise steam cracking petroleum naphtha (" SCN ", for example, C ₅-C ₁₀kind) and the overhead fraction of steam cracked gas oil (" SCGO "), this SCGO comprises weight>=90.0wt% atmospheric boiling point based on SCGO molecule (for example, C in approximately 400 °F to 550 °F (200 ℃ to 290 ℃) scopes ₁₀-C ₁₇kind), and (b) bottom fraction of contain>=90.0wt%SCT (for example tar stream), based on the weight of this bottom fraction, this SCT has approximately>=550 °F of boiling points (290 ℃) and comprises that molecular weight is>=about C ₁₅molecule and composition thereof.

Charging in this pyrolysis oven is the first mixture, contain >=10.0wt% of this first mixture hydrocarbon, and based on the weight of described the first mixture, for example, >=15.0wt%, for example >=25.0wt%, >=50.0wt%, for example >=0.65wt%.Although hydro carbons can comprise; for example; one or more light hydrocarbon is as methane; ethane; propane; butane etc., also can adopt the first mixture of the hydrocarbon with higher molecular weight that comprises remarkable quantity in the present invention, and this is because the pyrolysis of these molecules can produce more SCT compared with the pyrolysis of low molecular weight hydrocarbon conventionally.As an example, can advantageously make to be fed to multiple pyrolysis ovens whole comprise >=1.0wt% of the first mixture or >=25.0wt% is the hydrocarbon of liquid phase at ambient temperature and under atmospheric pressure, based on the weight of the first mixture.

The first mixture can further comprise thinner, for example, following one or more: nitrogen, water etc., for example, and the thinner of >=1.0wt%, based on the quality of described the first mixture, as >=25.0wt%.When described pyrolysis is steam cracking, this first mixture can and wrap vapoury thinner by hydro carbons, for example, with every kilogram of hydrocarbon of 0.1-1.0 kilogram of steam, or the ratio of every kilogram of hydrocarbon of 0.2-0.6 kilogram of steam, combine to produce.

In one or more embodiments, comprise >=10.0wt% of the hydrocarbon of described the first mixture, for example >=50.0wt%, one or more that for example >=90.0wt% (based on the weight of hydrocarbon) is following: petroleum naphtha, gas oil, vacuum gas oil, wax-like residual oil, long residuum, residual oil mixed compound, or crude oil; Comprise containing >=about 0.1wt% bitum those.Suitable crude oil comprises, for example, and high-sulfur straight run crude oil, as be rich in those of polynuclear aromatic compound.Optionally, the hydrocarbon of described the first mixture comprises sulphur, for example, and >=0.1wt% sulphur, the weight of the hydrocarbon based in described the first mixture.For example, >=1.0wt%, for example, in approximately 1.0% to approximately 5.0% weight range.Optionally, the sulfur-containing molecules of this of at least a portion the first mixture, for example, the sulfur-containing molecules of the first mixture of >=10.0wt%, comprises at least one aromatic ring (" aromatics sulphur ").When the hydrocarbon in (i) first mixture is the crude oil of comprise >=0.1wt% aromatics sulphur or crude oil fractions and (ii) when pyrolysis is steam cracking, SCT contains remarkable quantity and derives from the sulphur of aromatics sulphur in the first mixture.For example, in SCT, sulphur content is about 3 to 4 times higher than the hydrocarbon component concentration in the first mixture, take weight as benchmark.

In specific embodiment, the hydrocarbon of the first mixture comprises following one or more: crude oil and/or one or more crude oil fractions, which (" VPS ") obtaining as those which (" APS ") obtaining from normal pressure pipe still and/or electron tubes type water distilling apparatus.The optionally desalination before the first mixture comprises by crude oil and/or its cut.The example of the crude oil fractions utilizing in the first mixture be by by from crude separation APS bottom fraction and subsequently the VPS by APS bottom fraction process and produce.

Optionally, this pyrolysis oven has the gas/liquid tripping device (being sometimes called as flash drum or flash tank) of at least one and its integration, for upgrading the first mixture.When comprise >=about 0.1wt% bituminous matter of the hydrocarbon component in the first mixture, the weight of the hydrocarbon component based in the first mixture, for example >=during 5.0wt%, such gas/liquid tripping device is particularly suitable.Conventional gas/liquid tripping device can be used for carrying out this operation, but the present invention is not limited to this.The example of this traditional gas/liquid tripping device comprises and is disclosed in those in following U.S. Patent number: 7,138,047; 7,090,765; 7,097,758; 7,820,035; 7,311,746; 7,220,887; 7,244,871; 7,247,765; 7,351,872; 7,297,833; 7,488,459; 7,312,371; With 7,235,705, their full content is incorporated herein.Suitable gas/liquid tripping device is to be equally also disclosed in United States Patent (USP) 6,632, and in 351 and 7,578,929, their full content is incorporated herein.Conventionally, when using gas/liquid tripping device, the composition of gas phase that leaves this device is substantially identical with the composition of gas phase that enters this device, the composition of liquid phase that leaves equally flash tank is substantially identical with the composition of liquid phase that enters this device, that is, the separation in gas/liquid tripping device comprises that (or even consisting essentially of) enters the physical sepn of two phases of this tank.

In the embodiment of using gas/liquid tripping device and pyrolysis oven to integrate mutually, the hydrocarbon component of at least a portion the first mixture is provided for the convection zone entrance of pyrolysis unit, and to be wherein heated and to make the hydrocarbon of at least a portion be in gas phase to hydrocarbon.For example, when thinner (, steam) is when being used, the thinner composition of the first mixture in this part, be optionally (still preferably) add and mix to produce the first mixture with hydrocarbon component.Then by the first mixture, its at least a portion is in gas phase, and at least one gas/liquid tripping device, flash distillation is with for example, from the first mixture separation and be directed away the high molecular weight molecules of first mixture of at least a portion, bituminous matter.Bottom fraction can come from the guiding of gas/liquid tripping device, the bituminous matter of comprise >=10.0wt% of this bottom fraction (basis by weight) the first mixture.When the described pyrolysis hydrocarbon component that is steam cracking and the first mixture comprises one or more crude oil or its cut, steam cracker furnace can be with in the temperature range of about 600 °F to 950 °F (approximately 350 ℃ to approximately 510 ℃) and in the pressure range of approximately 275 kPas to approximately 1400 kPas, for example, in the temperature range of approximately 430 ℃ to approximately 480 ℃ and at approximately 700 kPas, integrate to the gas/liquid tripping device operating within the scope of 760 kpa pressures.The overhead fraction deriving from gas/liquid tripping device can be by further heating of experience in convection zone, then by cross manifold, introduce radiation section, wherein overhead fraction is exposed on to temperature >=760 ℃ and pressure >=0.5 bar (gauge pressure), for example, temperature in the scope of approximately 790 ℃ to approximately 850 ℃ and pressure at approximately 0.6 bar (gauge pressure) in approximately 2.0 bar (gauge pressure), for example, to carry out the pyrolysis (, cracking and/or reformation) of hydrocarbon component in the first mixture.

In the downstream of convection zone entrance and the advantage to the upstream of the cross manifold of radiation section with gas/liquid tripping device, be that it has increased the scope that can directly there is no pretreated hydrocarbon types as the hydrocarbon component in the first mixture.For example, can the comprise >=50.0wt% of hydrocarbon component of the first mixture, for example >=75.0wt%, one or more crude oil of for example >=90.0wt% (weight of the hydrocarbon based in described the first mixture), the crude oil of even high naphthenic acid content and cut thereof.The charging with high naphthenic acid content especially produce high quantity tar those and when at least one gas/liquid tripping device and pyrolysis oven are integrated, be specially suitable.If needed, the composition of the first mixture can change along with the time, for example, by utilizing the first mixture that contains the first hydrocarbon component and then utilize the second mixture that contains the second hydrocarbon component in very first time section within the second time period, described the first and second hydrocarbon are different hydrocarbon substantially or are different hydrocarbon mixtures substantially.Described the first and second time periods can be the time length substantially equating, but this is optional.The first and second time periods alternately can be carried out (for example, in " moudle type " operation) in order continuously or semi-continuously, if necessary.The present embodiment can be for the continuous pyrolysis of the first and second incompatible hydrocarbon components (that is, wherein the first and second hydrocarbon components are enough compatible mixtures with blend not under envrionment conditions).For example, comprise that the first hydrocarbon component of straight run crude oil can be for producing the first mixture and steam-cracked tar for producing the first mixture in the second time period in first time period.

In other embodiments, do not use vapor/liquid separation device.For example, when the hydrocarbon of the first mixture comprises crude oil and/or one or more its cuts, pyrolytical condition can be conventional steam cracking conditions.Suitable steam cracking condition comprises, for example, the first mixture is for example exposed to, under temperature (measuring in radiation exit) >=400 ℃ of conditions, in the scope of 400 ℃ to 900 ℃, and pressure >=0.1 bar, continue the cracking residence time approximately 0.01 second to 5.0 seconds scopes.In one or more embodiments, the first mixture comprises hydrocarbon and thinner, it is characterized in that, the alkyl of the first mixture is following one or more containing >=50.0wt% in the weight package of the hydrocarbon of the first mixture: wax-like residual oil, long residuum, petroleum naphtha, residual oil mixed compound, or crude oil.Thinner comprises, for example, >=95.0wt% water, based on the weight of thinner.When thinner that the first mixture comprises 10.0wt% to 90.0wt%, based on the weight of described the first mixture, this pyrolytical condition generally comprises following one or more: (i) temperature within the scope of 760 ℃ to 880 ℃; (ii) pressure in 1.0 to 5.0 bar (definitely) scopes; Or (iii) cracking residence time within the scope of 0.10 second to 2.0 seconds.

The second mixture is directed out pyrolysis oven, and the second mixture is by coming from the first mixture by pyrolysis.When the pyrolytical condition of regulation is utilized, the C of described generally comprise>=1.0wt% of the second mixture ₂unsaturates and>=TH of 0.1wt%, the weight of this weight percentage based on the second mixture.Optionally, the C of described comprise>=5.0wt% of the second mixture ₂unsaturates and/or>=TH of 0.5wt%, as the TH of>=1.0wt%.Although the second mixture generally contains required light olefin, SCN, SCGO, SCT, and in the first mixture unreacted component is (for example, water in steam cracking situation, but unreacted hydrocarbon in some cases) mixture, this wherein the relative populations of every kind of material for example generally depend on, the composition of the first mixture, pyrolysis oven structure, processing condition in pyrolytic process etc.The second mixture is deflected from pyrolysis part conventionally, for example, and for cooling and/or separation phase.

In one or more embodiments, the TH aggregation of comprise >=10.0wt% of the TH of the second mixture, it has the scope of mean number >=50 of mean sizes in 10.0 nanometer to 300.0 nanometer range and carbon atom, the weight of this weight percentage based on heavy tar in the second mixture at least one dimension.Conventionally, comprise >=50.0wt% of aggregation, for example >=80.0wt%, as >=90.0wt% there is C:H atomic ratio in the scope of 1.0-1.8, molecular weight is in 250 to 5000 scope and the TH molecule of fusing point within the scope of 100 ℃ to 700 ℃.

Although be not requirement, the present invention be with in pyrolysis oven downstream cooling the second mixture compatible, for example, the second mixture can be used the system that comprises transfer-line exchanger to carry out cooling.For example, transfer-line exchanger can process for cooling logistics to the temperature range of approximately 700 ℃ to approximately 350 ℃, effectively to produce extra high pressure steam, it can be utilized by this technological process or be conducted away.If needed, the second mixture can carry out direct quenching in the experience of the point between outlet of still and separation phase typically conventionally.Quenching can be by described the second mixture is contacted to realize with liquid quench logistics, to replace the processing that adopts transfer limes umformer, or except transfer limes umformer.When being combined with at least one transfer-line exchanger, quench liquid is preferably introduced at the point in transfer line interchanger downstream.Suitable quench liquid comprises liquid quench oil, as those quenching oil separating tanks by downstream obtain those, pyrolysis fuel oil and water, it can obtain from routine source, for example, the dilution steam generation of condensation obtains.

Separation phase is employed in the downstream of pyrolysis oven and the downstream of transfer limes interchanger and/or quench point conventionally for from separate following one or more of the second mixture: light olefin, SCN, SCGO, SCT, or water.Conventional separating device can be for separating of the stage, for example one or more flash drum, and separation column, water quench tower, indirect condensers etc., as at United States Patent (USP) 8,083, those described in 931.At separation phase, the 3rd mixture, it is tar stream, can from described the second mixture, separate, and the TH of described the 3rd comprise >=10.0wt% of mixture tar stream the second mixture, the weight of the TH based on the second mixture.When described pyrolysis is steam cracking, described tar stream generally includes SCT, it for example, from the bottoms of the main fractionating tower of SCGO logistics and/or steamed cracking unit, from flash drum bottoms (for example, be positioned at the bottoms of one or more flash drum of pyrolysis oven downstream and main fractionating tower upstream), or their combination obtains.

Tar stream can comprise TH aggregation.In one or more embodiments, the TH of the second mixture of comprise >=50.0wt% of tar stream, the weight of the TH based on the second mixture.For example, the TH of the second mixture of can comprise >=90.0wt% of tar stream, the weight of the TH based on the second mixture.Tar stream can have, for example, (i) sulphur content is in 0.5wt% to 7.0wt% scope, (ii) TH content is in 5wt% to 40.0wt% scope, the weight of this weight percentage based on described tar stream, (iii) density in the time of 15 ℃ is 1.01g/cm ³to 1.15g/cm ³scope in, as at 1.07g/cm ³to 1.15g/cm ³scope in, and (iv) 50 ℃ of viscosity in 200cSt to 1.0 × 10 ⁷in the scope of cSt.

The tar stream conventionally directed separation phase that leaves is that this effectiveness fluid generally includes the liquid phase part of the circulation of hydrotreater effluent for the hydrotreatment in the coal-tar middle oil logistics of one or more hydrotreatment stage under existing at effectiveness fluid.Effectiveness fluid example useful in the present invention is described now in more detail.

Effectiveness fluid

Effectiveness fluid is used for to hydrotreatment tar stream, for example, for effectively increasing the running length increasing during hydrotreatment and the performance that can improve the tar of hydrotreatment.Effectively effectiveness fluid composition comprises aromatic hydrocarbons,, comprises the molecule with at least one aromatic kernel that is.In one or more embodiments, this effectiveness fluid comprises and passes through ¹³measure>=40.0wt% aromatics carbon of C NMR (Nuclear Magnetic Resonance) spectrum, as>=60.0wt% aromatics carbon.In certain embodiments, effectiveness fluid comprises a part of liquid phase effluent.In other words, the total liquid product that a part is added to anti-treatment zone is circulated back to hydrotreater effectively.For example, total liquid phase part of can comprise >=50.0wt% of effectiveness fluid hydrotreatment stage effluent (liquid phase of hydrotreater effluent for simplicity), for example >=75.0wt%, or >=95.0wt%, or even >=99.0wt%, based on the weight of effectiveness fluid.The remainder (being remainder) of the hydrotreatment stage liquid phase effluent of hydrotreater effluent can deflect from from the method, and optionally for example, as low sulphur fuel oil blending component.Effluent from the hydrotreatment stage optionally passes through one or more separation phases.The limiting examples of separation phase can comprise: flash tank, distillation tower, vaporizer, stripper, steam stripped device, vacuum flashing, or vacuum still.These separation phases allow those skilled in the art to regulate the performance of liquid phase part of hydrotreater effluent with as effectiveness fluid.In can comprise >=90.0wt% of the liquid phase part of hydrotreater effluent hydrotreater effluent, there is the molecule of at least four carbon, based on the weight of hydrotreater effluent.In other embodiments, in comprise >=90.0wt% of the liquid phase of hydrotreater effluent hydrotreater effluent, there are atmospheric boiling point >=65.0 ℃, for example >=100.0 ℃, the molecule (based on the weight of hydrotreater effluent) of for example >=150.0 ℃.

In other embodiments, total liquid phase part of hydrotreater effluent is separated into light weight fluid and heavy liquid, what in contain >=90wt% of wherein said heavy liquid liquid phase, exist has atmospheric boiling point >=250 ℃, a molecule of for example >=350 ℃.Effectiveness fluid can comprise that from then on a part separates the light weight fluid obtaining.

Optionally, in other embodiments, the effectiveness fluid that comprises at least a portion liquid phase of hydrotreater effluent can be increased or be substituted by supplementary effectiveness fluid, described supplementary effectiveness fluid has ASTM D8610% and heats up in a steamer a little >=120 ℃, for example, >=140 ℃, such as >=150 ℃ and/or ASTM D8690% heat up in a steamer a little≤300 ℃.Between the starting period or this option of time period of cell failure or other operability part be useful especially, for example, when tar stream quality change.

Supplementing effectiveness fluid can be solvent or solvent mixture.In one or more embodiments, this supplementary effectiveness fluid (i) has the critical temperature in the scope of 285 ℃ to 400 ℃, and (ii) 1-cyclophane compounds of group and/or the 2-cyclophane compounds of group of comprise >=80.0wt%, comprise their alkyl functional derivative, based on the weight of this supplementary effectiveness fluid.For example, this supplementary effectiveness fluid can comprise, for example, the monocyclic aromatics of >=90.0wt%, comprises those with one or more hydrocarbyl substituents, as 1 to 3 or 1 to 2 's hydrocarbyl substituent.These substituting groups can be any alkyl consistent with all solvent distillation characteristicss.The example of this class alkyl include but not limited to and is selected from C ₁-C ₆those of alkyl, wherein this hydrocarbyl group can be side chain or straight chain with hydrocarbyl group can be identical or different.Optionally, supplement following one or more of weight comprise >=90.0wt% of effectiveness fluid based on supplementing effectiveness fluid: benzene, ethylbenzene, trimethylbenzene, dimethylbenzene, toluene, naphthalene, alkylnaphthalene is (for example, methylnaphthalene), tetraline, or alkyl tetrahydro naphthalene (for example, methyltetrahydro naphthalene).Conventionally need to supplement effectiveness fluid and be substantially devoid of the molecule with thiazolinyl function, especially in the embodiment of hydrotreating catalyst that adopts the tendency under these molecules exist with coke formation.In one embodiment, this supplementary comprise≤10.0wt% of effectiveness fluid comprises the C with thiazolinyl function ₁-C ₆the cyclic cpds of side chain, based on the weight of effectiveness fluid.

In certain embodiments, this supplementary effectiveness fluid comprises SCN and/or SCGO, for example, from the main fractionator in the downstream of the pyrolysis oven that operates under steam cracking operational condition from SCN and/or the SCGO of the second mixture separation.Conventionally, the C of SCN and/or SCGO preferably ₆₊cut.This SCN or SCGO can carry out hydrotreatment (for example, not adopting hydrogenation of tar processing) in different conventional hydrotreaters.This supplementary effectiveness fluid can comprise, for example, the gas oil that >=50.0wt% separates, based on the weight of supplementing effectiveness fluid.In certain embodiments, at least a portion effectiveness fluid obtains from the product of hydrotreatment, for example, and by the liquid phase part separating and circulation has the hydrotreater effluent of atmospheric boiling point≤300 ℃ again.

Generally speaking, supplement the molecule with one or more aromatic kernels that contains q.s in effectiveness fluid with the effectiveness fluid of product that increases the hydrotreatment that comprises circulation to be effectively increased in the running length in the hydrotreatment process of tar stream.For example, this supplementary can comprise >=50.0wt% of effectiveness fluid has the molecule of at least one aromatic kernel, for example, >=60.0wt%, for example >=70wt%, based on the gross weight of effectiveness fluid.In one embodiment, this supplementary effectiveness fluid comprises that (i)>=60.0wt% has the molecule of at least one aromatic kernel and (ii)≤1.0wt% comprises the C with alkenyl-functional groups ₁-C ₆the cyclic cpds of side chain, the weight of this weight percentage based on effectiveness fluid.

In hydrotreatment process, the relative populations of effectiveness fluid and tar stream is generally the effectiveness fluid from about 20.0wt% to the tar stream within the scope of about 95.0wt% and within the scope of from about 5.0wt% to about 80.0wt%, adds the gross weight of tar stream based on effectiveness fluid.For example, the effectiveness fluid of the relative populations of effectiveness fluid and tar stream within the scope of can being (i) about 20.0wt% to the tar stream within the scope of about 90.0wt% and about 10.0wt% to about 80.0wt% in hydrotreatment process, or (ii) about 40.0wt% is to the tar stream within the scope of about 90.0wt%, and about 10.0wt% is to the effectiveness fluid within the scope of about 60.0wt%.This effectiveness fluid of at least a portion can combine with this tar stream of at least a portion in hydrotreatment container or hydrotreatment district, but this is optional, and in one or more embodiments the effectiveness fluid of at least a portion and at least a portion tar stream be used as independent logistics provide and entering hydrotreatment container or hydroprocessing district before (for example: at its upstream) be combined into a feed stream.In certain embodiments, to the feed stream of hydrotreater, comprise the SCT of 40.0wt%-90.0wt% and the effectiveness fluid of 10.0wt%-40.0wt%, the weight of this weight percentage based on feed stream.For example: tar: effectiveness fluid proportional can be 0.50:1.0 to 3.0:1.0, for example 0.2 to 3.0 scope.

Hydrotreatment

Under effectiveness fluid exists, the hydrotreatment of tar stream can occur in one or more hydrotreatment stage, and this stage comprises one or more hydrotreatment containers or region.The container or the region that wherein occur in hydrotreatment stage of catalytic hydroprocessing activity generally comprise at least one hydrotreating catalyst.This catalyzer can be that mix or stacking, for example, when catalyzer is the form of one or more fixed beds in hydrotreatment container or region.

Conventional hydrotreating catalyst can be used to exist at effectiveness fluid the hydrotreatment process of tar stream in situation, as is given for those of hydrotreatment of residual oil and/or heavy oil, but the present invention is not limited to this.Suitable hydrotreating catalyst comprises having (i) one or more base metals and/or (ii) those of the metal of one or more on carrier.This metal can be simple substance form or exist with the form of compound.In one or more embodiments, hydrotreating catalyst comprises from the 5th to 10 families in the periodic table of elements any one (tabular periodic table of elements, the Merck index, Merck & Co., Inc., 1996).The example of this class catalytic metal includes, but not limited to vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, or their mixture.

In one or more embodiments, in this catalyzer, the total amount that has 5 to 10 family's metals of every gram of catalyzer is at least 0.0001 gram, or is at least 0.001 gram or be at least 0.01 gram, and in base, grams is calculated in elemental basis.For example, total weight range that catalyzer can comprise 5 to 10 family's metals is from 0.0001 gram to 0.6 gram, or from 0.001 gram to 0.3 gram, or from 0.005 gram to 0.1 gram, or be 0.01 gram to 0.08 gram.In a specific embodiment, catalyzer also comprises at least one the 15th family's element.Preferred the 15th family's element is phosphorus.When 15 family's elements are used, this catalyzer can comprise that the total amount in the scope of the 15th family's element is from 0.000001 gram to 0.1 gram, or from 0.00001 gram to 0.06 gram, or from 0.00005 gram to 0.03 gram, or from 0.0001 gram to 0.001 gram, wherein gram calculating is take element as benchmark.

In one embodiment, catalyzer comprises at least one the 6th family's metal.The example of preferred the 6th family's metal comprises chromium, molybdenum and tungsten.This catalyzer can contain, every gram of catalyzer, and the 6th family's total metal content is at least 0.00001 gram, or is at least 0.01 gram, or is at least 0.02 gram, and wherein gram calculating is take element as benchmark.For example, in every gram of catalyzer, comprise the 6th family's total metal content scope from 0.0001 gram to 0.6 gram, or from 0.001 gram to 0.3 gram, or from 0.005 gram to 0.1 gram, or be 0.01 gram to 0.08 scope, wherein grams is calculated take element as benchmark.

In relevant embodiment, catalyzer comprises at least one the 6th family's metal, and further comprises that at least one comes from the 5th family, the 7th family, the 8th family, the 9th family, or the metal of 10 families.This catalyzer can comprise, and for example, the mol ratio of the 6th family's metal and the 5th family's metal should be 0.1 to 20,1 to 10, or the combination of metal in 2 to 5 scope, and wherein said ratio is take element as benchmark.Or described catalyzer should be 0.1 to 20,1 to 10 by the mol ratio that contains total metal content in the 6th family's metal and the 7th to 10 families, or the combination of metal in 2 to 5 scope, wherein said ratio is take element as benchmark.

When comprising at least one the 6th family's metal and one or more, catalyzer comes from the 9th or the metal of the 10th family, for example, molybdenum-cobalt and/or tungsten-nickel, these metals can coexist, for example, the 6th family's metal and the 9th and the molar ratio range of the metal of the 10th family should be from 1 to 10, or 2 to 5, ratio is wherein for take element as benchmark.When catalyzer comprises at least one the 5th family's metal and at least one the 10th family's metal, these metals can coexist, and for example, the molar ratio range of the 5th family's metal and the 10th family should be 1 to 10, or from 2 to 5, ratio is wherein take element as benchmark.Catalyzer also comprises inorganic oxide, for example, and as tackiness agent and/or carrier, within the scope of the present invention.For example, catalyzer can comprise that (i) >=1.0% is selected from periodictable the 6th, 8,9 and 10 one or more metals of family and the inorganic oxide of (ii) >=1.0wt%, the weight of this weight percentage based on catalyzer.

The present invention's imagination is introduced (or depositing on carrier) one or more catalytic metals on carrier, if one or more metals of the 5th to 10 families and/or the 15th family are to form hydrotreating catalyst.This carrier can be porous material.For example, carrier can comprise one or more refractory oxide, porous carbon sill, zeolite or their combinations.Suitable refractory oxide comprises, for example, and aluminum oxide, silicon-dioxide, silica-alumina, titanium oxide, zirconium white, magnesium oxide, and their mixture.Suitable porous carbon sill comprises gac and/or porous graphite.The example of zeolite comprises, for example, and Y-zeolite, β zeolite, mordenite, ZSM-5 type zeolite, and ferrierite.Other example of solid support material comprises gama-alumina, θ-aluminum oxide, δ-aluminum oxide, Alpha-alumina, or their combination.Gama-alumina in every gram of support of the catalyst, δ-aluminum oxide, the total amount of Alpha-alumina or their combination, the scope of being controlled at is, for example 0.0001 gram to 0.99 gram, or from 0.001 gram to 0.5 gram, or be 0.01 gram to 0.1 gram, or maximum 0.1 gram, as measured by X-ray diffraction.In specific embodiment, hydrotreating catalyst is loaded catalyst, and this carrier comprises at least one aluminum oxide, for example, θ-aluminum oxide, its content is at 0.1 gram to 0.99 gram, or scope is from 0.5 gram to 0.9 gram, or from 0.6 gram to 0.8 gram, quantity is every gram of carrier.The amount of aluminum oxide for example can be used, and X-ray diffraction is determined.In alternate embodiment, carrier can comprise at least 0.1 gram, or is at least 0.3 gram, or is at least 0.5 gram, or the θ-aluminum oxide of at least 0.8 gram.

When carrier is used, this carrier can be with required metal impregnation to form hydrotreating catalyst.This carrier can be from 400 ℃ to 1200 ℃, or from 450 ℃ to 1000 ℃, or from the temperature range of 600 ℃ to 900 ℃ through Overheating Treatment, before with metal impregnation.In certain embodiments, hydrotreating catalyst can form to the heat treated mixture of one-tenth of carrier by the metal adding or merge the 5th to 10 families.Such formation is commonly called at the top of solid support material and covers these metals.Optionally, after in conjunction with carrier and one or more catalytic metals, described catalyzer is heat-treated, for example, in temperature from 150 ℃ to 750 ℃, or in the scope of 200 ℃ to 740 ℃ or in the temperature range of 400 ℃ to 730 ℃.Optionally, by catalyzer thermal treatment in warm air and/or oxygen-rich air in the temperature range of 400 ℃ and 1000 ℃, to remove volatile matter, make at least a portion metal of described the 5th 10 families of family to the be converted into their corresponding metal oxides.In other embodiments, this catalyzer can thermal treatment under the existence of oxygen (as air), and its temperature range is from 35 ℃ to 500 ℃, or from 100 ℃ to 400 ℃, or from 150 ℃ to 300 ℃.Thermal treatment can be carried out the time within the scope of 1 to 3 hour, and to remove most of volatile constituent, and the metal that need not transform the 5th to 10 families becomes their metal oxide form.The catalyzer of preparing by such method is commonly referred to as " not calcining " catalyzer or " being dried ".Such catalyzer can be prepared in conjunction with vulcanization process, and the metal of the 5th to 10 families is dispersed among carrier substantially.When metal that catalyzer comprises θ-alumina supporter and one or more the 5th to 10 families, this catalyzer heat-treats to form hydrotreating catalyst conventionally at the temperature of >=400 ℃.Typically, this thermal treatment is carried out at the temperature of≤1200 ℃.

Catalyzer can be in the form being shaped, for example, following one or more: dish, pellet, extrudate etc., although this is optional.The limiting examples of this shaping form comprises having cylinder symmetric and diameter from approximately 0.79 millimeter to approximately 3.2 millimeters (1/32 to 1/8 inch), from approximately 1.3 millimeters to approximately 2.5 millimeters (1/20 to 1/10 inch), or from approximately 1.3 millimeters to approximately 1.6 millimeters those in the scope of (1/20 to 1/16 inch).The shape of onesize non-cylindrical is to relate in the present invention, for example, and trilobal, quatrefoil etc.Optionally, this catalyzer have from 50-500 newton/centimetre, or 60-400 newton/centimetre, or 100-350 newton/centimetre, or 200-300 newton/centimetre, or 220-280 newton/centimetre scope in dull and stereotyped compressive strength.

Porous catalyst, comprises those with conventional pore character, all within the scope that the present invention relates to.When porous catalyst is used, the pore texture that this catalyzer can have, pore size, volume of voids, pore shape, pore surface area etc., in the scope of feature that is conventional hydrotreating catalyst, but the present invention is not limited to this.For example, this catalyzer can have the aperture of median magnitude, and so effectively hydrotreatment SCT molecule for example has the aperture of median magnitude from 30 dusts to 1000 dusts, or 50 dusts are to 500 dusts, or 60 dusts are to the catalyzer in the scope of 300 dusts.Aperture can be determined according to ASTM method D4284-07 mercury penetration method.

In specific embodiment, hydrotreating catalyst has the mean pore sizes that scope is 50 dust to 200 dusts.Or, hydrotreating catalyst have scope be 90 dusts to 180 dusts, or 100 dust to 140 dusts, or the mean pore sizes of 110 dust to 130 dusts.In another embodiment, the mean pore sizes scope of hydrotreating catalyst is 50 dust to 150 dusts.Or the scope that hydrotreating catalyst has a mean pore sizes is that 60 dusts are to 135 dusts, or from 70 dust to 120 dusts.In yet another alternative, have a hydrotreating catalyst with larger mean pore sizes and be utilized, for example, those have mean pore sizes from 180 dust to 500 dusts, or 200 dust to 300 dusts, or in the scope of 230 dust to 250 dusts.

Conventionally, the pore size distribution of hydrotreating catalyst is not activity or the selectivity in order to reach very greatly remarkable deteriorated catalyzer.For example, at hydrotreating catalyst, can have pore size distribution, wherein the aperture at least 60% hole is at 45 dusts of mean pore sizes, 35 dusts, or within 25 dusts.In certain embodiments, the scope that described catalyzer has mean pore sizes is from 50 dust to 180 dusts, or from 60 dust to 150 dusts, wherein the aperture at least 60% hole is at 45 dusts of mean pore sizes, within 35 dusts or 25 dusts.

When porous catalyst is used, this catalyzer can have, for example, pore volume >=0.3 cubic centimetre/gram, for example >=0.7 cubic centimetre/gram, or >=0.9 cubic centimetre/gram.In certain embodiments, the scope of pore volume can be from 0.3 cubic centimetre/gram to 0.99 cubic centimetre/gram, 0.4 cubic centimetre/gram to cubic centimetre/gram, or 0.5 cubic centimetre/gram to 0.7 cubic centimetre/gram.

In certain embodiments, relatively large surface area is desirable.As an example, surface-area >=60 meters squared per gram that can have at hydrotreating catalyst, or >=100 meters squared per gram, or >=120 meters squared per gram, or >=170 meters squared per gram, or >=220 meters squared per gram, or >=270 meters squared per gram; As from 100 meters squared per gram to 300 meters squared per gram, or 120 meters squared per gram to 270 meters squared per gram, or 130 meters squared per gram to 250 meters squared per gram, or in the scope of 170 meters squared per gram to 220 meters squared per gram.

Use the tar stream of hydrotreating catalyst to specified quantity of regulation and effectiveness fluid to carry out hydrotreatment and cause improved catalyst life, for example, allow hydrotreatment stage operate continuously at least 3 months, or at least 6 months, or at least 1 year and the not replacement of catalyzer in hydrotreatment district or zone of action, regeneration or upgrade.If compared with not adopting the situation of effectiveness fluid, the normally long >10 of catalyst life times, for example >=100 times, for example >=1000 times.

Hydrotreatment is under the condition existing at hydrogen, for example, (i) by the upstream binding molecule hydrogen in hydrotreatment and tar stream and/or effectiveness fluid and/or (ii), in one or more pipelines or circuit, guide molecular hydrogen to the hydrotreatment stage to carry out.Although relatively pure hydrogen molecule can be for hydrotreatment, conventionally need to utilize " processing gas ", wherein contain hydrotreatment needs enough molecular hydrogens and optional other species (for example, such as methane of nitrogen and light hydrocarbon), they generally can not cause disadvantageous effect or disturbance reponse or product.Untapped processing gas can recycle from hydrotreater effluent is separated, is generally removing unwanted impurity, for example hydrogen sulfide H ₂s and ammonia NH ₃afterwards.This processing gas can contain the hydrogen molecule of volume fraction >=approximately 50%, and for example, volume fraction >=approximately 75%, based on the cumulative volume of processing gas that is directed to the hydrotreatment stage.

Optionally, the feed rate scope of hydrotreatment stage molecular hydrogen is for approximately from 300SCF/B (standard cubic feet per barrel) (53S m ³/ m ³) to 5000SCF/B (890S m ³/ m ³), wherein B represents the bucket of tar stream.For example, hydrogen molecule can be 1000SCF/B (178S m in scope ³/ m ³) to 3000SCF/B (534S m ³/ m ³) provide.At the effectiveness fluid of regulation, under the regulation hydrotreating catalyst of molecular hydrogen and catalysis effective quantity exists, under catalytic hydroprocessing condition, tar stream is carried out to hydrotreatment and produce the product of hydrotreatment, it for example comprises, the SCT of upgrading.The example of suitable catalytic hydroprocessing condition will illustrate in greater detail below.The present invention is not limited to these conditions, and this description and do not mean that will get rid of other and hydroprocessing condition in relevant more wide region of the present invention.

This hydrotreatment is carried out conventionally under hydrocracking condition, for example, carrying out under following one or more condition: the hydrocracking (comprising selective hydrogenation cracking) of regulation tar stream, hydrogenization, hydrogen treatment, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), hydroisomerization or Hydrodewaxing.Hydrotreatment reaction can for example be positioned at at least one, in the hydrotreatment stage, in the container in pyrolysis phase and separation phase downstream or region, carries out.The tar stream of regulation conventionally in container or region with hydrotreating catalyst, under effectiveness fluid and molecular hydrogen exist, contact.Catalytic hydroprocessing condition can comprise, for example thinner-the tar stream of combination is exposed to from 50 ℃ to 500 ℃ or from 200 ℃ to 450 ℃ or from 220 ℃ to 430 ℃ or from the temperature range of 350 ℃ to 420 ℃ close to molecular hydrogen and hydrotreating catalyst.For example, from 300 ℃ to 500 ℃, or 350 ℃ to 430 ℃, or can be utilized in the temperature range of 360 ℃ to 420 ℃.When the utilize>=temperature of approximately 425 ℃ with comprise (i) cobalt and molybdenum and (ii) under the pressure of porous alumina-base carrier at>=approximately 70 bar (definitely) time, C in hydrotreater ₂₊compound significantly increases the transformation efficiency of methane.The liquid hourly space velocity (LHSV) of the thinner-tar stream of combination is generally 0.1h ^-1to 30h ^-1, or 0.4 to 25h ^-1, or 0.5h ^-1to 20h ^-1scope in.In some embodiments, LHSV is 5h at least ^-1, or 10h at least ^-1, or 15h at least ^-1.Molecular hydrogen dividing potential drop in hydrotreatment process is generally 0.1 MPa to 8 MPa or 1 MPa to 7 MPa, or 2 MPa to 6 MPas, or 3 MPas are to the scope of 5MPa.In some embodiments, molecular hydrogen dividing potential drop is≤7 MPas, or≤6 MPas, or≤5 MPas, or≤4 MPas, or≤3 MPas, or≤2.5 MPas, or≤2 MPas.The condition of hydrotreatment can comprise, for example following one or more: temperature range is at 300 ℃ to 500 ℃, pressure range is at 15 bar (definitely) to 135 bar, and the scope of space velocity is 0.1 to 5.0, and molecular hydrogen wear rate is approximately 50 standard cubic meter/cubic meter (S m ³/ m ³) to about 450S m ³/ m ³(300SCF/B to 2500SCF/B).In one or more embodiments, hydroprocessing condition comprises following one or more: 380 ℃ to 430 ℃ of temperature ranges, pressure range 20 bar (definitely) are to 120 bar (definitely), or 20 bar (definitely) to 100 bar (definitely), or 21 bar (definitely) to 81 bar (definitely), space velocity (LHSV) scope is 0.2 to 1.0, and molecular hydrogen wear rate is about 70S m ³/ m ³to about 265Sm ³/ m ³(400SCF/B to 1500SCF/B).When using the catalyzer of regulation while operating under these conditions, normally >=25.0%, this is take weight as basis for the transformation efficiency of TH hydrocracking, for example, and >=50.0%.

One embodiment of the invention are schematically showed in Fig. 1.To be provided and be comprised (i) tar by pipeline 1, the effectiveness fluid as the raw material of SCT and (ii) providing by pipeline 7 be directed to hydrotreating reactor 2 for carry out hydrotreatment under the hydroprocessing condition of one or more regulations by pipeline 8.Molecular hydrogen is processed gas and is introduced reactor 2 by one or more pipeline (not shown).The effluent of reactor is directed to separation phase 4 by pipeline 3.Total product liquid of a part of reactor effluent (from total liquid phase effluent of hydrotreater a part) is separated and deflects from separation phase 4 by pipeline 7 and be used as effectiveness fluid.Comprise, for example, molecular hydrogen, the waste gas of methane and hydrogen sulfide is Fen Li and deflect from by pipeline 6 separation phase 4 from reactor effluent.By pipeline 5, deflect from and comprise, for example C ₅₊the product of the hydrotreatment of hydrocarbon.

In certain embodiments, need to be by SCT hydrotreatment to reach useful blending characteristic and/or relatively low viscosity, for example≤20cSt, for example≤15cSt or≤viscosity of 10cSt.For accomplishing to use like this cobalt-molybdenum catalyzer of conventional sulfidation-oxidation aluminium load, can under existing, the effectiveness fluid of one or more regulations, under catalytic hydroprocessing condition, the SCT of one or more regulations be carried out to hydrotreatment, described catalytic hydroprocessing condition is included in temperature 375 ℃ to 425 ℃ scopes, for example 385 ℃ to 415 ℃ scopes; Pressure at 45 bar (definitely) to the scope of 135 bar (definitely), if 60 bar (definitely) are to 90 bar (definitely); Molecular hydrogen treatment rate (based on tar charging) is at 150S m ³/ m ³to 1200S m ³/ m ³in the scope of (840SCF/B to 6700SCF/B), as at 180S m ³/ m ³to 450S m ³/ m ³in the scope of (1000SCF/B to 2500SCF/B); In 0.1 to 2.0 scope, for example 0.25 to 0.50 LHSV is based on combined feed total feed (tar+effectiveness fluid) with LHSV.Observed C _4-the generation of by product to hydrotreatment during SCT expose temperature sensitive, and under defined terms when temperature is greater than approximately 425 ℃ the generation of these by products can increase.Although can be from the hydrotreater effluent circulation after separating of the tarry cut of hydrotreatment (optionally) for the effectiveness fluid of a little embodiments, this be requirement.In certain embodiments, adopt fresh effectiveness fluid, as have and the effectiveness fluid of the basic same composition of supplementary effectiveness fluid.Effectiveness fluid under these conditions: but tar ratio 0.05:1.0 to 2.0:1.0, for example 0.10:1.0 to 1.0:1.0, or 0.1:1.0 to 0.5:1.0.

Following embodiment further describes the aspect of certain embodiments of the invention.The present invention is not limited to these embodiment, and these embodiment do not mean that and get rid of more other embodiment within wide region in the present invention.

Embodiment 1

A kind of 3/8 inch of SS stainless steel tube (it has the cumulative volume of 20 cubic centimetres) of 56 cm long is used as reactor.In experimentation, 34 centimetres of this centres are maintained under the nearly thermostat temperature of 400 ℃.The volume of hot-zone is 14 cubic centimetres.The 80 order silica gel that pack 20 cubic centimetres of commercially available nickel molybdenum oxide hydrotreating catalysts (RT-621) on alumina supporter and 5 cubic centimetres in whole reactor into are used for Package gaps space.

With reference to Fig. 1, by pipeline 8 to the raw material that 100.0wt% is provided in reactor 2.This raw material contains by pipeline 1 introduces the SCT (having similar characteristic to SCT-1) of the 60.0wt% of technique and 40.0% effectiveness fluid, this effectiveness fluid becomes a part for the total liquid phase effluent of this reactor, it is introduced into pipeline 8 by pipeline 7, and this weight percentage is the weight based on described raw material.This is corresponding to the effectiveness fluid in 0.66 raw material and the weight ratio of tar stream.Raw material passes through pipeline 8 with 7cm ³the speed of/hr is transported in reactor.Molecular hydrogen is supplied to by conduit (not shown) and is delivered to reactor 2 with the speed of per minute 26 standard cubic centimeters (sccm), reactor is moved to 80 days under these conditions continuously, without significantly pressure drop (in initial drop approximately within 10.0%).

Hydroconversion condition in reactor 2 comprises approximately 70 bar (1000psig) pressure, 400 ℃ of temperature, the molecular hydrogen wear rate rate 200m based on raw material ³/ m ³(1100SCFB), and 0.44 space velocity (LHSV).Reactor effluent comprises gas phase and liquid phase, and liquid phase is total product liquid.The amount of total product liquid is about the 95.0wt% of total liquid feeding in total reactor.

The effluent of reactor 2 is directed to separation phase 4 by conduit 3.The part of the liquid phase effluent of reactor (effluent that comprises reactor described in 40.0 % by weight, based on the weight of reactor effluent) is used as effectiveness fluid from being deflected from the stage 4 through conduit 7.Stage 4 is also used to separate the C containing the 56.0wt% quantity of having an appointment from reactor effluent ₅₊the product of the hydrotreatment of hydrocarbon, based on the weight of described reactor effluent.Stage 4 is to be used to separate vapor product " waste gas " 6 from reactor effluent, and the molecular hydrogen that this vapor product comprises about 1.1wt% hydrogen sulfide and about 1.1wt%, based on the weight of reactor effluent.Waste gas also contains a small amount of other gas (as methane), obtains 100.0% total reactor effluent, this weight based on described raw material.

The liquid and gas of reactor effluent and the composition of raw material are analyzed by ordinary method.SCT has 1.11g/cm ³density, and the nitrogen of the sulphur that comprises 2.2wt% and 1600ppmw, this weight based on SCT.The product of this hydrotreatment comprises C ₅₊the nitrogen of hydrocarbon and 800ppmw.This hydrogenation products has 1.01g/cm ³density (at 15 ℃), the viscosity of 8.8cSt at 50 ℃, and mixed number I _napproximately 50.Reactor pressure depreciation is similar to 0.1 bar.

The product of this hydrotreatment only contains the sulphur of 0.4wt%.The boiling spread of raw material is 500 °F-650 °F (260 ℃-345 ℃) light gas oils of 25wt%, 650 °F-1050 °F (345 ℃-565 ℃) heavy gas oils of 50%, with 25% 1050 °F+(565 ℃+), this weight based on described raw material.The boiling spread of product is the C of 10wt% _12-400 °F-650 °F (205 ℃-345 ℃) light gas oils of 40%, 650 °F-1050 °F (345 ℃-565 ℃) heavy gas oils of 42%, and 8% 1050 °F+(565 ℃+), the weight of this product based on described hydrotreatment.

The method is useful, this be because it by its acidity, high viscosity, high-density tar stream is converted into more low viscosity, less dense, the logistics of <0.5wt% sulphur and have more perfect characteristic for being blended into final finished product fuel.

Embodiment 2

Repeat the experiment of embodiment 1, difference is the amount of the recycling part that is increased in Liquid-phase reactor effluent total in conduit 7, to produce the raw material that comprises 80.0wt% liquid product and 20.0wt%SCT, and this weight based on described raw material.This is corresponding to effectiveness fluid: the weight ratio of tar stream is at 4:1.In operation, reactor 2 shows the pressure decreased of increase after only going into operation in several hours.Go into operation after fortnight, voltage drop value is increased to and is greater than 20 bar (>300psi) and operates and must stop.

Embodiment 3

Repeat the experiment of embodiment 2, difference is that raw material packet contains the SCT of the total liquid product of 91.0wt% and 9.0wt%, this weight based on described raw material.This is corresponding to effectiveness fluid: the weight ratio of tar stream is at 10:1.In operation, observe immediately the reactor pressure decrease of increase.Go into operation after 12 hours, voltage drop value is increased to and is greater than 20 bar (>300psi) and operates and must stop.

These embodiment show that increasing effectiveness fluid (total Liquid-phase reactor effluent recirculation) ratio is fallen and worsened operability by increase reactor pressure decrease value astoundingly.For example, although do not wish to be bound by any theory, but believe that the relatively high effectiveness fluid content of utilization (, relatively large total product liquid recirculation) causes higher pressure drop, this is due to 565 ℃ of raw material ₊between the minimum solvability molecule of finding in cut due to uncompatibility.Believe that the raw material that contains 100wt% tar can stop up reactor, thereby this is because the bituminous matter gathering in catalyst pores produces the composition with poor quality transmission and long residence time.Under these conditions, the mutual thermal response of bituminous matter heat form coke.These embodiment show that the liquid product of the reactor effluent that reclaims small amount can realize the stable operation without stopping up.

Have been found that and under the weight ratio of relatively high effectiveness fluid and tar stream, operate the increase that can cause pressure drop.In order to use the equipment of smaller szie in the hydrotreatment stage, for lower pressure drop, be necessary.When raw material comprises that SCT is as the part of total liquid product of tar component and reactor effluent during as effectiveness fluid, when the ratio of total liquid product and SCT in raw material be≤4.0, for example, in 0.05:1.0 arrives the scope of 3.5:1.0, as 0.10:1.0 to 2.0:1.0,0.2:1.0 is during to 2.0:1.0 or 0.2:1.0 to 1.0:1.0, and the relatively low Pressure Drop hold-time is greater than 10 days.

All patents, test procedure, and the alternative document quoted herein, comprise priority document, is allowed to introduce the application.

Although the present invention is specifically described with exemplary form, should be understood that various other modifications will be apparent, and can be easily by those of ordinary skill in the art, be completed not departing from spirit of the present invention and scope of the disclosure.Therefore, the invention is not restricted to described in example and detailed content, these claims have been interpreted as covering all equivalences that it may occur to persons skilled in the art that and have replaced.

The present invention lists numerical lower limits and numerical upper limits, and the scope that is limited to the upper limit from is down all expected.

Claims

1. a hydroconversion process, comprising:

(e) under catalytic hydroprocessing condition at molecular hydrogen and effectiveness fluid: tar weight ratio is exposed at least a portion tar stream at least one hydrotreating catalyst to produce hydrotreater effluent under the effectiveness fluid of 0.05 to 3.5 scope exists; With

(f) from hydrotreater effluent, isolate liquid phase, comprise >=90.0wt% of described liquid phase has the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on the weight of hydrotreater effluent, wherein said effectiveness fluid comprises the liquid phase of the separation of quantity >=90.0wt%, based on the weight of effectiveness fluid.

2. method according to claim 1, wherein said effectiveness fluid comprise by NMR, measure >=the aromatics carbon of 60.0wt%, based on the weight of effectiveness fluid.

3. method according to claim 1 and 2, comprise >=90.0wt% of wherein said liquid phase has the molecule of the hydrotreater effluent of atmospheric boiling point >=65.0 ℃, based on the weight of hydrotreater effluent.

4. according to the method described in claim 1-3 any one, comprise >=90.0wt% of wherein said liquid phase has the molecule of the hydrotreater effluent of atmospheric boiling point >=100.0 ℃, based on the weight of hydrotreater effluent.

5. according to the method described in claim 1-4 any one, comprise >=90.0wt% of wherein said liquid phase has the molecule of the hydrotreater effluent of atmospheric boiling point >=150.0 ℃, based on the weight of hydrotreater effluent.

6. according to the method described in claim 1-5 any one, the density of wherein said effectiveness fluid at 15 ℃ is less than the density of described tar stream at 15 ℃.

7. according to the method described in claim 1-6 any one, the hydrocarbon of wherein said the first mixture comprises following one or more: petroleum naphtha, gas oil, vacuum gas oil, wax residual oil, long residuum, residual oil mixed compound or crude oil.

8. according to the method described in claim 1-7 any one, following one or more that wherein said the first mixture comprises weight >=50.0wt% based on the first mixture: petroleum naphtha, gas oil, vacuum gas oil, wax residual oil, long residuum, residual oil mixed compound or crude oil.

9. according to the method described in claim 1-8 any one, wherein said pyrolysis step (b) is steam cracking.

10. according to the method described in claim 1-9 any one, wherein said tar stream comprises that (i) >=10.0wt% is not bitum the have molecule of atmospheric boiling point >=565 ℃ and the metal of (ii)≤1000.0ppmw, the weight of this weight percentage based on this tar stream.

11. according to the method described in claim 1-10 any one, wherein said hydroprocessing condition comprises following one or more: temperature at 350 ℃ within the scope of 450 ℃, pressure is within the scope of 20 bar to 100 bar, space velocity (LHSV) is within the scope of 0.2-4.0, and hydrogen rate of consumption is at 50S m ³/ m ³to 450S m ³/ m ³in scope.

12. according to the method described in claim 1-11 any one, and wherein said effectiveness fluid comprises isolated liquid phase in the step (f) of quantity >=99.0wt%, based on the weight of effectiveness fluid.

13. according to the method described in claim 1-12 any one, wherein the effectiveness fluid of step (e): tar stream weight ratio is in 0.10 to 3.0 scope.

14. according to the method described in claim 1-13 any one, wherein the effectiveness fluid of step (e): tar stream weight ratio is in 0.2 to 3.0 scope.

15. according to the method described in claim 1-14 any one, further comprises the liquid phase that deflects from second section from the method, and this second section is used to produce fuel.

16. according to the method described in claim 1-15 any one, further comprise provide supplement effectiveness fluid to step (d) to replace the effectiveness fluid of at least a portion from a part of liquid phase in step (g), supplement effectiveness fluid and comprise aromatic substance and there is ASTM D8610% and heat up in a steamer a little >=60.0 ℃ and 90% and heat up in a steamer a little≤350.0 ℃.

17. 1 kinds of hydroconversion process, comprising:

(c) separating tar logistics from described the second mixture, the molecule that wherein said tar stream comprises atmospheric boiling point >=290 in 90.0wt% the second mixture ℃;

(e) under catalytic hydroprocessing condition, under molecular hydrogen and the existence of effectiveness fluid, at least a portion tar stream is exposed to at least one hydrotreating catalyst to produce hydrotreater effluent, wherein effectiveness fluid: tar weight ratio is in 0.05 to 3.5 scope;

18. methods according to claim 17, comprise >=90.0wt% of wherein said liquid phase has the molecule of the hydrotreater effluent of atmospheric boiling point >=65.0 ℃, based on the weight of hydrotreater effluent.

19. according to the method described in claim 17 or 18, and comprise >=90.0wt% of wherein said liquid phase has the molecule of the hydrotreater effluent of atmospheric boiling point >=100.0 ℃, based on the weight of hydrotreater effluent.

20. according to the method described in claim 17-19 any one, and comprise >=90.0wt% of wherein said liquid phase has the molecule of the hydrotreater effluent of atmospheric boiling point >=150.0 ℃, based on the weight of hydrotreater effluent.

21. according to the method described in claim 17-20 any one, and comprise >=90.0wt% of wherein said heavy liquid has the molecule of the liquid phase of atmospheric boiling point >=250.0 ℃.

22. according to the method described in claim 17-20 any one, and comprise >=90.0wt% of wherein said heavy liquid has the molecule of the liquid phase of atmospheric boiling point >=350.0 ℃.

23. according to the method described in claim 17-22 any one, also comprises from the method the light weight fluid of second section is deflected from.

24. 1 kinds of continuous hydroconversion process, comprising:

25. continuous hydroconversion process according to claim 24 wherein can not exceed initial drop more than 300% through the pressure drop of exposing step (d) after operate continuously 100 hours.