CN103764799B

CN103764799B - By hydrotreating upgrading hydrocarbon thermal decomposition product

Info

Publication number: CN103764799B
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: 2016-08-24
Anticipated expiration: 2032-08-31
Also published as: EP2751234A2; EP2751234B1; CA2843517A1; CN103764799A; WO2013033590A3; WO2013033590A2

Abstract

The present invention relates to the thermal decomposition product of upgrading, from the method for upgrading of the product that hydrocarbon pyrolysis obtains, the equipment used in the method, and the purposes of the thermal decomposition product of upgrading.The logistics containing tar reclaimed from pyrolysis effluent is mixed with effectiveness fluid and carries out hydrotreating subsequently.

Description

By hydrotreating upgrading hydrocarbon thermal decomposition product

Cross reference to related applications

This application claims and enjoy the U.S. Provisional Application 61/529 submitted on August 31st, 2011 565, on August 31st, 2011 submit to U.S. Provisional Application 61/529588 and 2012 6 The rights and interests of the U.S. Provisional Application 61/657299 that the moon 8 was submitted to and priority, entire contents It is incorporated herein.

Invention field

The present invention relates to the thermal decomposition product of upgrading, the product upgrading obtained will be pyrolyzed from hydro carbons heat Method, for the equipment of these methods, with the purposes of the thermal decomposition product of upgrading.

Background of invention

Pyrolytic process, such as steam cracking can be used for convert saturated hydrocarbons be high value-added product such as Light olefin, such as, ethylene and propylene.In addition to the product that these are useful, hydrocarbon pyrolysis may Also significant amount of low value-added product, such as steam cracker tar (" SCT ") are produced.

The SCT method for upgrading relating to Conventional catalytic hydrotreating is limited to the mistake of significant catalyst Live.The method can be within the temperature range of 250 DEG C to 380 DEG C and at 5400 kPas to 20500 KPa pressure limit in operate, this process can use containing in Co, Ni or Mo The catalyst of one or more；But significantly catalyst coking can be observed.Although catalysis Agent coking can be by the hydrogen partial pressure in rising, minimizing space velocity, and at 200 DEG C extremely Operating process in the temperature controlling range of 350 DEG C is reduced；But SCT under these conditions Hydrotreating is not required, this is because the increase of hydrogen dividing potential drop will make this process the most economical Property, due to hydrogen and the increase of equipment cost, and due to the hydrogen dividing potential drop increased, the sky of reduction Between speed, and reduce temperature range 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 includes:

A () provides the first mixture, it comprises weight >=10.0wt%'s based on the first mixture Hydrocarbon；

B () is pyrolyzed the first mixture and comprises >=the C of 1.0wt% to produce₂Unsaturates and >= Second mixture of 0.1wt% tar, this percetage by weight weight based on the second mixture；

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

D () provides effectiveness fluid, this effectiveness fluid includes >=40.0wt% aromatic carbon, based on effectiveness The weight of fluid；

E () incites somebody to action at least one under the conditions of catalytic hydrogenation treatment in the presence of molecular hydrogen and effectiveness fluid Part tar stream is exposed at least one hydrotreating catalyst and flows out to produce hydrotreater Thing, wherein effectiveness fluid: tar weight ratio is in the range of 0.05 to 3.5；With

F () isolates liquid phase from hydrotreater effluent, described liquid phase comprises >=90.0wt% There is the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on hydrotreater stream Go out the weight of thing,

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

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

D () provides effectiveness fluid, this effectiveness fluid include being measured by NMR >=40.0wt% virtue Race's carbon, weight based on effectiveness fluid；

E () incites somebody to action at least one under the conditions of catalytic hydrogenation treatment in the presence of molecular hydrogen and effectiveness fluid Part tar stream is exposed at least one hydrotreating catalyst and flows out to produce hydrotreater Thing, wherein said effectiveness fluid: tar weight ratio is in the range of 0.05 to 3.5；

F () isolates liquid phase from hydrotreater effluent, described liquid phase comprises >=90.0wt% There is the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on hydrotreater stream Go out the weight of thing；

G () isolates light liquids and heavy liquid, wherein said heavy liquid from described liquid phase There is the molecule in the liquid phase of atmospheric boiling point >=300 DEG C containing 90wt%；

Wherein said effectiveness fluid includes that quantity is the >=light liquids of the separation of 90.0wt%, base Weight in effectiveness fluid.

In still another embodiment, the present invention relates to a kind of hydroconversion process continuously, should Method includes:

C () provides effectiveness fluid, this effectiveness fluid include being measured by NMR >=40.0wt% virtue Race's carbon, weight based on effectiveness fluid；

(d) under the conditions of operation persistent period >=24 hour catalytic hydrogenation treatment, at effectiveness fluid With 50.0S m³/m³To 890.0S m³/m³At (i) LHSV about 1.0 in the presence of molecular hydrogen ×10^-1To in the range of about 10.0, (ii) temperature the scope of 300.0 DEG C to 500.0 DEG C, (iii) pressure is in the range of 25 bars (definitely) to 100 bars (definitely), and (iv) effectiveness Fluid: tar stream weight rate is by Jiao based on the second mixture in the range of 0.1 to 3.5 The tar of weight of oil >=50.0wt% the second mixture is exposed at least one hydrorefining catalyst Agent, to produce hydrotreater effluent；With

E () isolates liquid phase from hydrotreater effluent, described liquid phase comprises >=95.0wt% There is the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on hydrotreater stream Going out the weight of thing, wherein said effectiveness fluid includes the liquid phase of the separation of quantity >=99.0wt%, base Weight in effectiveness fluid.

In certain embodiments, the present invention relates to, compared with tar charging, there is improvement and blend spy Property the tar of hydrotreating, such as, the tar of this hydrotreating can be with other containing heavy hydrocarbon Logistics blend and there is less asphaltene precipitation, compared to the tar using non-hydrotreating Situation.Therefore the tar of this hydrotreating be suitable as blending stock, such as, for upgrading width The relatively low value heavy hydrocarbon of scope.

Accompanying drawing explanation

Fig. 1 schematically illustrates embodiment of the present invention, wherein in the hydrotreating stage Downstream utilizes separation level to come with the Overall Liquid product separating and circulating a part of reactor effluent As effectiveness fluid.

Detailed Description Of The Invention

The present invention is based partially on following discovery: catalyst coking can comprise significant amount of list By this SCT of hydrotreating in the presence of the effectiveness fluid of ring or polynuclear aromatic compound Can be reduced.Being different from traditional SCT hydrotreating, this process can be relative to aromatic hydrocarbons Hydrogenization adds operation under the temperature and pressure that being hydrocracked is reacted needed for being conducive to.Send out The liquid phase effluent of existing a part of hydrotreater can circulate and be used as to make effectiveness fluid.

Term " SCT " refers to that (a) has one or more aromatic kernel and optional (b) non-aromatic thing Matter and/or the hydrocarbon mixture of non-hydrocarbon molecule, this mixture comes from hydrocarbon pyrolysis and has boiling point model Enclose >=about 550 °F (290 DEG C), such as, the SCT molecule of >=90.0wt% have atmospheric boiling point >= 550°F(290℃).SCT can include weight based on SCT, such as, >=50.0wt%, >= The hydrocarbon molecule (including their mixture and their aggregation) of 75.0wt%, >=90.0wt%, Described hydrocarbon molecule has (i) one or more aromatic kernel and (ii) >=about C₁₅Molecular weight.

Have been found that SCT includes significant amount of heavy tar (" TH ").For this explanation In book and claims, term " heavy tar " refers to the thermal decomposition product of hydrocarbon, this TH There are atmospheric boiling point >=565 DEG C and weight based on this product contains >=5.0% and has multiple aromatics The molecule of core.This TH is typically solid at 25.0 DEG C and is commonly included at 25.0 DEG C insoluble The SCT fraction (" conventional extraction into heptane ") of the pentane in 5:1 (volume: volume) ratio: SCT. This TH can include high molecular weight molecules (such as MW >=600), such as asphalitine and other macromolecule Amount hydrocarbon.Term " asphalitine " is defined as heptane insolubles, and measures according to ASTM D3279. Such as, this TH can comprise >=the 10.0wt% high molecular weight molecules that contains aromatic kernel, its can by with Under one or more: the alkane of (i) relatively low molecular weight and/or alkene, such as, C₁To C₃ Alkane and/or alkene, (ii) C₅And/or C₆Naphthenic ring, or (iii) thiphene ring.In general, The carbon atom of this TH of >=60.0wt% is comprised in one or more aromatic kernel, based on this TH Carbon atom weight, such as, in the range of 68.0wt% to 78.0wt%.While not wishing to Fettered by any theory or model, it is also believed that this TH forms the gathering with relatively flat form Thing, this is due to the result of the Van der Waals'attractive force between TH molecule.This TH aggregation Large scale, it can be such as in their maximum dimension, ten nanometers to hundreds of nanometer (" nm ") In the range of, under the conditions of catalytic hydrogenation treatment, cause low aggregation mobility and diffusibility. In other words, conventional TH converts impaired in serious quality transmission restriction, and it causes TH to convert The high selectivity of coke.Have been found that SCT combines with effectiveness fluid and decompose this aggregation Become single molecule, such as, its in their maximum dimension≤5.0nm and molecular weight exist In the range of about every mole 200 grams Dao every mole 2500 grams.By causing, the TH's of SCT is bigger for this Mobility and diffusibility, thus cause the catalyst contact time shortened under hydroprocessing conditions With the less conversion to coke.Result is, SCT converts can be at relatively low pressure, such as, Running under 500psig to 1500psig (34.5-103.4 bar gauge pressure), this will significantly reduce Cost and complexity, relative to the hydrotreating of higher pressure.It is also an advantage of the present invention that This SCT is not the light hydrocarbon making to produce in certain embodiments of overcracking, such as, C₄Or lighter material, less than about 5.0wt%, it causes the independence of polycyclic compound to form, With reduce further the consumption of hydrogen in hydroprocessing processes.

In certain embodiments, the present invention relates to a kind of hydrotreating tar such as hydrotreating Steam-cracked tar, it has the viscosity of improvement and blends characteristic.In these embodiments, The tar of hydrotreating can pass through in the presence of effectiveness fluid under the conditions of catalytic hydrogenation treatment Tar being carried out catalytic hydrogenation treatment and obtains, this catalytic hydrogenation treatment condition is included in temperature Spend 375 DEG C to 425 DEG C scopes, such as 385 DEG C to 415 DEG C scopes；Pressure is at 45 bars (absolutely Right) in the range of 135 bars (definitely), such as 60 bars (definitely) to 90 bars (definitely)；Molecular hydrogen Processing speed (feeding based on tar) is at 150S m³/m³To 1200S m³/m³(840SCF/B To 6700SCF/B) in the range of, as at 180S m³/m³To 450S m³/m³(1000SCF/B To 2500SCF/B) in the range of；With LHSV in the range of 0.1 to 2.0, such as 0.25 LHSV to 0.50 is based on combined feed (tar+effectiveness fluid).This effectiveness fluid can be at hydrogenation Reason device effluent circulation (optionally after separating the tarry distillate of hydrotreating), or from outward Source, portion obtains.This catalyst it may be that such as, the cobalt of the alumina load of conventional sulfuration- Molybdenum catalyst.Have been observed that the tar producing hydrotreating under these conditions may result in less Undesirable side-product, it has molecular weight less than or equal to C4 (C_4-Side-product).

SCT parent material is different from the hydrocarbon mixture of other of a relatively high molecular weight, such as crude oil Residue (" residual oil "), usual with other including reduced crude and decompression residuum, such as, The logistics run in oil and petrochemistry are processed.Pass through C¹³The aromatics of the SCT that NMR measures Carbon content is significantly greater than the aromatic carbon content of Residual oil.Such as, in SCT, aromatic carbon content is typically More than 70.0wt%, the aromatic carbon content in residual oil is typically smaller than 40.0wt%.Clear in order to study Some differences between Chu's residual oil and SCT, two kinds of representative SCT samples and three kinds have table slag The performance of the selection of oil samples is as shown in table 1 below.The signal portion of SCT asphalitine has normal pressure Boiling point is less than 565 DEG C.Such as, in SCT1, only the asphalitine of 32.5wt% has normal pressure boiling Point is more than 565 DEG C.This is not meant to the situation of decompression residuum, the Colophonium of the most substantially 100% Atmospheric boiling point >=565 DEG C of matter.Even if solvent extraction is faulty technical process, result shows Asphalitine in decompression residuum, great majority are to have heavier point more than 565 DEG C of atmospheric boiling point Son.When with under conditions of those of decompression residuum are roughly the same, experience heptane solvent extraction Time, the asphalitine obtained from SCT contains bigger percentage ratio (on the basis of weight) and has normal pressure < molecule of 565 DEG C, when for decompression residuum for boiling point.The metal that exists for and containing The relative quantity of nitrogen compound, SCT is also different from residual oil.In SCT, the total amount of metal is≤ 1000.0ppmw (parts per million, weight), weight based on SCT, such as ,≤100.0 Ppmw, such as≤10.0ppmw.During present in SCT, total nitrogen is generally less than crude oil decompression residuum The nitrogen content existed.

Two kinds of representative SCT samples and three kinds have the performance such as following table of the selection of table residual oil sample Shown in.

Table 1

* N.M.=is unmeasured

Compared with residual oil in SCT aliphatic carbons quantity and carbon number amount is the most more present in the long-chain Low.Although the total carbon at SCT is the most slightly lower and oxygen content (weight basis) aspect and residual oil Similar, but the metal in SCT, hydrogen, and nitrogen content (weight basis) scope are at a fairly low. At kinematic viscosity generally >=100cSt at 50 DEG C of SCT, or >=1000cSt, even if phase Quantity is had >=SCT of the atmospheric boiling point of 565 DEG C is much smaller than slag oil condition.

The product that SCT is pyrolyzed typically by hydrocarbon obtains.This method for pyrolysis includes, such as, Heat pyrolysis, such as, utilize the hot pyrolytic process of water.A kind of such pyrolytic process, steam cracking, Will be described in greater detail below.The present invention is not limited to steam cracking, and this description is not Mean to get rid of in the more broad range of the present invention, use other pyrolytic process.

SCT is obtained by pyrolysis

The pyrolysis oven that conventional steam cracking is utilized has two main section: convection section and spoke The section of penetrating.Raw material (the first mixture) enters the convection section of this stove, wherein by the first mixture Hydrocarbon component by with from radiant section hot flue gases mediate contact and by with the first mixture The directly contact of middle steam component carries out heating and vaporizing.The hydrocarbon mixture of steam-vaporization then by Introduce radiant section and cracking reaction occurs wherein.From pyrolysis oven, the second mixture is guided out Coming, the second mixture includes the product that obtains from the pyrolysis of the first mixture and the first mixture Any unreacted component.At least one separation phase is usually located at the downstream of pyrolysis oven, this point It is used for separating following one or more from the second mixture from the stage: light olefin, SCN, Unreacted hydrocarbon component etc. in SCGO, SCT, water and the first mixture.This separation phase can include, Such as, main fractionating tower.Generally, cooling stage, typically directly quenching or indirect heat exchange are positioned at Between pyrolysis oven and separation phase.

In one or more embodiments, SCT as in one or more pyrolysis ovens, example As, in one or more steam cracker furnace, the product of pyrolysis obtains.In addition to SCT, this Stove generally produces (i) gas-phase product, such as acetylene, and ethylene, propylene, one or more in butylene, (ii) liquid product, it comprises one or more C₅₊Molecule and its mixture.Liquid product Generally enter into separation phase, such as, main fractionator in the lump, for separate following one or Multiple: (a) include steam cracking naphtha (" SCN ", such as, C₅-C₁₀Kind) and steam The overhead fraction of cracked gasoil (" SCGO "), this SCGO include weight based on SCGO >= 90.0wt% atmospheric boiling point molecule in the range of about 400 °F to 550 °F (200 DEG C to 290 DEG C) (such as, C₁₀-C₁₇Kind), and the bottom fraction that (b) is containing >=90.0wt%SCT is (such as burnt Oil logistics), weight based on this bottom fraction, this SCT has boiling point about >=550 °F (290 DEG C) And it is >=about C including molecular weight₁₅Molecule and mixture.

Charging in this pyrolysis oven is the first mixture, and this first mixture contains >=10.0wt% Hydrocarbon, weight based on described first mixture, such as, >=15.0wt%, such as >=25.0wt%, >=50.0wt%, such as >=0.65wt%.Although hydro carbons can include, such as, a kind of or many The light hydrocarbon such as methane planted, ethane, propane, butane etc., it is also possible to use bag in the present invention Including the first mixture of significant amount of hydrocarbon with higher molecular weight, this is the pyrolysis due to these molecules More SCT compared with the pyrolysis of low molecular weight hydrocarbon would generally be produced.As an example, Ke Yiyou Make sharply whole first mixture being fed to multiple pyrolysis oven comprise >=1.0wt% or >= 25.0wt% at ambient temperature and under atmospheric pressure hydrocarbon in liquid phase, based on the first mixture Weight.

First mixture can comprise diluent, such as, following one or more further: Nitrogen, water etc., such as, and the diluent of >=1.0wt%, quality based on described first mixture, Such as >=25.0wt%.When described pyrolysis is steam cracking, this first mixture can pass through hydrocarbon Class and the vapoury diluent of bag, such as with every kilogram of hydrocarbon of 0.1-1.0 kilogram of steam, or The ratio of 0.2-0.6 every kilogram of hydrocarbon of kilogram of steam, combines and produces.

In one or more embodiments, the hydrocarbon of described first mixture comprises >=10.0wt%, Such as >=50.0wt%, such as >=90.0wt% (weight based on hydrocarbon) below one or more: Petroleum, gas oil, vacuum gas oil (VGO), wax-like residual oil, reduced crude, residual oil mixed compound, Or crude oil；Including containing those of >=about 0.1wt% asphalitine.Suitably crude oil includes, example As, high-sulfur virgin crude, as rich in polynuclear aromatic compound.Optionally, described The hydrocarbon of one mixture includes sulfur, and such as, >=0.1wt% sulfur, based in described first mixture The weight of hydrocarbon.Such as, >=1.0wt%, such as in about 1.0% to about 5.0% weight range. Optionally, the sulfur-containing molecules of this first mixture at least one of, such as, >=10.0wt% The sulfur-containing molecules of the first mixture, comprise at least one aromatic ring (" aromatics sulfur ").As (i) Hydrocarbon in first mixture is to comprise >=crude oil of 0.1wt% aromatics sulfur or crude oil fractions and (ii) heat When solution is steam cracking, then SCT contains notable quantity and derives from aromatics sulfur in the first mixture Sulfur.Such as, in SCT sulfur content higher than the hydrocarbon constituent content in the first mixture be about 3 to 4 times, on the basis of weight.

In particular embodiments, the hydrocarbon of the first mixture includes following one or more: Crude oil and/or one or more crude oil fractions, obtain from normal pressure pipe still such as those which Which (" VPS ") that (" APS ") and/or electron tubes type distilling apparatus obtain a bit.By crude oil and / or the Optional desalination that includes at the first mixture of its fraction.First mixture utilizes The example of crude oil fractions be by will be from crude separation APS bottom fraction with pass through APS subsequently The VPS of bottom fraction processes and produces.

Optionally, this pyrolysis oven has at least one gas liquid separation device being integrated with (sometimes It is referred to as flash tank or flash tank), for upgrading the first mixture.Hydrocarbon in the first mixture Component comprises >=about 0.1wt% asphalitine, weight based on the hydrocarbon component in the first mixture, Such as >=5.0wt% time, such gas liquid separation device is particularly suitable.Conventional gas/ Liquid separating apparatus can be used for performing this operation, but the present invention is not limited to this.This traditional The example of gas liquid separation device includes those being disclosed 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. Suitably gas liquid separation device is also disclosed in United States Patent (USP) 6,632,351 He In 7,578,929, their full content is incorporated herein.Generally, when using gas liquid separation dress When putting, the composition of the gas phase leaving this device is substantially identical with the composition of the gas phase entering this device, The basic composition phase with the liquid phase entering this device of composition of the liquid phase leaving flash tank equally With, i.e. the separation in gas liquid separation device includes that (or the most consisting essentially of) enters and is somebody's turn to do The physical separation of two phases of tank.

In the embodiment using gas liquid separation device and pyrolysis oven to integrate mutually, at least partially The hydrocarbon component of the first mixture is provided to the convection section entrance of pyrolysis unit, and wherein hydrocarbon is heated Making at least one of hydrocarbon is in the gas phase.When diluent (such as, steam) is used, The thinner composition of the first mixture in this part be optionally (it is preferred that) add and with Hydrocarbon component mixes to produce the first mixture.Then by the first mixture, it is at least partially In gas phase, at least one gas liquid separation device, flash distillation is to separate from the first mixture and to guide Open the high molecular weight molecules of at least one of first mixture, such as asphalitine.Bottom fraction Can guide from gas liquid separation device and come, this bottom fraction includes >=10.0wt% (base by weight Plinth) asphalitine of the first mixture.When described pyrolysis is the hydrocarbon group of steam cracking and the first mixture Subpackage containing one or more crude oil or during its fraction, steam cracker furnace can with at about 600 °F Within the temperature range of 950 °F (about 350 DEG C to about 510 DEG C) and about 275 kPas to about 1400 KPa pressure limit in, such as, within the temperature range of about 430 DEG C to about 480 DEG C and about Integrate to the gas liquid separation device carrying out operating in the range of 760 kpa pressures for 700 kPas.Source Overhead fraction in gas liquid separation device can be heated further by experience in convection section, Then by cross pipeline introduce radiant section, wherein overhead fraction is exposed on temperature >= 760 DEG C and pressure >=0.5 bar (gauge pressure), such as, temperature is at the model of about 790 DEG C to about 850 DEG C Enclose interior and pressure in about 0.6 bar (gauge pressure) to about 2.0 bars (gauge pressure), to carry out the first mixing The pyrolysis (such as, cracking and/or reformation) of hydrocarbon component in thing.

The upstream of the downstream at convection section entrance and the cross pipeline to radiant section has gas/liquid and divides An advantage from device be to which increase the hydrocarbon component can being directly used as in the first mixture and There is no the scope of the hydrocarbon types of pretreatment.Such as, the hydrocarbon component of the first mixture can comprise >= 50.0wt%, such as >=75.0wt%, such as >=90.0wt% are (based in described first mixture The weight of hydrocarbon) one or more crude oil, the crude oil of the highest naphthenic acid content and fraction thereof.Tool The charging having high naphthenic acid content especially produces those of high quantity tar and when at least one Gas liquid separation device is specially suitable when integrating with pyrolysis oven.If it is required, the first mixture Composition can change over time, such as, by utilizing containing the in first time period First mixture of one hydrocarbon component and then utilizing containing the second hydrocarbon component within the second time period Second mixture, described first and second hydrocarbon are substantially different hydrocarbon or the most different Hydrocarbon mixture.Described first and second time periods can be the persistent period being substantially identical, but It is that this is optional.The first and second time periods alternately can connect the most continuously or partly Carry out (such as, operate at " modular "), if necessary continuously.The present embodiment can For incompatible the first and second hydrocarbon components (i.e., wherein the first and second hydrocarbon components be Under environmental condition and be insufficient to compatible with blended mixture) continuous pyrolysis.Such as, including straight Evaporate the first hydrocarbon component of crude oil may be used for producing in first time period the first mixture and Steam-cracked tar is for producing the first mixture in the second time period.

In other embodiments, vapor/liquid separation device is not used.Such as when the first mixing When the hydrocarbon of thing includes crude oil and/or one or more its fractions, pyrolytical condition can be conventional steam Cracking conditions.Suitably steam cracking conditions includes, such as, the first mixture is exposed to temperature Degree (radiation exit measure) >=400 DEG C under the conditions of, such as the scope of 400 DEG C to 900 DEG C In, and pressure >=0.1 bar, continue the cracking time of staying about 0.01 second to 5.0 seconds scopes. In one or more embodiments, the first mixture comprises hydrocarbon and diluent, it is characterised in that The alkyl of the first mixture comprises >=50.0wt% following in the weight of the hydrocarbon of the first mixture One or more: wax-like residual oil, reduced crude, Petroleum, residual oil mixed compound, or crude oil. Diluent includes, such as, >=95.0wt% water, weight based on diluent.When the first mixing When thing comprises the diluent of 10.0wt% to 90.0wt%, weight based on described first mixture, This pyrolytical condition generally comprises following one or more: (i) is 760 DEG C to 880 DEG C scopes Interior temperature；(ii) pressure in the range of 1.0 to 5.0 bars (definitely)；Or (iii) is 0.10 The cracking time of staying in the range of second to 2.0 seconds.

Second mixture is directed out pyrolysis oven, and the second mixture is by coming from by pyrolysis One mixture.When the pyrolytical condition of regulation is utilized, described second mixture generally comprises >= The C of 1.0wt%₂Unsaturates and the TH of >=0.1wt%, this percetage by weight is based on the second mixing The weight of thing.Optionally, described second mixture comprises the >=C of 5.0wt%₂Unsaturates and/ Or the TH of >=0.5wt%, such as the TH of >=1.0wt%.Although the second mixture typically contains required Light olefin, in SCN, SCGO, SCT, and the first mixture, unreacted component (such as, is being steamed Water in the case of vapour cracking, but the most unreacted hydrocarbon) mixture, the most often The relative populations planting material is generally dependent on such as, the composition of the first mixture, pyrolysis oven structure, Process conditions in pyrolytic process etc..Second mixture is generally deflected from pyrolysis section, example As, for cooling and/or separation phase.

In one or more embodiments, the TH of the second mixture includes >=TH of 10.0wt% Aggregation, it has putting down in 10.0 nanometers to 300.0 nanometer range at least one dimension All scopes of average >=50 of size and carbon atom, this percetage by weight is based in the second mixing The weight of heavy tar in thing.Generally, aggregation includes >=50.0wt%, such as >=80.0wt%, Having C:H atomic ratio in the range of 1.0-1.8 such as >=90.0wt%, molecular weight is 250 With fusing point TH molecule in the range of 100 DEG C to 700 DEG C in the range of 5000.

Although not required to, the present invention is with to cool down the second mixture in pyrolysis oven downstream compatible, Such as, the second mixture can use the system including transfer-line exchanger to cool down.Such as, Within the temperature range of transfer-line exchanger can be with bosher's process stream to about 700 DEG C to about 350 DEG C, Effectively to produce extra high pressure steam, it can be utilized by this technical process or be conducted away.As Fruit needs, and the second mixture generally can be at typically some warp between outlet of still and separation phase Go through and be directly quenched.Quenching can be by connecing described second mixture with liquid quenching logistics Touch and realize, with replace use pipeline changer process, or except pipeline changer with Outward.When being used in combination with at least one transfer-line exchanger, quench fluid is preferably at transfer line The point in heat exchanger downstream introduces.Suitably quench fluid includes liquid quenching oil, under passing through such as those Those of the quenching oil knockout drum acquisition of trip, pyrolysis fuel oil and water, it can be from usual sources Obtaining, such as, the dilution steam generation of condensation obtains.

Separation phase is generally employed in the downstream of pyrolysis oven and pipeline exchanger and/or quenching The downstream of point is for separating following one or more from the second mixture: light olefin, SCN, SCGO, SCT, or water.Conventional separation equipment may be used for separation phase, such as one or many Individual flash drum, fractionating column, water flash cold column, indirect condenser etc., as in United States Patent (USP) 8,083,931 Described in those.At separation phase, the 3rd mixture, it is tar stream, can be from institute State in the second mixture and separate, and described 3rd mixture tar stream comprises >=10.0wt% The TH of the second mixture, the weight of TH based on the second mixture.When described pyrolysis is steam Cracking, described tar stream generally includes SCT, it such as, from SCGO logistics and/or steam The bottoms of the main fractionating tower of cracking unit, (such as, is positioned at pyrolysis from flash drum bottoms The bottoms of one or more flash drum of stove downstream and main fractionating tower upstream), or their group Close and obtain.

Tar stream can include TH aggregation.In one or more embodiments, tar stream Comprise >=the TH of second mixture of 50.0wt%, the weight of TH based on the second mixture.Example As, tar stream can include >=the TH of second mixture of 90.0wt%, based on the second mixing The weight of the TH of thing.Tar stream can have, and such as, (i) sulfur content is at 0.5wt% extremely In the range of 7.0wt%, (ii) TH content in the range of 5wt% to 40.0wt%, this weight hundred Mark weight based on described tar stream, (iii) density when 15 DEG C is 1.01g/cm³ To 1.15g/cm³In the range of, as at 1.07g/cm³To 1.15g/cm³In the range of, and (iv) 50 DEG C of viscosity at 200cSt to 1.0 × 10⁷In the range of cSt.

Tar stream be generally routed away from separation phase be in order in the presence of effectiveness fluid one Individual or the hydrotreating of multiple hydrotreating stage coal-tar middle oil logistics, this effectiveness fluid generally includes The liquid phase part of the circulation of hydrotreater effluent.It is more fully described in the present invention now and has Effectiveness fluid example.

Effectiveness fluid

Effectiveness fluid is used for hydrotreating tar stream, such as, for effectively increasing hydrogenation The running length increased during process and the performance of the tar that can improve hydrotreating.Effectively Effectiveness fluid composition include aromatic hydrocarbons, i.e. include the molecule with at least one aromatic kernel.? In one or more embodiments, this effectiveness fluid comprises and passes through¹³C NMR (Nuclear Magnetic Resonance) spectrum is measured >=40.0wt% aromatic carbon, such as >=60.0wt% aromatic carbon.In certain embodiments, effectiveness stream Body includes a part of liquid phase effluent.In other words, a part is added total liquid phase in inverse processing region Product is circulated back to hydrotreater effectively.Such as, effectiveness fluid can include >=50.0wt% For simplicity, total liquid phase part of hydrotreating stage effluent (hydrotreater effluent Liquid phase), such as >=75.0wt%, or >=95.0wt%, or even >=99.0wt%, based on effectiveness The weight of fluid.The remainder of the hydrotreating stage liquid phase effluent of hydrotreater effluent Divide (i.e. remainder) can deflect from from the method, and the most such as, as low sulphur fuel oil Blending components.From the effluent in hydrotreating stage optionally by one or more separation Stage.The limiting examples of separation phase comprises the steps that flash tank, distillation column, vaporizer, Stripper, steam stripping device, vacuum flashing, or vacuum distillation tower.These separation phases allow Those skilled in the art regulate the performance of the liquid phase part of hydrotreater effluent for use as effectiveness Fluid.The liquid phase part of hydrotreater effluent can include >=90.0wt% hydrotreater outflow Thing has the molecule of at least four carbon, weight based on hydrotreater effluent.At other In embodiment, the liquid phase of hydrotreater effluent includes >=90.0wt% hydrotreater outflow Thing has atmospheric boiling point >=65.0 DEG C, such as >=100.0 DEG C, the molecule of such as >=150.0 DEG C (weight based on hydrotreater effluent).

In other embodiments, total liquid phase part of hydrotreater effluent is separated into gently Matter liquid and heavy liquid, wherein said heavy liquid contains >=90wt% liquid phase present in have There are atmospheric boiling point >=250 DEG C, the molecule of such as >=350 DEG C.Effectiveness fluid can include a part from This separates the light liquids obtained.

Optionally, in other embodiments, including at least one of hydrotreater effluent The effectiveness fluid of separatory phase can be increased by supplementary effectiveness fluid or substitute, described supplementary effectiveness stream Body has ASTM D8610% and evaporates point >=120 DEG C, such as, >=140 DEG C, such as >=150 DEG C and/ Or ASTM D8690% evaporates point≤300 DEG C.During starting or cell failure or other operability This option of time period of part is useful especially, such as when tar stream mass change.

Supplementing effectiveness fluid can be solvent or solvent mixture.In one or more embodiments In, this supplementary effectiveness fluid (i) has the critical temperature in the range of 285 DEG C to 400 DEG C, And (ii) comprises >=the 1-aromatic compound of 80.0wt% and/or 2-aromatic compound, bag Include their alkyl functionalized derivant, weight based on this supplementary effectiveness fluid.Such as, should Supplementing effectiveness fluid can include, such as, the monocyclic aromatics of >=90.0wt%, including tool There are those of one or more hydrocarbyl substituent, as the alkyl of 1 to 3 or 1 to 2 replaces Base.These substituent groups can be any alkyl consistent with all solvent distillation characteristics.This kind of The example of alkyl include but not limited to selected from C₁-C₆Those of alkyl, wherein this hydrocarbyl group Can be side chain or straight chain and hydrocarbyl group can be same or different.Optionally, mend Fill effectiveness fluid weight based on supplementary effectiveness fluid include >=the following one of 90.0wt% or Multiple: benzene, ethylbenzene, trimethylbenzene, dimethylbenzene, toluene, naphthalene, alkylnaphthalene (such as, methyl naphthalene), Tetrahydronaphthalene, or alkyl tetrahydro naphthalene (such as, methyltetrahydro naphthalene).Typically require and supplement effect It is essentially free of the molecule with thiazolinyl function with fluid, is especially using at these molecules In the presence of have coke formed tendency hydrotreating catalyst embodiment in.At one In embodiment, this supplementary effectiveness fluid comprises≤and 10.0wt% comprises and has thiazolinyl function C₁-C₆The cycle compound of side chain, weight based on effectiveness fluid.

In certain embodiments, this supplementary effectiveness fluid includes SCN and/or SCGO, such as, Mix from second from the main fractionator in the downstream of the pyrolysis oven of operation under the conditions of steam cracking operations SCN and/or SCGO that compound separates.Generally, it is preferred to be the C of SCN and/or SCGO₆₊Fraction. (such as, this SCN or SCGO can carry out hydrotreating in different conventional hydro processors Hydrogenation of tar is not used to process).This supplementary effectiveness fluid can include, such as, and >=50.0wt% The gas oil separated, weight based on supplementary effectiveness fluid.In certain embodiments, at least A part of effectiveness fluid obtains from the product of hydrotreating, such as, by separating and recirculating There is the liquid phase part of the hydrotreater effluent of atmospheric boiling point≤300 DEG C.

Containing q.s, there is one or more aromatic kernel it is said that in general, supplement in effectiveness fluid Molecule to increase the effectiveness fluid of product of the hydrotreating including circulation to be effectively increased at Running length in the hydroprocessing processes of tar stream.Such as, this supplementary effectiveness fluid is permissible Comprise >=50.0wt% has the molecule of at least one aromatic kernel, such as, >=60.0wt%, such as >=70wt%, gross weight based on effectiveness fluid.In one embodiment, this supplementary effectiveness stream Body comprises (i) >=60.0wt% and has the molecule of at least one aromatic kernel and (ii)≤1.0wt% includes There is the C of alkenyl-functional groups₁-C₆The cycle compound of side chain, this percetage by weight is based on effectiveness fluid Weight.

In hydroprocessing processes, the relative populations of effectiveness fluid and tar stream is usually from about Tar stream in the range of 20.0wt% to about 95.0wt% and from about 5.0wt% to about Effectiveness fluid in the range of 80.0wt%, adds the gross weight of tar stream based on effectiveness fluid. Such as, in hydroprocessing processes, the relative populations of effectiveness fluid and tar stream can be (i) Tar stream in the range of about 20.0wt% to about 90.0wt% and about 10.0wt% are to about In the range of effectiveness fluid in the range of 80.0wt%, or (ii) about 40.0wt% to about 90.0wt% Tar stream, and the effectiveness fluid in the range of about 10.0wt% to about 60.0wt%.At least one Partly this effectiveness fluid can be with this tar stream at least some of at hydroprocessing vessel or hydrogenation Treatment region is combined, but this is optional, and in one or more embodiments At least one of effectiveness fluid and at least some of tar stream are provided as single logistics With before entering hydroprocessing vessel or hydroprocessing district (such as: be combined at its upstream) one Individual feed stream.In certain embodiments, the feed stream to hydrotreater includes The effectiveness fluid of SCT and 10.0wt%-40.0wt% of 40.0wt%-90.0wt%, this weight percent Base is in the weight of feed stream.Such as: tar: effectiveness fluid proportional can be 0.50:1.0 To 3.0:1.0, the such as scope of 0.2 to 3.0.

Hydrotreating

In the presence of effectiveness fluid, the hydrotreating of tar stream can occur at one or more hydrogenation In processing stage, this stage includes one or more hydroprocessing vessel or region.Wherein occur Container or region in the hydrotreating stage of catalytic hydrogenation treatment activity generally comprise at least one Hydrotreating catalyst.This catalyst can be mixing or stacking, such as, when catalyst be In hydroprocessing vessel or region during the form of one or more fixed beds.

Conventional hydrotreating catalyst can be used for tar stream in the case of effectiveness fluid exists Hydroprocessing processes, as being given for the hydrotreating of residual oil and/or heavy oil, but The present invention is not limited to this.Suitably hydrotreating catalyst includes having (i) one or more bases Those of body metal and/or (ii) one or more metals on carrier.This metal can be single Matter form or presented in compound.In one or more embodiments, hydrotreating Catalyst comprises any one (tabular element week of the 5th to 10 race in the periodic table of elements Phase table, Merck index, Merck & Co., Inc., 1996).The example of this kind of catalytic metal includes, but not It is limited to, vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, ferrum, cobalt, nickel, ruthenium, palladium, rhodium, osmium, Iridium, platinum, or their mixture.

In one or more embodiments, in this catalyst, every gram of catalyst has 5 to 10 The total amount of race's metal is at least 0.0001 gram, or at least 0.001 gram or at least 0.01 gram, In base, grams calculates in elemental basis.Such as, catalyst can comprise 5 to 10 race's metals Total weight range 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 it it is 0.01 gram to 0.08 gram.In a specific embodiment, urge Agent also comprises at least one the 15th race's element.Preferred 15th race's element is phosphorus.When 15 When race's element is used, this catalyst can include the total amount in the range of the 15th race's element be 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 on the basis of element.

In one embodiment, catalyst comprises at least one the 6th race's metal.Preferred The example of 6 race's metals includes chromium, molybdenum and tungsten.This catalyst can contain, every gram of catalyst, and the 6th Race's total metal content is at least 0.00001 gram, or at least 0.01 gram, or at least 0.02 Gram, wherein gram calculating is on the basis of element.Such as, every gram of catalyst comprises the 6th race's metal Always weight range 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 being the scope of 0.01 gram to 0.08, wherein grams calculates with element as base Accurate.

In relevant embodiment, catalyst comprises at least one the 6th race's metal, goes forward side by side one Step includes that at least one comes from the 5th race, the 7th race, the 8th race, the 9th race, or 10 races Metal.This catalyst can comprise, such as, the 6th race's metal and the 5th race's metal mole Ratio should be 0.1 to 20, the combination of metal in the range of 1 to 10, or 2 to 5, wherein said Ratio is on the basis of element.Or, described catalyst will containing the 6th race's metal and the 7th to In 10 races, the mol ratio of total metal content should be 0.1 to 20, in the range of 1 to 10, or 2 to 5 The combination of metal, wherein said ratio is on the basis of element.

When catalyst comprises at least one the 6th race's metal and one or more come from the 9th or the The metal of 10 races, such as, molybdenum-cobalt and/or tungsten-nickel, these metals can coexist, such as, The molar ratio range of the metal of the 6th race's metal and the 9th and the 10th race should be from 1 to 10, or 2 To 5, ratio therein is on the basis of element.When catalyst comprises at least one the 5th race's gold Belong to and at least one the 10th race's metal, these metals can coexist, such as, the 5th race's metal with The molar ratio range of the 10th race should be 1 to 10, or from 2 to 5, ratio therein is with element On the basis of.Catalyst also includes inorganic oxide, such as, as binding agent and/or carrier, Within the scope of the present invention.Such as, catalyst can include (i) >=1.0% selected from periodic chart the 6th, 8, one or more metals of 9 and 10 races and the inorganic oxide of (ii) >=1.0wt%, this is heavy Amount percent weight based on catalyst.

It is contemplated by the invention that introduce (or at deposited on supports) one or more catalytic gold on carrier Belonging to, one or more metals such as the 5th to 10 race and/or the 15th race are urged to form hydrotreating Agent.This carrier can be porous material.Such as, carrier can include one or more infusibilities Oxide, porous carbon sill, zeolite or their combinations.Suitably refractory oxides includes, Such as, aluminium oxide, silicon dioxide, silica-alumina, titanium oxide, zirconium oxide, oxidation Magnesium, and their mixture.Suitably porous carbon sill includes activated carbon and/or porous stone Ink.The example of zeolite includes, such as, Y-zeolite, β zeolite, modenite, ZSM-5 type Zeolite, and ferrierite.Other example of carrier material includes gama-alumina, θ-aluminium oxide, δ-aluminium oxide, Alpha-alumina, or combinations thereof.Gamma oxidation in every gram of catalyst carrier Aluminum, δ-aluminium oxide, Alpha-alumina or the total amount of combinations thereof, control in scope be, example Such as 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 most 0.1 gram, as measured by X-ray diffraction.In certain embodiments, Hydrotreating catalyst is loaded catalyst, and this carrier comprises at least one aluminium oxide, such as, θ-aluminium 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 aluminium oxide can use such as, X-ray diffraction determines.In an alternate embodiment, carrier can include at least 0.1 gram, Or at least 0.3 gram, or at least 0.5 gram, or the θ-aluminium 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 DEG C to 1200 DEG C, or from 450 DEG C to 1000 DEG C, or Through Overheating Treatment within the temperature range of 600 DEG C to 900 DEG C, before with metal impregnation.At certain In a little embodiments, hydrotreating catalyst can be by adding or merge the gold of the 5th to 10 race The mixture belonging to the one-tenth heat treatment to carrier is formed.Such formation is commonly called The top of carrier material covers these metals.Optionally, urge with one or more combining carrier After changing metal, described catalyst is carried out heat treatment, such as, in temperature from 150 DEG C to 750 DEG C, Or in the range of 200 DEG C to 740 DEG C or within the temperature range of 400 DEG C to 730 DEG C.Optionally Ground, by catalyst within the temperature range of 400 DEG C and 1000 DEG C at hot-air and/or oxygen-enriched air Middle heat treatment, to remove volatile material so that at least of described 5th race to the 10th race Parting genus is converted into they corresponding metal-oxides.In other embodiments, this catalysis Agent can in the presence of oxygen (such as air) heat treatment, its temperature range from 35 DEG C to 500 DEG C, Or from 100 DEG C to 400 DEG C, or from 150 DEG C to 300 DEG C.Heat treatment can be carried out 1 to 3 Time in the range of hour, to remove major part volatile component, and the 5th to 10 need not be converted The metal of race becomes their metal oxide form.The catalyst prepared by such method Commonly referred to as " calcining " catalyst or " being dried ".Such catalyst can be in conjunction with Prepared by vulcanization process, and the metal of the 5th to 10 race is substantially dispersed among carrier.When When catalyst comprises the metal of θ-alumina support and one or more the 5th to 10 races, this is urged Agent generally carries out heat treatment to form hydrotreating catalyst at a temperature of >=400 DEG C.Typical case Ground, this heat treatment is carried out at a temperature of≤1200 DEG C.

Catalyst can be at the form shaped, such as, following one or more: dish, grain Material, extrudate etc., although this is optional.The limiting examples of this shaping form Including have cylindrical symmetry and diameter from about 0.79 millimeter to about 3.2 millimeter (1/32 to 1/8 inch), from about 1.3 millimeters to about 2.5 millimeter (1/20 to 1/10 inch), or from about 1.3 millimeters of those arrived in the range of about 1.6 millimeters (1/20 to 1/16 inch).Onesize Non-cylindrical shape be that the present invention relates to, such as, trilobal, quatrefoil etc..Appoint Selection of land, this catalyst 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 In the range of flat board compressive resistance.

Porous catalyst, including having those of conventional pore character, all the present invention relates to Within the scope of.When porous catalyst is used, the pore structure that this catalyst can have, hole Gap size, pore volume, pore shape, pore surface area etc., is being that conventional hydro process is urged In the range of the feature of agent, but the present invention is not limited to this.Such as, this catalyst can have The aperture of median magnitude, so can effective hydrotreating SCT molecule, such as there is intermediate value big Little aperture from 30 angstroms to 1000 angstroms, or 50 angstroms to 500 angstroms, or 60 angstroms to 300 angstroms In the range of catalyst.Aperture can determine according to ASTM method D4284-07 mercury injection method.

In particular embodiments, hydrotreating catalyst have scope be 50 angstroms to 200 Angstrom mean pore sizes.Or, it is 90 angstroms to 180 angstroms that hydrotreating catalyst has scope, or 100 angstroms to 140 angstroms, or the mean pore sizes of 110 angstroms to 130 angstroms.In another embodiment In, the mean pore sizes scope of hydrotreating catalyst is 50 angstroms to 150 angstroms.Or, at hydrogenation Reason catalyst has mean pore sizes in the range of 60 angstroms to 135 angstroms, or from 70 angstroms to 120 angstroms. In yet another alternative, there is a hydrotreating catalyst with bigger mean pore sizes Being utilized, such as, those have mean pore sizes from 180 angstroms to 500 angstroms, or 200 angstroms extremely In the range of 300 angstroms, or 230 angstroms to 250 angstroms.

Generally, the pore-size distribution of hydrotreating catalyst is not configured to very big and reaches significantly to deteriorate The activity of catalyst or selectivity.Such as, can have pore-size distribution at hydrotreating catalyst, The aperture at least a part of which 60% hole is at 45 angstroms of mean pore sizes, within 35 angstroms, or 25 angstroms.? In some embodiment, described catalyst has mean pore sizes in the range of from 50 angstroms to 180 Angstrom, or from 60 angstroms to 150 angstroms, the aperture in the hole of at least a part of which 60% is the 45 of mean pore sizes Angstrom, within 35 angstroms or 25 angstroms.

When porous catalyst is used, this catalyst can have, such as, and pore volume >=0.3 Cubic centimetre/gram, such as >=0.7 cubic centimetre/gram, or >=0.9 cubic centimetre/gram.At certain In a little embodiments, the scope of pore volume can be from 0.3 cubic centimetre/gram to 0.99 cube li Rice/gram, 0.4 cubic centimetre/gram to cubic centimetre/gram, or 0.5 cubic centimetre/gram is to 0.7 Cubic centimetre/gram.

In certain embodiments, relatively large surface area is desirable.As an example, In surface area >=60 meters squared per gram that hydrotreating catalyst can have, or >=100 square metres/ 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 is to 270 meters squared per gram, or 130 meters squared per gram are to 250 meters squared per gram, or In the range of 170 meters squared per gram to 220 meters squared per gram.

Tar stream and the effectiveness fluid of specified quantity are entered by the hydrotreating catalyst using regulation Row hydrotreating causes the catalyst life improved, such as, it is allowed to the hydrotreating stage grasps continuously Make at least 3 months, or at least 6 months, or at least 1 year and not in hydrotreating district Or the replacement of catalyst in contact area, regenerate or update.If with the feelings not using effectiveness fluid Condition is compared, and catalyst life is typically long > 10 times, such as >=100 times, such as >=1000 times.

Hydrotreating is in the presence of hydrogen, such as, and (i) upper by hydrotreating Swim binding molecule hydrogen and tar stream and/or effectiveness fluid and/or (ii) at one or more pipelines Or circuit guides molecular hydrogen carry out to the hydrotreating stage.Although relatively pure hydrogen molecule May be used for hydrotreating, it usually needs utilize " place's process gases ", wherein contain hydrotreating The enough molecular hydrogens needed and optional other species (such as, nitrogen and light hydrocarbon such as methane), They typically do not result in adverse effect or interference reaction or product.Untapped place process gases Can be recycled by separation from hydrotreater effluent, typically remove unwanted impurity, Such as hydrogen sulfide H₂S and ammonia NH₃Afterwards.At this, process gases can contain volume fraction >=about 50% Hydrogen molecule, such as, volume fraction >=about 75%, based on being directed to the hydrotreating stage The cumulative volume of place's process gases.

Optionally, the quantity delivered scope of hydrotreating multi-stage molecular hydrogen is about from 300SCF/B (mark Quasi-cubic feet/bucket) (53S m³/m³) arrive 5000SCF/B (890S m³/m³), wherein B table Show the bucket of tar stream.Such as, hydrogen molecule can be 1000SCF/B (178S m in scope³/m³) To 3000SCF/B (534S m³/m³) provide.At the effectiveness fluid of regulation, molecular hydrogen and urging Focus under the conditions of catalytic hydrogenation treatment in the presence of changing the regulation hydrotreating catalyst of effective quantity Oil logistics carries out hydrotreating and produces the product of hydrotreating, and it includes such as, the SCT of upgrading. The suitably example of catalytic hydrogenation treatment condition is described in more detail below.The present invention does not limit In these conditions, and this description is not meant to getting rid of other relevant to the present invention more Hydroprocessing condition in the range of width.

This hydrotreating is generally carried out under the conditions of hydro-conversion, such as, is carrying out following one Or under conditions of multiple: regulation tar stream be hydrocracked (including selective hydrogenation cracking), Hydrogenization, hydrogenation treatment, hydrodesulfurization, hydrodenitrogeneration, HDM, hydroisomerizing Change effect or Hydrodewaxing.Hydrotreating reaction can be positioned at such as at least one, at hydrogenation Processing stage, carried out in pyrolysis phase and the container in separation phase downstream or region.Regulation Tar stream generally in container or region with hydrotreating catalyst, at effectiveness fluid and molecule Contact in the presence of hydrogen.Catalytic hydrogenation treatment condition can include, such as by combination diluent- Tar stream be exposed to from 50 DEG C to 500 DEG C or from 200 DEG C to 450 DEG C or from 220 DEG C to 430 DEG C or within the temperature range of 350 DEG C to 420 DEG C close to molecular hydrogen and hydrorefining catalyst Agent.Such as, from 300 DEG C to 500 DEG C, or 350 DEG C to 430 DEG C, or 360 DEG C to 420 DEG C Within the temperature range of can be utilized.When utilizing >=temperature of about 425 DEG C with comprise (i) cobalt and molybdenum And (ii) Woelm Alumina-base carrier under the pressure of >=about 70 bars (definitely) time, at hydrogenation C in processor₂₊The conversion ratio of methane is dramatically increased by compound.Diluent-tar the thing of combination The liquid hourly space velocity (LHSV) (LHSV) of stream is generally 0.1h^-1To 30h^-1, or 0.4 to 25h^-1, or Person 0.5h^-1To 20h^-1In the range of.In some embodiments, LHSV is at least 5h^-1, Or at least 10h^-1, or at least 15h^-1.Molecular hydrogen partial pressure in hydroprocessing processes is usually 0.1 MPa to 8 MPas or 1 MPa to 7 MPas, or 2 MPas to 6 MPas, or 3 MPas To 5MPa.In some embodiments, molecular hydrogen partial pressure is≤7 MPas, or ≤ 6 MPas, or≤5 MPas, or≤4 MPas, or≤3 MPas, or≤2.5 million Handkerchief, or≤2 MPas.The condition of hydrotreating can include, such as following is one or more: Temperature range at 300 DEG C to 500 DEG C, pressure limit at 15 bars (definitely) to 135 bars, space The scope of speed is 0.1 to 5.0, and molecular hydrogen wear rate is about 50 standard cubic meters/vertical Side rice (S m³/m³) to about 450S m³/m³(300SCF/B to 2500SCF/B).At one or In multiple embodiments, hydroprocessing condition includes following one or more: temperature range 380 DEG C to 430 DEG C, pressure limit 20 bar (definitely) is to 120 bars (definitely), or 20 bars are (absolutely Right) to 100 bars (definitely), or 21 bars (definitely) are to 81 bars (definitely), space velocity (LHSV) Scope is 0.2 to 1.0, and molecular hydrogen wear rate is about 70S m³/m³To about 265S m³/m³(400SCF/B to 1500SCF/B).When using the catalyst of regulation under these conditions During operation, the conversion ratio of TH hydro-conversion is typically >=25.0%, and this is based on weight, example As, >=50.0%.

One embodiment of the invention is schematically illustrated in Fig. 1.To be provided by pipeline 1 Including (i) tar, the effectiveness fluid provided by pipeline 7 such as raw material and (ii) of SCT is passed through Pipeline 8 is directed to hydrotreating reactor 2 for the hydrotreating bar in one or more regulations Hydrotreating is carried out under part.At molecular hydrogen, process gases is drawn by one or more pipeline (not shown) Enter reactor 2.The effluent of reactor is directed to separation phase 4 by pipeline 3.By a part Total product liquid of reactor effluent (i.e. from hydrotreater total liquid phase effluent one Part) separate and deflect from separation phase 4 by pipeline 7 to come as effectiveness fluid.Including, such as, The waste gas of molecular hydrogen, methane and hydrogen sulfide separate separation phase 4 from reactor effluent and Deflected from by pipeline 6.Deflected from by pipeline 5 and include, such as C₅₊The product of the hydrotreating of hydrocarbon.

In certain embodiments, need SCT hydrotreating to reach useful blending characteristic And/or relatively low viscosity, such as≤20cSt, such as≤15cSt or≤10cSt's is viscous Degree.For accomplishing so to use the cobalt-molybdenum catalyst of the sulfidation-oxidation aluminum load of routine, can be one By one or more under the conditions of catalytic hydrogenation treatment in the presence of the effectiveness fluid of kind or multiple regulation The SCT of regulation carries out hydrotreating, and described catalytic hydrogenation treatment condition is included in temperature at 375 DEG C To 425 DEG C of scopes, such as 385 DEG C to 415 DEG C scopes；Pressure at 45 bars (definitely) to 135 In the range of bar (definitely), such as 60 bars (definitely) to 90 bars (definitely)；Molecular hydrogen processing speed (base Feed in tar) at 150S m³/m³To 1200S m³/m³(840SCF/B to 6700SCF/B) In the range of, as at 180S m³/m³To 450S m³/m³(1000SCF/B to 2500SCF/B) In the range of；With LHSV in the range of 0.1 to 2.0, the LHSV of such as 0.25 to 0.50 Based on combined feed (tar+effectiveness fluid).Have been observed that C_4-The generation of by-product to hydrogenation at The temperature that reason period SCT exposes is sensitive, and is greater than about 425 DEG C when temperature under conditions of regulation Time these by-products generation can increase.Although the effectiveness fluid for a little embodiments can be from Hydrotreater effluent circulation (optionally after the separation of the tarry distillate of hydrotreating), This is not required.In certain embodiments, use fresh effectiveness fluid, as have with Supplement the effectiveness fluid of the essentially identical composition of effectiveness fluid.Effectiveness fluid under these conditions: But tar ratio 0.05:1.0 to 2.0:1.0, such as 0.10:1.0 to 1.0:1.0, or 0.1:1.0 to 0.5:1.0.

Below embodiment further describes the aspect of certain embodiments of the invention.The present invention is not Be limited to these embodiments, and these embodiments be not meant to get rid of wider range of the present invention it Other interior embodiment.

Embodiment 1

(it has 20 cubic centimetres total for 3/8 inch of SS stainless steel tube of a kind of 56 centimeter length Volume) it is used as reactor.In experimentation, 34 centimetres, this centre is maintained at 400 DEG C Under nearly thermostat temperature.The volume of hot-zone is 14 cubic centimetres.20 are loaded in whole reactor The nickel molybdenum oxide hydrotreating catalyst on the alumina support that cubic centimetre is commercially available (RT-621) the 80 mesh silica gel of and 5 cubic centimetres are used for Package gaps space.

With reference to Fig. 1, in reactor 2, provided the raw material of 100.0wt% by pipeline 8.This is former The material SCT containing the 60.0wt% introducing technique by pipeline 1 (has similar spy to SCT-1 Property) and the effectiveness fluid of 40.0%, this effectiveness fluid becomes the total liquid phase of this reactor and flows out A part for thing, it is introduced into pipeline 8 by pipeline 7, and this percetage by weight is based on described The weight of raw material.This is corresponding to the weight ratio of the effectiveness fluid in the raw material of 0.66 Yu tar stream Rate.Raw material passes through pipeline 8 with 7cm³The speed of/hr is transported in reactor.Molecular hydrogen quilt It is fed through conduit (not shown) to carry with the speed of 26 standard cubic centimeters (sccm) per minute To reactor 2, reactor is run 80 days the most continuously, without notable pressure drop ( Within initial drop about 10.0%).

Hydroconversion condition in reactor 2 includes about 70 bar (1000psig) pressure, 400 DEG C of temperature Degree, molecular hydrogen wear rate rate 200m based on raw material³/m³(1100SCFB), and 0.44 Space velocity (LHSV).Reactor effluent includes gas phase and liquid phase, the liquid product that liquid phase is the most total Thing.The amount of total product liquid is about in total reactor the 95.0wt% of total liquid feedstock.

The effluent of reactor 2 is directed to separation phase 4 by conduit 3.The liquid phase of reactor A part for effluent (comprises the effluent of reactor described in 40.0 weight %, based on reactor The weight of effluent) it is used as effectiveness fluid and is deflected from the stage 4 from through conduit 7.Stage 4 also by For separating the C containing about 56.0wt% quantity from reactor effluent₅₊The hydrotreating of hydrocarbon Product, weight based on described reactor effluent.Stage 4 is to be used to flow out from reactor Separating vapor product " waste gas " 6 in thing, this vapor product comprises about 1.1wt% hydrogen sulfide with big The molecular hydrogen of about 1.1wt%, weight based on reactor effluent.Waste gas is possibly together with a small amount of Other gas (such as methane), obtains the total reactor effluent of 100.0%, and this is based on described former The weight of material.

The liquid and gas of reactor effluent and the composition of raw material are carried out point by conventional method Analysis.SCT has 1.11g/cm³Density, and comprise the sulfur of 2.2wt% and 1600ppmw Nitrogen, this weight based on SCT.The product of this hydrotreating comprises C₅₊Hydrocarbon and 800ppmw's Nitrogen.This hydrogenation products has 1.01g/cm³Density (at 15 DEG C), 8.8cSt at 50 DEG C Viscosity, and mixed number I_nAbout 50.Reactor pressure depreciation is similar to 0.1 bar.

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

The method is useful, this is because it is acid by it, and high viscosity, high density tar thing Circulation turns to more low viscosity, less dense, < logistics of 0.5wt% sulfur and there is more perfect spy Property for being blended into final finished fuels.

Embodiment 2

Repeating the experiment of embodiment 1, difference is to increase Liquid-phase reactor total in conduit 7 The amount of the recycle sections of effluent, comprises 80.0wt% fluid product and 20.0wt% to produce The raw material of SCT, this weight based on described raw material.This is corresponding to effectiveness fluid: tar stream Weight ratio is at 4:1.In operation, show after reactor 2 is in only going into operation several hours The pressure increased reduces.Going into operation after fortnight, voltage drop value increases to greater than 20 bar (> 300psi) Must stop with operation.

Embodiment 3

Repeat embodiment 2 experiment, difference be raw material comprise the total fluid product of 91.0wt% and The SCT of 9.0wt%, this weight based on described raw material.This is corresponding to effectiveness fluid: tar thing The weight ratio of stream is at 10:1.In operation, it may be immediately observed that the reactor pressure decrease of increase.Go into operation After 12 hours, voltage drop value increases to greater than 20 bar (> 300psi) and operate and must stop.

These embodiments show increase effectiveness fluid (total Liquid-phase reactor effluent astoundingly Recirculation) ratio by increase reactor pressure decrease value drop and deteriorate operability.While not wishing to by appointing The constraint what is theoretical, it is believed that utilize relatively high effectiveness fluid content (such as, relatively large Total product liquid recirculation) cause higher pressure drop, this is due to 565 DEG C of raw material₊In fraction Between the minimum dissolubility molecule found caused by incompatibility.Believe containing 100wt% tar Raw material can block reactor, and this is due to the asphaltene aggregation in catalyst pores thus to produce and have Poor quality transmission and the compositions of long residence time.Under these conditions, asphalitine is the hottest Reaction heat also forms coke.These embodiments show to reclaim the liquid of less amount of reactor effluent Phase product is capable of the stable operation without blocking.

Have been found that operation can under the of a relatively high effectiveness fluid weight ratio with tar stream To cause the increase of pressure drop.In order to smaller size of equipment can be used in the hydrotreating stage, It is necessary for relatively low pressure drop.When raw material includes that SCT is as tar component and reactor stream When going out the part of total fluid product of thing as effectiveness fluid, when fluid product total in raw material with The ratio of SCT is≤4.0, such as, in the range of 0.05:1.0 to 3.5:1.0, as When 0.10:1.0 to 2.0:1.0,0.2:1.0 to 2.0:1.0 or 0.2:1.0 to 1.0:1.0, The relatively low pressure drop retention time is more than 10 days.

All patents, test program, and alternative document cited herein, including preferential Power file, is allowed to introduce the application.

Although the present invention is specifically described with exemplary form, it should be appreciated that various other is repaiied Change and will be apparent from, and can easily not taken off by those of ordinary skill in the art Complete in the spirit and scope of the disclosure of the present invention.Therefore, the invention is not restricted to example Described in detailed content, these claims are interpreted to cover all those skilled in the art It is contemplated that equivalence replacement.

The present invention lists numerical lower limits and numerical upper limits, and the scope being limited to the upper limit from down is all can be pre- Phase.

Claims

1. a hydroconversion process, including:

B () is pyrolyzed the first mixture and comprises >=the C of 1.0wt% to produce₂Unsaturates and >= Second mixture of 1.0wt% steam cracker tar, this percetage by weight is based on the second mixture Weight；

C () separates the tar stream comprising steam cracker tar from described second mixture, its In (i) described tar stream comprise >=90.0wt% the second mixture in atmospheric boiling point >=290 DEG C Molecule and (ii) described tar stream have >=the aromatic carbon content of 70.0wt%, and based on described The weight of tar stream；

E () incites somebody to action at least one under the conditions of catalytic hydrogenation treatment in the presence of molecular hydrogen and effectiveness fluid Part tar stream is exposed at least one hydrotreating catalyst and flows out to produce hydrotreater Thing, wherein said effectiveness fluid: tar stream weight ratio is in the range of 0.05 to 3.5；With

F () isolates liquid phase from hydrotreater effluent, described liquid phase comprises >=90.0wt% There is the molecule of the hydrotreater effluent of at least 4 carbon atoms, based on hydrotreater stream Going out the weight of thing, wherein said effectiveness fluid includes the liquid phase of the separation of quantity >=90.0wt%, base Weight in effectiveness fluid.

Method the most according to claim 1, wherein said effectiveness fluid includes passing through NMR Measure >=aromatic carbon of 60.0wt%, weight based on effectiveness fluid.

Method the most according to claim 1 and 2, wherein said liquid phase comprises >=90.0wt% There is the molecule of the hydrotreater effluent of atmospheric boiling point >=65.0 DEG C, based on hydrotreater The weight of effluent.

Method the most according to claim 1, wherein said liquid phase comprises >=90.0wt% tool There is the molecule of the hydrotreater effluent of atmospheric boiling point >=100.0 DEG C, based on hydrotreater stream Go out the weight of thing.

Method the most according to claim 1, wherein said liquid phase comprises >=90.0wt% tool There is the molecule of the hydrotreater effluent of atmospheric boiling point >=150.0 DEG C, based on hydrotreater stream Go out the weight of thing.

Method the most according to claim 1, close at 15 DEG C of wherein said effectiveness fluid Degree is less than described tar stream density at 15 DEG C.

Method the most according to claim 1, the hydrocarbon of wherein said first mixture include as Under one or more: Petroleum, gas oil, waxiness residual oil, reduced crude, residual oil blend Thing or crude oil.

Method the most according to claim 7, wherein said gas oil is vacuum gas oil (VGO).

Method the most according to claim 1, wherein said first mixture comprises based on Following one or more of the weight >=50.0wt% of one mixture: Petroleum, gas oil, wax Matter residual oil, reduced crude, residual oil mixed compound or crude oil.

Method the most according to claim 9, wherein said gas oil is vacuum gas oil (VGO).

11. methods according to claim 1, wherein said tar stream include (i) >= 10.0wt% be not the molecule with atmospheric boiling point >=565 DEG C of asphalitine and (ii)≤ The metal of 1000.0ppmw, this percetage by weight weight based on this tar stream.

12. methods according to claim 1, wherein said hydroprocessing condition includes as follows One or more: temperature in the range of 350 DEG C to 450 DEG C, pressure at 20 bars to 100 bars In the range of, liquid hourly space velocity (LHSV) is in the range of 0.2-4.0, and hydrogen consumption rate is at 50S m³/m³To 450 S m³/m³In the range of.

13. methods according to claim 1, wherein said effectiveness fluid include quantity >= Isolated liquid phase in the step (f) of 99.0wt%, weight based on effectiveness fluid.

14. methods according to claim 1, wherein the effectiveness fluid of step (e): tar thing Stream weight rate is in the range of 0.10 to 3.0.

15. methods according to claim 1, wherein the effectiveness fluid of step (e): tar thing Stream weight rate is in the range of 0.2 to 3.0.

16. methods according to claim 1, farther include to deflect from from the method second The liquid phase of part, this Part II is used for producing fuel.

17. methods according to claim 1, farther include to provide supplementary effectiveness fluid to arrive Step (d), should to replace at least partially from the effectiveness fluid of liquid phase a part of in step (f) Supplement effectiveness fluid include aromatic compounds and have ASTM D86 10% evaporate point >=120.0 DEG C and 90% evaporates point≤350.0 DEG C.

18. 1 kinds of hydroconversion process, including:

C () separates the tar stream comprising steam cracker tar from described second mixture, its In (i) described tar stream comprise atmospheric boiling point >=290 DEG C in 90.0wt% the second mixture Molecule and (ii) described tar stream have >=the aromatic carbon content of 70.0wt%, and based on described The weight of tar stream；

(e) under the conditions of catalytic hydrogenation treatment at molecular hydrogen and effectiveness fluid: tar stream weight ratio In the presence of the effectiveness fluid of 0.05 to 3.5 scope, at least some of tar stream is exposed to Few a kind of hydrotreating catalyst is to produce hydrotreater effluent；

G () isolates light liquids and heavy liquid, wherein said heavy liquid from described liquid phase There is the molecule of the liquid phase of atmospheric boiling point >=300 DEG C containing 90wt%；

19. methods according to claim 18, wherein said liquid phase comprises >=90.0wt% There is the molecule of the hydrotreater effluent of atmospheric boiling point >=65.0 DEG C, based on hydrotreater The weight of effluent.

20. according to the method described in claim 18 or 19, and wherein said liquid phase comprises >= 90.0wt% has the molecule of the hydrotreater effluent of atmospheric boiling point >=100.0 DEG C, based on adding The weight of hydrogen processor effluent.

21. methods according to claim 18, wherein said liquid phase comprises >=90.0wt% There is the molecule of the hydrotreater effluent of atmospheric boiling point >=150.0 DEG C, based on hydrotreater The weight of effluent.

22. methods according to claim 18, wherein said heavy liquid comprises >= 90.0wt% has the molecule of the liquid phase of atmospheric boiling point >=250.0 DEG C.

23. methods according to claim 18, wherein said heavy liquid comprises >= 90.0wt% has the molecule of the liquid phase of atmospheric boiling point >=350.0 DEG C.

24. methods according to claim 18, also include Part II from the method Light liquids deflect from.

25. 1 kinds of continuous hydroconversion process, including:

B () is pyrolyzed the first mixture and comprises >=the C of 1.0wt% to produce₂Unsaturates and >= Second mixture of 1.0wt% steam cracker tar, this percetage by weight is based on the second mixture Weight, wherein said steam cracker tar has >=the aromatic carbon content of 70.0wt%, base Weight in described steam cracker tar；

(d) under the conditions of operation persistent period >=24 hour catalytic hydrogenation treatment, at effectiveness fluid With 50.0S m³/m³To 890.0S m³/m³In (i) liquid hourly space velocity (LHSV) 1.0 in the presence of molecular hydrogen ×10^-1In the range of 10.0, (ii) temperature is at the scope of 300.0 DEG C to 500.0 DEG C, (iii) Absolute pressure is in the range of 25 bars to 100 bars, and (iv) effectiveness fluid: tar stream weight Amount ratio be in the range of 0.1 to 3.5 by tar weight based on the second mixture >= The tar of 50.0wt% the second mixture is exposed at least one hydrotreating catalyst, to produce Hydrotreater effluent；With

26. continuous hydroconversion process according to claim 25, wherein in continuous operation 100 Through the pressure drop of exposing step (d) not over initial drop more than 300% after hour.