CN103764800A

CN103764800A - Preheating feeds to hydrocarbon pyrolysis products hydroprocessing

Info

Publication number: CN103764800A
Application number: CN201280041823.8A
Authority: CN
Inventors: J·H·毕驰; 徐腾; K·G·里德; D·T·菲卢赫利
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: CN103764800B; WO2013033582A1; EP2751235A1; SG2014011100A; EP2751235B1; CA2845002C; CA2845002A1

Abstract

The invention relates to 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, preheated and subsequently hydroprocessed.

Description

The preheating of charging in the hydrotreatment of hydrocarbon pyrolysis product

The cross reference of related application

It is 61/529 that the application requires the application number that on August 31st, 2011 submits to, application number 565, that on August 31st, 2011 submits to is 61/529, application number 588 and that on June 8th, 2012 submits to is 61/657, the benefit of priority of 299 U.S. Provisional Application, it is all incorporated herein by reference.

Technical field

The present invention relates to upgrading pyrolysis product, from hydrocarbon pyrolysis obtain the method for upgraded product, for the equipment of aforesaid method.

Background technology

Pyrolytic process is such as steam cracking can be for being converted into high value products such as light olefin by stable hydrocarbon, for example, and ethene and propylene.Except these useful products, hydrocarbon pyrolysis can also produce a large amount of low value products relatively such as steam cracking tar (" SCT ").

The SCT method for upgrading that comprises conventional catalytic hydroprocessing is perplexed by significant catalyst deactivation.The method can, at 250 ℃ to 380 ℃ of temperature, pressure 5400kPa to 20, operate under 500kPa, and the catalyzer of use comprises Co, Ni, or one or more in Mo; But observe significant catalyzer coking.Although can operate and reduce catalyzer coking at 200 ℃ to 350 ℃ by rising hydrogen dividing potential drop, reduction space velocity and temperature; But, SCT hydrotreatment is undesirable under these conditions, because improve hydrogen dividing potential drop, increase hydrogen and cost of equipment and cause method variation economically, and because rising hydrogen dividing potential drop, reduction space velocity and reduction temperature have been encouraged undesired hydrogenation.

Summary of the invention

The present invention relates in one embodiment hydrocarbon conversion processes, it comprises:

(a) provide the first mixture, its comprise >=10.0wt.% hydrocarbon, based on the weight of the first mixture;

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

(c) from the second mixture separation tar stream, the wherein molecule of atmospheric boiling point >=290 of the second mixture of comprise >=90wt.% of this tar stream ℃;

(d) provide effectiveness fluid (utility fluid), comprise >=1.0wt.% of this effectiveness fluid aromatic hydrocarbons, based on the weight of effectiveness fluid;

(e) provide the hydrogen stream that comprises molecular hydrogen;

(f) by (i) this tar stream, be exposed to (ii) this effectiveness fluid at 200.0 ℃-400.0 ℃ and be exposed at temperature >=400.0 ℃ and then the effectiveness fluid of this tar stream and heating merged, and/or (iii) this hydrogen stream is exposed at temperature >=400.0 ℃ and then one or more modes in the hydrogen stream merging of this tar stream and heating is heated to this tar stream;

(g) in hydrotreatment region the hydrogen stream of (i) this hydrogen stream and/or heating and (ii) the effectiveness fluid of this effectiveness fluid and/or heating exist lower to effectiveness fluid: tar stream weight ratio is the product of the tar stream that heats of catalytic hydroprocessing condition hydrotreatment at least a portion of 0.05 to 3.0 with generation hydrotreatment, the product content of the hydrotreatment that wherein this effectiveness fluid comprises is >=10.0 % by weight, based on the weight of effectiveness fluid.

The present invention relates in another embodiment hydrocarbon conversion processes, it comprises: the first mixture (a) is provided, and its comprise>=50.0wt.% hydrocarbon, based on the weight of the first mixture; (b) water vapor exist under pyrolysis the first mixture to produce the second mixture, the C of its comprise>=1.0wt.% ₂unsaturates and>=1.0wt.% tar, the weight of this weight percentage based on the second mixture; (c) from the second mixture separation tar stream, the wherein molecule of atmospheric boiling point>=290 of comprise>=90wt.% of this tar stream the second mixture ℃; (d) provide effectiveness fluid, the weight of comprise>=1.0wt.% of this effectiveness fluid aromatic hydrocarbons based on effectiveness fluid; (e) provide the hydrogen stream that comprises molecular hydrogen; (f) by (i), guide this tar stream through at least one well heater; (ii) guide this tar stream through the first channel of at least one interchanger and guide heat-transfer fluid to pass interchanger second passage to extract heat from this heat-transfer fluid to this tar stream, or (iii) heating this effectiveness fluid to temperature>=425.0 ℃ and by one or more modes in the effectiveness fluid merging of this tar stream and heating; (g) under this hydrogen stream and the existence of this effectiveness fluid, in hydrotreatment region, press this tar stream of catalytic hydroprocessing condition hydrotreatment at least a portion, this hydroprocessing condition comprises 300 ℃ to 500 ℃ of temperature ranges, pressure range 15 bar (absolute pressure) are to 135 bar (absolute pressure), and effectiveness fluid: tar weight ratio 0.05-3.0, the product content of this hydrotreatment that wherein (i) this effectiveness fluid comprises is>=50.0wt.%, based on the weight of effectiveness fluid; And (ii) the product content of this hydrotreatment that this heat-transfer fluid comprises is>=50.0wt%, based on the weight of heat-transfer fluid.

Accompanying drawing explanation

Fig. 1 illustrates the process layout for hydrotreating reactor part with schematic diagram, and this reactor part is used effectiveness fluid to assist SCT hydrotreatment.Mark potential high coking region.Fig. 2-4 use schematic diagram illustrates the process layout's example in the scope of the invention.The present invention is not limited to these embodiments, and this specification sheets is not to get rid of the more embodiment in broad range of other the present invention.Fig. 2 illustrates hydrotreating reactor part, and it uses the first reactor region of lesser temps so that reactor preheat sequence coking and fouling danger reduces to minimum.Fig. 3 illustrates hydrotreater reactor part, and it makes tar charging around this reactor feed/effluent interchanger and well heater is adjusted in charging so that coking and fouling risk reduces to minimum.Fig. 4 illustrates hydrotreater reactor part, and the catalyst bed heating of its reactor head makes coking and fouling risk reduce to minimum.Fig. 5 is presented under differing temps size, run through two suite lines of the pressure drop relative time of reactor.

Detailed Description Of The Invention

SCT obtains usually used as hydrocarbon pyrolysis product.This method for pyrolysis can comprise, for example, high temperature pyrolysis, such as the high temperature pyrolysis method of answering water.Above-mentioned a kind of method for pyrolysis, steam cracking is open more in detail below.The present invention is not limited to steam cracking, and describes some embodiment according to steam cracking, is not to get rid of the more method for pyrolysis in broad range of other the present invention.

Part of the present invention can reduce catalyzer coking by hydrotreatment SCT under existing at effectiveness fluid based on finding, this effectiveness fluid comprises a large amount of aromatic hydrocarbons, for example, and list or polycyclic aromatic hydrocarbons.Preliminary heating device coking when requiring heating SCT and effectiveness fluid mixture to desired hydrotreatment temperature simultaneously to avoid doing like this.

Be different from conventional SCT hydrotreatment, the method service temperature and pressure are conducive to desired hydrocarbon hydrocracking reaction and exceed aromatic hydrogenation.This term " SCT " means (a) and has one or more fragrant core and optional (b) hydrocarbon mixture non-aromatics and/or non-hydrocarbon molecule, this mixture is derived from hydrocarbon pyrolysis and boiling range >=approximately 550 °F (290 ℃), for example, SCT molecule atmospheric boiling point >=550 of >=90.0wt% °F (290 ℃).Based on SCT weight, SCT can comprise, and for example>=50.0wt.%, for example>=75.0wt.%, such as>=90.0wt.%, has (i) one or more fragrant cores and (ii) molecular weight>=about C ₁₅hydrocarbon molecule (comprising its mixture and aggregation).

Hydrotreatment SCT has improved the suitability of tar as oil fuel, and this to be viscosity by reducing it improve with the consistency of other oil fuel, reduce it boiling point distribution, improve its hydrogen richness and transform bituminous matter and bituminous matter precursor improves the thermostability of tar thus.The fuel oil product obtaining can be, for example than untreated tar, have the significantly more global business-like alternative product of high value.

Fig. 1 illustrates the hydrotreating reactor part for hydrotreatment SCT with schematic diagram.As shown in Figure 1, in charging stock tank 30, SCT material stream 10 merges 20 with effectiveness fluid, by pump 40 pumpings, through pipeline 50, is then mixed with hydrogeneous material stream 60.This mixture 61 is then arranging the reactor inlet temperature in (process trim) well heater 90 facing to preheating in the interchanger 70 of this reactor effluent 120 succeeded by supplementing to be preheated in technique.Then this preheated mixture 100 is directed into the hydrotreating reactor 110 with three isopyknic in fact catalyst beds 115,116,117.Optionally, in each bed, use same catalyst.This catalyzer can be for example conventional hydrotreating catalyst, such as RT-621, from Albermarle, obtains.

Then this hydrotreater outflow material is flowed through and is introduced to and is left interchanger 70 to one or more segregation section 130 by pipeline 122, for flow out material flow point from this hydrotreater, from (i), via the directed sweeping gas material stream leaving of pipeline 132, (comprise, for example, excessive or with cross processing gas), (ii) via the product of the directed hydrotreatment of leaving of pipeline 134, (comprise, for example, hydrotreatment SCT), and (iii) via pipeline 133, guide the lighter-than-air gas material stream leaving (for example to comprise, methane and hydrogen sulfide) for upgrading and/or use, for example, as combustion gas.Separation in addition can be implemented in separation phase, for example, and for going out light-weight fuel oil and/or heavy oil from the product separation of hydrotreatment.The Supplementary Division body (for example, molecular hydrogen) of regulating the flow of vital energy can enter segregation section 130 via pipeline 131 guiding.Fu Qing processes gas and leaves 130 sections via pipeline 60 guiding, to be recycled to hydrotreater 110.Any H ₂s and NH ₃at least a portion was removed in 130 sections before this processing gas enters pipeline 60.

Although improve thermostability in SCT hydrotreatment, preheating SCT extremely desired reactor inlet temperature exists thermally labile SCT to form fouling risk, such as coking.Above-mentioned coking meeting tends to make this preliminary heating device, Reactor inlet and this catalyst bed top fouling.

Can find out and use quartz filling reactor, for example, when this effectiveness fluid/tar/hydrogen mixture of heating, not produce any catalyzer dirt.This quartz is inertia, to simulate any equipment that is exposed to heated mixt.This reactor is in 400 ℃ and 425 ℃ operation and measure and run through this reactor pressure and fall.It is the signal of indication coking and fouling that Pressure Drop increases in time.Condition is as follows:

Reactor: 3/8OD pipe, 18in. (45.72cm) is long, 12in. (30.48) cm heating

Feed composition: SCT tar 60wt.%; 40wt% Three methyl Benzene effectiveness fluid

Top hole pressure: 1000psi (68.9 bar)

Liquid stream: 0.05cc/min (3ml/hr)

H ₂stream: 26.7sccm (3000scfb charging)

Fig. 5 by the Pressure Drop that runs through this reactor of observing to impinging upon each temperature expression of results of plotting lower working time.Attention Pressure Drop and time scale in two graphic representations are different.At 400 ℃, under these conditions, it is later almost negligible that this Pressure Drop exceedes 80 hours in operation.But, at 425 ℃, operation only after 5 or 6 hours Pressure Drop increase fast, cause reactor operation less than just to be stopped for 27 hours.In 425 ℃ of graphic representations, observed Pressure Drop vibration shows coking and fouling and stops up flowing of charging and hydrogen.

Above-mentioned coking and fouling can limit the conversion process time span of operation continuously.Once coking makes key equipment incrustation, conversion process need to interrupt removing coking.In order to can be used for that this conversion process of industry operation should be able to be moved continuously and at least 1 day, (8.6 × 10 ⁴second), preferably at least 1 week (6.0 × 10 ⁵second), more preferably January (2.6 × 10 at least ⁶second), most preferably at least 1 year (3.2 × 10 ⁷second) do not make the fouling of hydrotreatment overequipment or the excessive coking of hydrotreating catalyst.

For example, for industrial operation, the Pressure Drop that runs through hydrotreating reactor or miscellaneous equipment should be no more than approximately 3.0,4.0 or 5.0 times of under design current velocity initial (SOR) Pressure Drop.

For needing safety limit, industrial operation estimating to occur below the temperature of serious scale.In addition well heater or interchanger metal temperature can be higher than fluid bulk temperatures, and it can cause scorchingger hot metallic surface coking and fouling.Therefore, the desirable maximum value of fluid bulk temperature of tar is set to significantly lower than 425 ℃ of temperature observing excessive incrustation, and for example, scope is 200.0 ℃-400.0 ℃, such as 300.0 ℃-400.0 ℃.In steam cracking, practice shows to keep tar bulk temperature lower than 300 ℃ of equipment coking and fouling risk minimizations.The each embodiment illustration of the present invention keep SCT or the SCT that mixes with effectiveness fluid and/or hydrogen lower than 300 ℃.It will be understood by those skilled in the art that for particular case and can just select than 300 ℃ of higher or lower temperature without undo experimentation.

Specifically, in the embodiment describing at Fig. 1, definite feeding side reactor feed/effluent interchanger 70 under certain condition and Reactor inlet charging arranges well heater (trim heater) 90 and has coking and fouling risk, if SCT, optionally merge preheating at the temperature that exceedes approximately 572 °F (300 ℃) in this equipment with effectiveness fluid and/or molecular hydrogen.Therefore, in certain embodiments, this tar stream 10 enters this hydrotreater and is then heated to 700 °F-800 °F of hydrotreater reactor inlet temperatures (370 ℃-425 ℃) between 200 °F-572 °F (90 ℃-300 ℃).Fig. 1 shows hydrotreatment layout and has tar stream (or the tar merging with effectiveness fluid and/or molecular hydrogen) device location of coking possibility before its hydrogen treatment.In certain embodiments, this effectiveness fluid comprises, for example, and the product of recirculation hydrotreatment in conversion process, or similar material.This effectiveness fluid is heat-staple and is different from fresh (untreated) tar stream, is not inclined to coking in preliminary heating device under 700 °F-800 °F of general reactor preheating temperatures (370 ℃-425 ℃).There is the risk of the coal-tar middle oil component of charging coking and fouling when heating exceedes approximately 572 °F (300 ℃) in the device location highlighting by dashed circle in Fig. 1.

Certain embodiments of the invention are the exploitation based on untreated tar stream (such as SCT) being preheated to the method for hydrotreating reactor temperature in to a certain extent.It alleviates and even eliminates preliminary heating device fouling (or reducing catalyzer coking formation) to allow flow reactor operation.Other embodiment of the present invention is high based on utilizing-exploitation of the hydrogenation of tar treatment process of active catalyst.In this embodiment, for the pre-heat demand in hydrotreatment tar upstream, reduce or eliminate because this hydrotreating catalyst is active enough at a lower temperature.These methods can be used alone or in combination.The further application of method as described below, can allow conversion process to move continuously at least 1 day (8.6 × 10 ⁴second), preferably at least 1 week (6.0 × 10 ⁵second), more preferably January (2.6 × 10 at least ⁶second), or most preferably at least 1 year (3.2 × 10 ⁷second).

The feature of SCT

Have been noted that SCT comprises a large amount of tar heavies (" TH ").With regard to this specification sheets and appended claims, this term " tar heavies " means hydrocarbon pyrolysis product, and TH atmospheric boiling point >=565 ℃ and comprise >=5.0wt.% have the molecule of multiple fragrant cores, based on product weight.TH 25.0 ℃ be generally solid and generally include SCT fraction its at the 25.0 ℃ of Skellysolve A that is insoluble to 5:1 (vol.:vol.) ratio: SCT (" conventional pentane extraction process ").TH can comprise that high molecular weight molecules (for example, MW >=600) is such as bituminous matter and other height-molecular weight hydrocarbon.This term " bituminous matter " is defined as heptane insolubles, and tolerance is according to ASTM D3279.For instance, comprise>=10.0wt.% of TH has by (i) relative low molecular weight alkanes and/or alkene, for example, and C ₁-C ₃alkane and/or alkene, (ii) C ₅and/or C ₆ring paraffinic hydrocarbon (cycloparaffinic) ring, or (iii) high molecular weight molecules of one or more fragrant cores that link together in thiophene (thiophenic) ring.Conventionally, the carbon atom of the TH of >=60.0wt.% is included in one or more fragrant core based on TH carbon atom weight, and for example, scope is 68.0wt.%-78.0wt.%.Do not wish retrained by any particular theory or model simultaneously, it is believed that in addition due to van der waals force between TH molecule, the aggregation that TH forms has relative Two-dimensional morphology.TH aggregation large size, scope is for for example, and their overall dimension ten nanometers are to hundreds of nanometer (" nm "), cause under catalytic hydroprocessing condition aggregation mobility and diffusivity low.In other words, conventional TH transforms and perplexed by harsh quality-transport restrictions, and it causes TH to be converted into the highly selective of coking.Have been found that the SCT that merges effectiveness fluid is decomposed into each molecule by this aggregation, for example, their overall dimension≤5.0nm and molecular weight ranges are between approximately 200 grams every mole to 2500 grams every mole.This causes mobility and diffusivity that in SCT, TH is larger, causes catalyzer-duration of contact shorter under hydroprocessing condition and is converted into coking still less.Therefore, SCT transforms and can under lower pressure, carry out, and for example, 500psig to 1500psig (34.5 to 103.4 bar gauge pressure), causes relatively high pressure hydrotreatment cost and complicacy obviously to reduce.In addition the invention has the advantages that SCT is not excessive fragmentation, so that the light hydrocarbon quantity of preparation for example, C ₄or light, be less than 5wt%, it reduces the quantity of hydrogen consumption in hydrotreating step further.

SCT parent material be different from other higher-hydrocarbon mixture of molecular weight, such as the thick dregs of fat (" residual oil ") had for example not only comprised residual oil normal pressure but also that comprise vacuum and other, the material stream conventionally running in oil and petroleum chemistry processing.The aromatic carbon content of this SCT's passes through ¹³cNMR measures substantially higher than residual oil.For instance, in SCT, the quantity of aromatic carbon is generally greater than 70wt% and is conventionally less than 40wt% in the quantity of aromatic carbon in residual oil.The important fraction atmospheric boiling point of SCT bituminous matter is less than 565 ℃, for instance, SCT1 studies on asphaltene only 32.5wt% atmospheric boiling point very higher than 565 ℃.Vacuum resid is not just like this.Even if solvent extraction is uncompleted method, result shows that the bituminous matter major part in vacuum resid is heavy molecules, and its atmospheric boiling point is higher than 565 ℃.When substantially carrying out heptane solvent extraction under the same condition for vacuum resid, compared with vacuum resid situation, the molecule of (based on weight) atmospheric boiling point <565 ℃ that the bituminous matter obtaining from SCT comprises much higher per-cent.SCT is be metal and nitrogenous compound relative contents different from residual oil in addition.In SCT, total metal content≤1000.0ppmw (1,000,000/, weight) is based on SCT weight, for example, and≤100.0ppmw, for example≤10.0ppmw.Be present in the nitrogen content that nitrogen total amount in SCT is less than thick oily vacuum resid conventionally.

Two typical SCT samples selecting and the performance of three typical residual oil samples are enumerated in following form.

Table 1

* N.M.=undetermined arrives

SCT aromatics carbon content is substantially higher than residual oil.Compared with residual oil, in SCT aliphatic carbon and in long-chain the percentage ratio of carbon substantially lower.Although SCT total carbon is only slightly high and oxygen level (based on wt.) is similar to residual oil, metal, hydrogen and nitrogen content (based on the wt.) scope of SCT is very low.In 50 ℃ of SCT kinematic viscosity (cSt) normally >=1000, or >=100, even if SCT atmospheric boiling point >=565 of relative populations are ℃ much lower compared with vacuum resid situation.

SCT obtains usually used as hydrocarbon pyrolysis product.This pyrolytic process can comprise, for example high temperature pyrolysis, such as utilizing the high temperature pyrolysis method of water.A kind of above-mentioned pyrolytic process, steam cracking are below disclosed more in detail.The present invention is not limited to steam cracking, and this specification sheets is not to get rid of and to utilize other method for pyrolysis within scope widely in the present invention.

By pyrolysis, obtain SCT

Pyrolyzer is used in conventional steam cracking, and it has two major sections: convection zone and radiation section.The convection zone that this raw material charging (the first mixture) generally enters stove wherein the hydrocarbon component of the first mixture by indirect contact from this radiation section hot flue gas and directly contact the heated and vaporization of the steam component of this first mixture.Then this steam-vaporised hydrocarbon mixture is introduced into this radiation section, and most of cracking is in wherein carrying out.Guide the second mixture to leave pyrolyzer, the second mixture comprises by the product of the first mixture pyrolysis generation and any unreacted component of the first mixture.Common at least one segregation section is positioned at this pyrolyzer downstream, and this segregation section is for going out one or more of light olefin, SCN, SCGO, SCT, water, the first mixture unreacting hydrocarbon component etc. from the second mixture separation.This segregation section can comprise for example primary fractionator.Conventionally, cooling section, general direct quenching or indirect heat exchange are between this pyrolyzer and this segregation section.

In one or more embodiments, SCT is as for example, at one or more pyrolyzer, the product of carrying out pyrolysis and obtaining in one or more steam cracking furnaces.Except SCT, above-mentioned stove conventionally produce (i) gaseous product such as in acetylene, ethene, propylene, butylene one or more, and (ii) liquid product comprise, for example, one or more C ₅₊molecule and composition thereof.This liquid product guides to segregation section conventionally together, for example, and primary fractionator, one or more for separating of (a) and (b), (a) are overhead fraction, and it comprises steam-cracking naphtha (" SCN ", for example, C ₅-C ₁₀material) and steam cracking gas oil (" SCGO "), based on SCGO weight, comprise>=90.0wt.% of this SCGO normal pressure boiling range is molecule (for example, the C of approximately 400 °F-550 °F (200 ℃-290 ℃) ₁₀-C ₁₇material), and (b) be bottoms, its comprise>=90.0wt.%SCT, based on bottoms weight, SCT boiling range>=approximately 550 °F (290 ℃) and comprise molecular weight>=about C ₁₅molecule and composition thereof.

To the charging of this pyrolyzer be the first mixture, comprise >=10.0wt.% of the first mixture hydrocarbon, based on the first mixture weight, for example, >=25.0wt.%, >=50.0wt.%, such as >=65.0wt.%.Although this hydrocarbon can comprise, for example, one or more lighter hydrocarbons are such as methane, ethane, propane, butane etc., and useful is especially to be combined application the present invention with the first mixture that comprises a large amount of high-molecular-weight hydrocarbons because these molecule pyrolysis produce conventionally than the more SCT of low molecular weight hydrocarbon pyrolysis.For instance, useful is for the first amount of the mixture be fed to multiple pyrolyzer with comprise >=1.0wt.% or >=25.0wt.% hydrocarbon in liquid phase under envrionment temperature and barometric point, based on the first mixture weight.

In addition, the first mixture can comprise thinner, for example, in nitrogen, water etc. one or more.For example, >=1.0wt.% thinner, based on the first mixture weight, such as >=25.0wt.%.When this pyrolysis is steam cracking, the first mixture can and comprise steam diluent combination by this hydrocarbon and prepare, for example, and the every kg hydrocarbon of ratio 0.1-1.0kg steam, or the every kg hydrocarbon of ratio 0.2-0.6kg steam.

In one or more embodiments; comprise >=10.0wt.% of the hydrocarbon of the first mixture; for example; >=50.0wt.%, such as one or more in >=90.0wt.% (based on hydrocarbon composition weight) petroleum naphtha, gas oil, vacuum gas oil, wax-like residual oil, long residuum, mixtures of residua or crude oil; Comprise comprising >=about 0.1wt.% bitum those.Suitable crude oil comprises, for example, the original crude oil of height-sulphur, such as being rich in those of polynuclear aromatics.Optionally, the hydrocarbon of the first mixture comprises sulphur, and for example, >=0.1wt.% sulfenyl is in the hydrocarbon composition weight of the first mixture, and for example, >=1.0wt.%, such as scope is that about 1.0wt.% is to about 5.0wt.%.Optionally, the sulfur-containing molecules 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 (" aromatic hydrocarbons sulphur ").When the hydrocarbon of (i) first mixture is crude oil or the crude oil fraction of comprise >=0.1wt.% aromatic hydrocarbons sulphur and (ii) when this pyrolysis is steam cracking, SCT comprises a large amount of sulphur derived from the first mixture aromatic hydrocarbons sulphur.For example, based on weight, in SCT, SCT sulphur content can be than the high about 3-4 of the hydrocarbon component of the first mixture doubly.

In specific embodiments, the hydrocarbon of the first mixture comprises one or more crude oil and/or one or more crude oil fractions, such as from normal pressure pipe still (" APS ") and/or vps vacuum pipe-still (" VPS "), obtain those.The optionally desalination before being included into the first mixture of this crude oil and/or its fraction.The crude oil fraction example that the first mixture is used produces by the APS bottoms combination of processing by the APS bottoms from crude separation and succeeded by VPS.

Optionally, this pyrolyzer has at least one vapour/liquefaction tripping device (being sometimes referred to as flash vaporization kettle or flash tank) of integrating with it, for upgrading the first mixture.When the hydrocarbon composition weight of comprise >=about 0.1wt.% bituminous matter of the hydrocarbon component of the first mixture based on the first mixture, for example, during >=about 5.0wt.%, above-mentioned vapour/liquefaction tripping device is specially suitable.Can complete these with conventional vapour/liquefaction tripping device, but the present invention is also not limited to this.It is 7,138,047 that the example of above-mentioned conventional vapour/liquefaction tripping device is included in the patent No.; 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, those disclosed in 705 United States Patent (USP)s, it all introduces the application as a reference.Suitable vapour/liquefaction tripping device is also disclosed in U.S. Pat 6,632, and in 351 and US7,578,929, it all introduces the application as a reference.Conventionally, when using vapour/liquefaction tripping device, the gas phase composition that leaves this device is substantially identical with the gas phase composition that enters this device, and it is substantially identical with the liquid phase composition that enters this device similarly to leave this flash tank liquid phase composition, that is, gas/liquid tripping device separates and substantially the two-phase physical sepn that enters this tank, consists of.

In the embodiment of using with the gas/liquid tripping device of pyrolyzer combination, hydrocarbon component at least a portion of the first mixture is provided to the import of pyrolysis unit convection zone, wherein heat hydrocarbon so that this hydrocarbon of at least a portion in gas phase.For example, when (steam) is used thinner, the thinner composition optional (but preferably) of the first mixture adds this section and mixes to produce the first mixture that first mixture at least a portion is gas phase with this hydrocarbon component,, then at least one gas/liquid tripping device flash distillation leaving the molecule of the high molecular of at least a portion the first mixture from the first mixture separation and guiding, such as bituminous matter.At the bottom of tower, fraction can be left from the guiding of this steam-liquid separation device, and at the bottom of this tower, fraction comprises, for example, and the bituminous matter of >=10.0% (based on weight) first mixture.When this pyrolysis hydrocarbon component that is steam cracking and this first mixture comprise one or more crude oil or and level timesharing, this steam cracking furnace can combine with gas/liquid tripping device, this gas/liquid tripping device temperature range of operation is that approximately 600 °F (315 ℃) to approximately 950 °F (510 ℃) and pressure range are that about 275kPa is to about 1400kPa, for example, temperature range is that approximately 430 ℃ to approximately 480 ℃ and pressure range are about 700kPa to 760kPa.Overhead fraction from gas/liquid tripping device can further heat in convection zone, and within then introducing radiation section via crossover pipe (crossover piping), wherein overhead fraction is exposed to temperature >=760 ℃ under pressure >=0.5 bar (g), for example, temperature range is that approximately 790 ℃ to approximately 850 ℃ and pressure range are that approximately 0.6 bar (g) is to approximately 2.0 bar (g), for example, to implement the hydrocarbon component pyrolysis (cracking and/or reformation) of the first mixture.

One of convection zone import downstream and advantage of having gas/liquid tripping device to the crossover pipe upper reaches of radiation section are that it has for example increased the kind scope of the hydrocarbon that just can directly use as the first mixture hydrocarbon component without pre-treatment, can the comprise >=50.0wt.% of hydrocarbon component of the first mixture, for example, >=75.0wt.%, such as >=one or more crude oil of 90.0wt.% (the hydrocarbon composition weight based on the first mixture), crude oil and the fraction thereof of even higher naphthenic acid content.The charging with high naphthenic acid content is one of those of a large amount of tar of preparation and is specially suitable when at least one gas/liquid tripping device and pyrolyzer combination.If requirement, the composition of the first mixture can change in time, for example, by application during the cycle very first time, there is the first mixture of the first hydrocarbon component, then the first mixture that application has the second hydrocarbon component is during the second time cycle, and the first and second hydrocarbon is in fact different hydrocarbon or different hydrocarbon mixture substantially.First and can there is the substantially equal time second cycle, but this is dispensable.The first and second periods alternately can be implemented (for example, in " sealing " operation) continuously or semi-continuously, if asked.Can use the order pyrolysis of this embodiment for inconsistent the first and second hydrocarbon components (that is, wherein the first and second hydrocarbon components are mixtures, and it is not enough to compatible to blending under envrionment conditions).For example, the first hydrocarbon component that comprises original crude oil can during the cycle very first time in order to prepare the first mixture and during the second time cycle steam cracking tar in order to prepare the first mixture.

In other embodiment, do not use gas/liquid tripping device.One or more grade of timesharing that comprises crude oil and/or crude oil when the hydrocarbon of the first mixture for instance, this pyrolytical condition can be conventional steam cracking condition.Suitable steam cracking condition comprises, for example, the first mixture is exposed to temperature (measuring in heating outlet) >=400 ℃, and for example, scope is 400 ℃-900 ℃, and pressure >=0.1 bar, cracking residence time periodic regime approximately 0.01 second to 5.0 seconds.In one or more embodiments, the first mixture comprises hydrocarbon and thinner, the wherein weight of the hydrocarbon based on the first mixture, in the wax-like residual oil of comprise >=50.0wt.% of the hydrocarbon of the first mixture, long residuum, petroleum naphtha, mixtures of residua or crude oil one or more.This thinner comprises, and for example, >=95.0wt.% water, based on the weight of thinner.When the first mixture comprises 10.0wt.%-90.0wt.% thinner, based on the weight of the first mixture, this pyrolytical condition generally comprises 760 ℃-880 ℃ of (i) temperature ranges; (ii) pressure range 1.0-5.0 bar (absolute pressure), or (iii) cracking residence time scope is one or more in 0.10-2.0 second.

From pyrolyzer, guide the second mixture to leave, the second mixture is derived from the first mixture by pyrolysis.When using regulation pyrolytical condition, the C of 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 comprise>=5.0wt.% of the second mixture ₂unsaturates and/or>=TH of 0.5wt.%, such as the TH of>=1.0wt.%.For example, although the second mixture generally comprises the needed light olefin of mixture, SCN, SCGO, SCT and the unreacted component of the first mixture (water in steam cracking situation, and unreacted hydrocarbon sometimes), in these, relative quantity generally depends on separately, for example, the composition of the first mixture, pyrolyzer layout, processing condition etc. during pyrolysis.Conventionally guiding is left the second mixture for pyrolysis section, for example, and for cooling and segregation section.

In one or more embodiments, comprise >=10.0wt.%TH of the TH of the second mixture aggregation, this aggregation is mean particle size 10.0nm-300.0nm and carbon atom mean number >=50 at least one dimension, the tar heavies weight of this weight percentage based on the second mixture is common, comprise >=50.0wt.% of this aggregation, for example, >=80.0wt.%, such as the TH molecule of >=90.0wt.%, the C:H atomic ratio scope of this TH molecule is 1.0-1.8, molecular weight ranges 250-5000, and 100 ℃-700 ℃ of melting ranges.

Although do not require, it is cooling that the present invention is applicable to pyrolyzer downstream side the second mixture, for example, can use system cools the second mixture that comprises transfer line interchanger.For example, it is approximately 700 ℃-350 ℃ that this transfer line interchanger can be cooled to this process stream temperature, and for the efficient hyperpressure steam that produces, it can be used or directed leaving by the method.If asked, generally position between this furnace outlet and this segregation section, the second mixture can carry out direct quenching.The second mixture contact liq quench stream replaces or with transfer line exchanger processing, can complete this quenching in addition.If used in conjunction with at least one transfer line exchanger, this quench liquid is preferably introduced position, transfer line exchanger downstream side.Suitable quench liquid comprises liquid quench oil, such as by downstream side quenching oil gas-liquid separator (knock-out drum), pyrolysis fuel oil and water, obtain those, it can obtain from the dilution steam generation of conventional source, for example condensation.

Segregation section conventionally in lower pyrolyzer trip side and transfer line exchanger downstream side and/or quenching location application for separating of one or more in the second mixture light olefin, SCN, SCGO, SCT or water.In segregation section, can use conventional separating device, for example, one or more flash tanks, fractionator, water quick cooling tower, indirect condenser etc., such as being disclosed in U.S. Pat 8,083, those in 931.In segregation section, can be from the second mixture separation as the 3rd mixture of tar stream, make the TH of the 3rd comprise >=10.0wt.% of mixture tar stream the second mixture, the TH weight based on the second mixture.When this pyrolysis is steam cracking, this tar stream generally comprises SCT, it obtains certainly, for example, the tower bottoms stream of the steam crackers of SCGO material stream and/or primary fractionator, flash tank bottom thing (for example, being positioned at the bottom material of one or more flash tank of pyrolyzer downstream side and primary fractionator upstream side), or its combination.

In one or more embodiments, the TH of comprise >=50.0wt.% of this tar stream the second mixture, the TH weight based on the second mixture.For example, the TH of can comprise >=90.0wt.% of this tar stream the second mixture, the TH weight based on the second mixture.This tar stream can have, for example, (i) sulphur content scope 0.5wt.-7.0wt.%, (ii) TH content range is 5.0wt.%-40.0wt.%, this weight percentage, based on tar stream weight, is (iii) 1.01g/cm 15 ℃ of density ranges ³-1.15g/cm ³, for example, 1.07g/cm ³-1.15g/cm ³, and (iv) 50 ℃ of range of viscosities 200cSt-1.0x10 ⁷cSt.

This tar stream can comprise TH aggregation.In one or more embodiments, the TH aggregation of comprise >=50.0wt.% of this tar stream the second mixture, the TH aggregation weight based on the second mixture.For example, the TH aggregation of can comprise >=90.0wt.% of this tar stream the second mixture, the TH aggregation weight based on the second mixture.

This tar stream is left for tar stream hydrotreatment effectiveness fluid exists from this segregation section guiding conventionally.Now open for effectiveness examples of fluids of the present invention.The present invention is not limited to these effectiveness fluids of application, and this specification sheets is not other effectiveness fluid that will get rid of in broad range of the present invention.

Effectiveness fluid

In this tar stream of hydrotreatment, use this effectiveness fluid, for example, for effectively increasing duration of runs during hydrotreatment and improving the product property of hydrotreatment.Effectively effectiveness fluid aromatic hydrocarbons, comprises the molecule with at least one fragrant core that is.In one or more embodiments comprise >=40.0wt.% of this effectiveness fluid aromatic carbon, such as >=60.0wt.% aromatic carbon, by NMR, measure.Hydrotreater is got back in liquid phase, effective recirculation of the product that this effectiveness fluid comprises a part of hydrotreatment in one or more embodiments.All the other hydrotreatment product liquid phases can guide from this process leaves and is optionally used as low sulphur fuel oil blend component.The product of this hydrotreatment can optionally pass through one or more segregation section.Segregation section limiting examples can comprise: flash tank, distillation tower, vaporizer, stripper, steam stripped device, vacuum flashing or vacuum tower.These segregation sections allow that those skilled in the art adjust the performance as the liquid phase of effectiveness fluid.The weight of the product of the molecule that can comprise >=90.0wt.% of the liquid phase of the product of hydrotreatment has a product of the hydrotreatment of four carbon atom at least based on hydrotreatment.In other embodiment, in the product of comprise >=90.0wt.% of this liquid phase hydrotreatment, there are atmospheric boiling point >=65.0 ℃, >=150.0 ℃, the molecule of >=260.0 ℃, the weight of the product based on hydrotreatment.

In another embodiment, the whole liquid phase separation of the product of hydrotreatment are light weight fluid and heavy liquid, and wherein heavy liquid comprises 90wt.% atmospheric boiling point >=300 ℃ molecule, and it is present in this liquid phase.This effectiveness fluid comprises a part, and this separates the light weight fluid obtaining.Optionally, in other embodiment, the effectiveness fluid of the product that comprises hydrotreatment can add or replace with the supplementary effectiveness fluid such as following.

In other embodiment, this effectiveness fluid comprises aromatic hydrocarbons (that is, comprising the molecule with at least one fragrant core) and ASTM D8610% distillation point >=60 ℃ and 90% distillation point≤350 ℃.Optionally, this effectiveness fluid (it can be solvent or solvent mixture) ASTM D8610% distills point >=120 ℃, for example, >=140 ℃, such as >=150 ℃ and/or ASTM D8690% distillation point≤300 ℃.

In one or more embodiments, this effectiveness fluid (i) critical temperature is 285 ℃-400 ℃ and (ii) 1-Polycyclic aromatic hydrocarbons and/or the 2-Polycyclic aromatic hydrocarbons of comprise >=80.0wt.%, comprise its alkyl functional derivative, based on the weight of effectiveness fluid.For example, this effectiveness fluid can comprise, and for example, >=90.0wt.% is mono--Polycyclic aromatic hydrocarbons, comprise those with one or more hydrocarbon substituents, such as 1-3 or 1-2 hydrocarbon substituent.Above-mentioned substituting group can be any hydrocarbyl group, and it is consistent with the overall distillation characteristics of this effectiveness fluid.Above-mentioned hydrocarbyl group example includes but are not limited to, C ₁-C ₆alkyl, wherein this alkyl can side chain or straight chain and this hydrocarbyl group can be identical or different.Optionally, based on the weight of effectiveness fluid, for example, for example, in comprise >=90.0wt.% of this effectiveness fluid ethylbenzene, Three methyl Benzene, dimethylbenzene, toluene, naphthalene, alkylnaphthalene (methylnaphthalene), tetralin or alkyl tetralin (methyl tetralin) one or more.Conventionally need to not basically contain the molecule with alkenyl functionality by this effectiveness fluid, in the embodiment under above-mentioned molecule exists, applying especially hydrotreating catalyst has the trend that forms coking.In embodiments, based on the weight of effectiveness fluid, comprise≤10.0wt.% of this effectiveness fluid ring compound, this ring compound has C ₁-C ₆side chain, this side chain has alkenyl functionality.

In certain embodiments, this effectiveness fluid is included in SCN and/or the SCGO from the second mixture separation in the downstream side primary fractionator of the pyrolyzer moving under steam cracking condition, for example, and SCN and/or SCGO.This SCN or SCGO can be in different conventional hydrotreaters hydrogen treatment (for example not hydrogen treatment together with this tar).This effectiveness fluid can comprise, and for example >=50.0wt.% separates gas oil, based on the weight of effectiveness fluid.In certain embodiments, at least a portion effectiveness fluid obtains from the product of hydrotreatment, for example, and by separating and the product of the hydrotreatment of recirculation part atmospheric boiling point≤300 ℃.

Conventionally, this effectiveness fluid comprises sufficient amount molecule, and it has one or more fragrant core effectively to increase the cycle of operation during hydrotreatment.For example, the molecule of can comprise >=50.0wt.% of this effectiveness fluid, it has at least one fragrant core, for example, >=60.0wt.%, such as >=70wt.%, based on effectiveness fluid gross weight.In embodiments, this effectiveness fluid comprises (i)>=60.0wt.% and has the C of the molecule of at least one fragrant core and (ii)≤1.0wt.% ₁-C ₆side chain has alkenyl functionality, the weight of this weight percentage based on effectiveness fluid.

In this tar stream of hydrotreatment, use this effectiveness fluid, for example, for being effectively increased in the cycle of operation during hydrotreatment.During hydrotreatment, the normally about 20.0wt.% of effectiveness fluid and tar stream relative populations, to about 95.0wt.% tar stream and extremely about 80.0wt.% effectiveness fluid of about 5.0wt.%, adds tar stream gross weight based on effectiveness fluid.For example, during hydrotreatment effectiveness fluid and tar stream relative populations normally (i) about 20.0wt.% to about 90.0wt.% tar stream and about 10.0wt.% to about 80.0wt.% effectiveness fluid, or (ii) about 40.0wt.% to about 90.0wt.% tar stream and about 10.0wt.% to about 60.0wt.% effectiveness fluid.Optionally, effectiveness fluid in hydrotreater charging: tar weight ratio 0.05:1.0-3.0:1.0.This effectiveness fluid of at least a portion can merge with this tar stream of at least a portion within this hydrotreatment container or hydrotreatment region, but this is dispensable, and in one or more embodiments this effectiveness fluid of at least a portion and this tar stream of at least a portion as separate material flow, supply with and entering before (for example) this hydrotreatment container or upstream, hydrotreatment region) be merged into a feed steam.In certain embodiments, comprise 40.0wt.%-90.0wt.%SCT and 10.0wt.%-60.0wt.% effectiveness fluid, the weight of this weight percentage based on feed steam to the feed steam of this hydrotreater.

Hydrotreatment

Under effectiveness fluid exists, tar stream hydrotreatment can be carried out in one or more hydrotreatment sections, and this section comprises one or more hydrotreatment containers or region.Container and/or the region of wherein carrying out within the hydrotreatment section of catalytic hydroprocessing operation generally comprise at least one hydrotreating catalyst.This catalyzer can mix or be stacking, such as when this catalyzer is one or more fixed bed form in container or hydrotreatment region.

Conventional hydrotreating catalyst can be for this tar stream of hydrotreatment under existing at effectiveness fluid, and such as specifying those that are used for residual oil and/or heavy-oil hydrogenation processing, but the present invention is not restricted to this.Suitable hydrotreating catalyst comprises that those comprise (i) one or more base metals (bulk metals) and/or (ii) metal on one or more carriers.This metal can be element form or compound form.In one or more embodiments, this hydrotreating catalyst comprise at least one metal periodictable 5-10 family element (as the Periodic Chart of the Elements announce, The Merck Index, Merck & Co., Inc., 1996).Above-mentioned catalyst metal example includes but are not limited to, vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, or its mixture.

In one or more embodiments, at least 0.0001 gram of the catalyzer that these catalyzer 5 family of family to 10 total metal contents are every gram, or at least 0.001 gram or at least 0.01 gram, wherein grams is calculated based on element.For example, it is 0.0001 gram-0.6 gram that this catalyzer comprises 5-10 family total metal content scope, or 0.001 gram-0.3 gram, or 0.005 gram-0.1 gram, or 0.01 gram-0.08 gram.In specific embodiment, this catalyzer further comprises at least one 15 family's elements.Preferably 15 family's element examples are phosphorus.When using 15 family element, this catalyzer comprises that the total amount of 15 family's elements is 0.000001 gram-0.1 gram, or 0.00001 gram-0.06 gram, or 0.00005 gram-0.03 gram, or 0.0001 gram-0.001 gram, wherein grams is calculated based on element.

In embodiments, this catalyzer comprises at least one 6 family's metal.Preferably 6 family's metal examples comprise chromium, molybdenum and tungsten.The total amount of 6 family's metals that this catalyzer can comprise is at least 0.00001 gram of every gram of catalyzer, or at least 0.01 gram, or at least 0.02 gram, wherein grams is calculated based on element.For example, 6 family's total metal contents that this catalyzer can comprise are 0.0001 gram-0.6 gram of every gram of catalyzer, or 0.001 gram-0.3 gram, or 0.005 gram-0.1 gram, or 0.01 gram-0.08 gram, grams is based on element calculating number.

In relevant embodiment, this catalyzer comprises at least one 6 metal and further comprises at least one 5 family, 7 families, 8 families, 9 families or 10 family's metals.Above-mentioned catalyzer can comprise 6 family's metallographic phase for example to 0.1 to 20,1 to 10 or 2 to 5 the metallic combination in molar ratio of 5 family's metals, and wherein this ratio calculates based on element.Alternatively, this catalyzer comprises that for example 6 family's metallographic phase are to 0.1 to 20,1 to 10 or 2 to 5 the metallic combination in molar ratio of 7-10 family metal, and wherein this ratio calculates based on element.

When this catalyzer comprises at least one 6 family's metal and one or more 9 families or 10 family's metals, for example molybdenum-cobalt and/or tungsten-nickel, these metals, for example, by 6 family's metallographic phase, to the molar ratio of 9 and 10 family's metals, be that 1-10 or 2-5 exist, wherein this ratio calculates based on element.When this catalyzer comprises at least one 5 family's metal and at least one 10 family metal, these metals, can be that 1-10 or 2-5 exist to 10 family's metal molar ratios by for example 5 family's metallographic phase, and wherein ratio calculates based on element.Within the scope of the invention, catalyzer also comprises inorganic oxide, for example, as bonding agent and/or carrier.For example, this catalyzer can comprise one or more metals of (i) >=1.0wt.%, and it is selected from periodictable 6 families, 8 families, 9 families and 10 families and (ii) >=1.0wt.% inorganic oxide, the weight of this weight percentage based on catalyzer.

The present invention comprises and is incorporated into carrier (or thereon deposition) one or catalyst metal, and for example one or more 5 family-10 families and/or 15 family's metals are to form hydrotreating catalyst.This carrier is a kind of porous material.For example, this carrier can comprise one or more refractory oxides, porous carbon-sill, zeolite or its combination.Suitable refractory oxides comprises, for example, aluminum oxide, silicon-dioxide, silica-alumina,, titanium dioxide, zirconium white, magnesium oxide, and composition thereof.Suitable porous carbon-sill comprises, activated carbon and/or porous graphite.Zeolite examples comprises, for example, and Y-zeolite, β zeolite, mordenite, ZSM-5 zeolite, and ferrierite.The other example of solid support material comprises gamma-alumina, θ aluminum oxide, δ aluminum oxide, α-aluminum oxide or its combination.The support of the catalyst of every gram, the quantity of gamma-alumina, δ aluminum oxide, α-aluminum oxide or its combination, can be 0.0001 gram-0.99 gram, or 0.001 gram-0.5 gram, or 0.01 gram-0.1 gram, or 0.1 gram at the most, by X-ray diffraction, measure.In specific embodiment, this hydrotreating catalyst is CatalystT, and this carrier comprises at least one aluminum oxide, for example, θ aluminum oxide, content is 0.1 gram-0.99 gram, or 0.5 gram-0.9 gram, or 0.6 gram-0.8 gram, this quantity is every gram of carrier.The quantity of aluminum oxide can be to use, and for example X-ray diffraction is measured.In the embodiment of replacing, this carrier can comprise at least 0.1 gram, or at least 0.3 gram, or at least 0.5 gram, or at least 0.8 gram of θ aluminum oxide.

When using carrier, this carrier can infiltrate needed metal to form this hydrotreating catalyst.Before impregnating metal, this carrier can be through 400 ℃-1200 ℃ or 450 ℃-1000 ℃ or 600 ℃ of-900 ℃ of heat treated.In certain embodiments, this hydrotreating catalyst can form by adding to the in type carrier mixture through heat treated or in conjunction with 5 family-10 family metals.This class forms and is commonly referred to covering metal on this solid support material.Optionally, after this carrier is in conjunction with one or more these catalyst metal for example at 150 ℃-750 ℃ or 200 ℃-740 ℃ or 400 ℃ of-730 ℃ of these catalyzer of heat treated.Optionally, this catalyzer at 400 ℃-1000 ℃ under the air of warm air and/or oxygen enrichment exists heat treated to remove volatile matter, make at least a portion 5-10 family metallic transition as they corresponding metal oxides.In other embodiment, this catalyzer can (for example, air) in 35 ℃-500 ℃ or 100 ℃-400 ℃ or 150 ℃-300 ℃ heat treated under oxygen exists.The time that thermal treatment can be carried out 1-3 hour does not make 5 family-10 family metals be converted into their metal oxide form to remove most of volatile constituent.The catalyzer of preparing by aforesaid method is commonly referred to " not calcining " or " being dried " catalyzer.Can prepare above-mentioned catalyzer with formation sulfide Combination of Methods, 5 family-10 family metals are dispersed among carrier substantially.When this catalyzer comprises θ alumina supporter and one or more 5 family-10 families metal, this catalyzer generally at >=400 ℃ thermal treatment to form this hydrotreating catalyst.Generally, at≤1200 ℃, implement above-mentioned thermal treatment.

This catalyst shape can be, for example, disk, one or more in pellet, extrudate etc., although these are dispensable.The limiting examples of above-mentioned shape comprises those symmetrical right cylinders, its diameter is that about 0.79mm is to about 3.2mm (1/32-1/8 inch), about 1.3mm is to about 2.5mm (1/20-1/10 inch), or about 1.3mm is to about 1.6mm (1/20-1/16 inch).The shape of the non-cylinder of equally-particle diameter within the scope of the present invention, for example, the shape of three leaves, quaterfoil shape etc.Optionally, the dull and stereotyped crushing strength of this catalyzer (flat plate crush strength) is 50-500N/cm, or 60-400N/cm, or 100-350N/cm, or 200-300N/cm, or 220-280N/cm.

The catalyzer of porous, including having those of conventional stomata characteristics, within the scope of the invention.When using porous catalyst, the vesicular structure of this catalyzer, aperture, pore volume, hole shape, aperture surface area etc., within the scope of conventional hydrotreating catalyst sign, although the invention is not restricted to this.For example, this catalyzer aperture intermediate value is that effectively above-mentioned catalyzer aperture intermediate value scope is 30 dust-1000 dusts, or 50 dust-500 dusts, or 60 dust-300 dusts for hydrotreatment SCT molecule.Aperture can be measured according to ASTM method D4284-07 mercury penetration method.

In specific embodiment, these hydrotreatment aperture intermediate value 50 dust-200 dusts.Alternatively, these hydrotreatment aperture intermediate value 90 dust-180 dusts, or 100 dust-140 dusts, or 110 dust-130 dusts.In another embodiment, these hydrotreatment aperture intermediate value 50 dust-150 dusts.Alternatively, these hydrotreatment aperture intermediate value 60 dust-135 dusts, or 70 dust-120 dusts.In another alternative embodiment, use the more hydrotreating catalyst of wide aperture intermediate value, for example, aperture intermediate value 180 dust-500 dusts, or 200 dust-300 dusts, or those of 230 dust-250 dusts.

Conventionally, hydrotreating catalyst pore size distribution is not wide, so that reduces indistinctively catalyst activity or selection rate.For example, hydrotreating catalyst has pore size distribution, and wherein the aperture at least 60% hole is within 45 dusts, 35 dusts or 25 dust aperture intermediate values.In certain embodiments, these catalyzer aperture intermediate value 50 dust-180 dusts or 60 dust-150 dusts, and the aperture at least 60% hole is within 45 dusts, 35 dusts or 25 dust aperture intermediate values.

When using porous catalyst, this catalyst pore volume, for example>=0.3cm ³/ g, as>=0.7cm ³/ g, or>=0.9cm ³/ g.In certain embodiments, pore volume is, for example, and 0.3cm ³/ g-0.99cm ³/ g, 0.4cm ³/ g-0.8cm ³/ g, or 0.5cm ³/ g-0.7cm ³/ g.

In certain embodiments, relatively large surface-area is desirable.For instance, hydrotreating catalyst surface-area>=60m ²/ g, or>=100m ²/ g, or>=120m ²/ g, or>=170m ²/ g, or>=220m ²/ g, or>=270m ²/ g; Such as 100m ²/ g-300m ²/ g, or 120m ²/ g-270m ²/ g, or 130m ²/ g-250m ²/ g, or 170m ²/ g-220m ²/ g.

Use and specify hydrotreating catalyst hydrotreatment specified amount tar and effectiveness fluid to cause improving catalyst life, for example, allow this hydrotreatment section operation at least 3 months (7.8 × 10 ⁶second), or at least 6 months (1.6 × 10 ⁷second), or at least 1 year (3.2 × 10 ⁷second) and without the catalyzer substituting in hydrotreatment or zone of action.Catalyst life is conventionally than the multiple >10 that does not use the situation of effectiveness fluid to grow, and for example, >=100 times of length, such as length >=1000 times.

Under existing, hydrogen carries out hydrotreatment, for example, by (i) hydrotreatment upstream, merge molecular hydrogen and this tar stream and/or effectiveness fluid and/or (ii) in one or more pipelines or pipeline, guide molecular hydrogen to this hydrotreatment section.Although purified molecule hydrogen can be for this hydrotreatment relatively, but conventionally desirable is that application " is processed gas ", it for this hydrotreatment and optional other mass (for example comprises enough molecular hydrogens, nitrogen and lighter hydrocarbons are such as methane), it generally can not adversely hinder or affect this reaction or this product.Generally remove unwanted such as H ₂s and NH ₃and so on impurity after, no processing gas can be with the product separation of hydrotreatment for applying again.Optionally comprise >=about 50vol.% molecular hydrogen of this processing gas, for example, >=about 75vol.%, enters the processing volume of gas of this hydrotreatment section based on guiding.

Optionally, the quantity that offers the molecular hydrogen of this hydrotreatment section is about 300SCF/B (every barrel of standard cubic foot) (53S m ³/ m ³) to 5000SCF/B (890S m ³/ m ³), wherein B refers to tar stream bucket.For example, the molecular hydrogen that provides is 1000SCF/B (178S m ³/ m ³) to 3000SCF/B (534S m ³/ m ³).Under the appointment hydrotreating catalyst of specifying effectiveness fluid, molecular hydrogen and effective catalytic amount exists, the product of the hydrotreatment that under catalytic hydroprocessing condition prepared by hydrotreatment tar stream comprises, for example, and upgrading SCT.Suitable catalytic hydroprocessing condition example is now disclosed more in detail.The present invention is not limited to these conditions, and this specification sheets is not other hydroprocessing condition that will get rid of in broad range of the present invention.

This hydrotreatment is implemented conventionally under hydroconversion process condition, for example,, under one or more condition of the hydrocracking for implementing to specify tar stream (including selecting hydrocracking), hydrogenation, hydrotreatment, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), Hydrodearomatization, hydroisomerization or Hydrodewaxing.This hydrotreatment reaction can be carried out at least one container or region, and it is positioned at, for example, and within the hydrotreatment section of pyrolysis section and the downstream of segregation section.This appointment tar stream generally contacts hydrotreating catalyst in container or region under effectiveness fluid and molecular hydrogen existence.Operable catalytic hydroprocessing condition can comprise, for example, the thinner-tar stream of merging is exposed to 50 ℃-500 ℃ or 200 ℃-450 ℃ or 220 ℃-430 ℃ or 350 ℃-420 ℃ and approaches molecular hydrogen and hydrotreating catalyst.For example, temperature range is 300 ℃-500 ℃, or 350 ℃-430 ℃, or 360 ℃-420 ℃.Effectiveness fluid tar stream weight hourly space velocity (WHSV) general range merging is 0.1h ^-1-30h ^-1, or 0.1h ^-1-25h ^-1, or 0.1h ^-1-4.0h ^-1.In some embodiments, LHSV is at least 0.1h ^-1, 5h ^-1, or 10h at least ^-1, or 15h at least ^-1.During hydrotreatment, the common scope of molecular hydrogen dividing potential drop is 0.1MPa-8MPa, or 1MPa-7MPa, or 2MPa-6MPa, or 3MPa-5MPa.In some embodiments, molecular hydrogen dividing potential drop is≤7MPa, or≤6MPa, or≤5MPa, or≤4MPa, or≤3MPa, or≤2.5MPa, or≤2MPa.This hydroprocessing condition can comprise, for example 300 ℃-500 ℃ of temperature, and pressure 15 bar (absolute pressure)-135 bar, space velocity 0.1-5.0WHSV, and molecular hydrogen rate of consumption is every volume tar approximately 53 standard cubic meter/cubic meter (S m ³/ m ³) to about 445S m ³/ m ³(300SCF/B-2500SCF/B).In one or more embodiments, this hydroprocessing condition generally comprises 380 ℃-430 ℃ of temperature, pressure 21 bar (absolute pressure)=81 bar (absolute pressure), space velocity 0.2-1.0, and the about 71S m of rate of consumption of hydrogen ³/ m ³to about 267S m ³/ m ³(400SCF/B-1500SCF/B) one or more in.When using this appointment catalyzer while operating under these conditions, TH hydrogenation conversion is conventionally >=25.0% based on weight, for example, and >=50.0%.

Alleviate preliminary heating device fouling/coking

Preliminary heating device coking and fouling problem can reduce or eliminate by for example certain embodiments of the present invention, refers now to more openly some embodiment of the invention described above of Fig. 2-4.Know that very much these methods can be used alone or in combination.The present invention is not limited to these embodiments, and this specification sheets is not other the method for minimizing incrustation that will get rid of in broad range of the present invention.

In Fig. 2-4, the essentially identical device of enforcement effect and Fig. 1 identifies by same reference numerals.

Fig. 2 describes lesser temps the first reactor region in embodiment and is used for making reactor preheat sequence coking and fouling risk to reduce to minimum.This embodiment is used additional heating source: pre-heaters 51 and 53.Thermal source 51 can be that for example, in order to further to preheat the interchanger of this hydrotreater charging by the heat shedding from this hydrotreater effluent, this effluent guides via pipeline 121 in interchanger 70 downstream sides.Thermal source 53 can be that for example, in adjustment well heater 90, second overlaps pipeline.This embodiment is also used the first lesser temps section 110 hydrotreating reactors, and wherein the first reactor region material stream 54 is only heated to 500 °F-600 °F (260 ℃-315 ℃) and can make

reactor feed preheater

51 and 53 incrustation in this temperature.In fact, the first reactor region (or region) operates at least than temperature at low 100 ℃ of the second hydrotreater section (or region) 111.Optionally, the first reactor region can be at the temperature of low at least 50 ℃ or 25 ℃ than second segment operation from effluent 55 expections of first paragraph reactor 110, be to be further preheated after heat-staple and optional and without the risk of coking and fouling.

The first hydrotreatment section the highest precursor of 110 hydrotreatment coking activity (bituminous matter, cyclic diolefine, aromatic vinyl, alkene, diene, oxygen carrier) thus the first paragraph reactor effluent 55 that produces can further in preheater 90, be heated to second segment reactor inlet temperature and without coking.The feeding side of charging/effluent interchanger 70 also can prevent coking by this layout.This embodiment can also be by selecting high activated catalyst for catalyst bed 115, and it allows that first paragraph reactor operates under lower temperature.

By use, having more active hydrotreating catalyst, to make lower than the lower reactor inlet temperature of tar generation coking be feasible, and this hydrotreating catalyst includes, but are not limited to:

A.Nebula20 obtains from Albemarle

b.Criterion?DN3651,DN3551

c.Albermarle?KF860

In this reactor feed, increase effectiveness fluid/tar ratio and can reduce charging coking, until a bit.If diagrammatic method in Fig. 2 and effectiveness fluid/tar ratio are that 40wt% effectiveness fluid/60wt% tar is consistent.This ratio that raises can tend to reduce coking because effectiveness fluid does not form coking, for example, and the effectiveness fluid that wherein reactor feed has: tar weight is quantitatively for >=0.7, for example, >=1.0, such as >=3.0.

Fig. 3 has described embodiment, and wherein SCT charging is adjusted well heater to avoid tar coking risk around this reactor feed/effluent interchanger and charging.In this embodiment, this SCT10 adjusts and in well heater 90, does not heat but to make temperature approach within this Reactor inlet or this reactor feed divider when it mixes with effectiveness fluid and hydrogen 91 hydrogen fully overheated in reactor feed/effluent interchanger 70 and reactor feed adjustment well heater 90 in this reactor feed/effluent interchanger 70 or reactor feed.Hydrogen 60 and effectiveness fluid 20 mix and guide to the feeding side of reactor feed/effluent interchanger 70 and then adjust well heater 90 and be heated to above required reactor inlet temperature to reactor feed.Then hot mixt 91 mixes with SCT50 and entire mixture 100 enters the existing reactor 110 in required reactor inlet temperature.At reactor feed/effluent interchanger 70 and the coal-tar middle oil coking and fouling risk of reactor feed adjustment well heater 90, alleviated or eliminated, because SCT charging does not preheat.Optionally, in the embodiment not showing at another Fig. 3, only this effectiveness fluid is through this charging/effluent interchanger.Tar charging, effectiveness fluid, and then recycle hydrogen can be adjusted in well heater and heat in reactor feed.

This embodiment ultimate principle is that this tar stream of not preheating is to the temperature higher than producing coking problem.On the contrary, by heat that this effectiveness fluid and hydrogen to institute requires on reactor inlet temperature and then or be in close proximity to this Reactor inlet place and mix effectiveness fluid and the hydrogen that this tar stream and temperature are higher this pre-thermal energy is provided, be wherein mixed to and want needed reactor inlet temperature and contact catalyst and beginning hydrotreatment immediately to react.

It is standby that well heater is adjusted in this reactor feed/effluent interchanger and charging in another embodiment.The impact that any tar coking and fouling produces has been alleviated in this selection.This careful way can be allowed online or off-line decoking and more be waited and importantly allow that flow reactor operates.Feed heater downstream side can comprise that tank is to reclaim the coking of peeling off in decoking operating period.This ultimate principle is also used to any method layout and alleviates anti-coking risk to supplement.

Application charging is adjusted heater structure to pass through design than (until 4394kg/sec m in conventional heating device ²vs. general 1465kg/sec m ²) more high quality flux, be less than 31,500W/m ²lower heat flux and the highest film temperature that is less than 910 °F (488 ℃) minimize coking.

Fig. 4 describes an embodiment and wherein to the catalyst bed of this reactor head, applies heat so that coking and fouling risk is minimized.SCT adjusts not preheating in well heater 90 in this reactor feed/effluent interchanger 70 or reactor feed, but carries out gradually and progressively reach temperature by supplying with external heat the 102 at least the first catalyst bed 118 with reaction within reactor 110 itself.For example the first catalyst bed can be designed as tubular reactor, make catalyzer in pipe and heat-transfer fluid in shell.In one embodiment this heat by heat simultaneously and the

material stream

102 and 101 of charging in heat-transfer fluid provide.

In other embodiment,

material stream

102 and 101 can represent process fluid or any other thermal source of steam or heat, for example, and outside electrical equipment wall well heater.Observe this method and reduced or eliminated incrustation in bench-scale testing factory research.It is found that at this catalyzer and have this tar of preheating simultaneously, effectiveness fluid and hydrogen contacts than with catalyzer that preheating before causes much more successfully, the not operation of coking.The catalyst bed structure that should be appreciated that tubular reactor is structure within those skilled in the art's scope of human knowledge.Equally, consider that heat is added to thermopositive reaction region, temperature controlling system can be designed by process control field technician.

This effectiveness fluid and hydrogen can be optionally in well heater 90 is adjusted in this reactor feed/effluent interchanger 70 and reactor feed on request preheating so that energy more efficient and be reduced in hydrotreater reactor in thermal source add heat request.This SCT not preheating in this reactor feed/effluent interchanger 70 or reactor feed adjustment well heater 90.At Fig. 4 another do not show embodiment in this SCT can be preheated to enough low temperatures to avoid coking or incrustation.

In embodiment at application hydrotreatment product liquid recycled matter as this effectiveness fluid, this recycled matter can be degassed by obtaining this recycled matter from stabilizer tower distillation tower (stabilizer distillation column) bottoms.This liquid recycled matter can also obtain from flash separator bottoms.

Embodiment

Be in Fig. 2-4, to describe embodiment example below, calculate and use process simulation software, obtains from Invensys Inc.

process simulation software is a kind of simulator of stable state, can improve Process Design and operational analysis.It is that the strict quality and the energy balance that are designed to can implement for many chemical processes are calculated.Be used for

analogue reactor charging and Characterization of The Products are based on boiling point curve (simulation distil GC, ASTM D2887) and from the density of experimental data.

For all embodiment, with reference to Fig. 1,2,3,4, segregation section 130 represents the separating device of hydrotreatment routine, comprises high temperature and low-temperature separator, stabilizer tower, and acid gas removal, and utility appliance is such as interchanger and recycle gas compressors.Optionally, provide light fuel and low-volatility fuel separating of oil to prepare the product of two kinds of hydrotreatments.In this selects, this light-weight fuel oil is as effectiveness fluid 20.

Hydrotreater flows out streams 122 and enters segregation section 130.In segregation section, aforesaid device is separated into by this material stream the product 134 that product and by product comprise this hydrotreatment, purges gas stream 132, and lighter-than-air gas material stream 133, and it can be used as combustion gas.If optional light fuel and heavy fuel oil (HFO) separation column are provided, material stream 134 represents two kinds of independently product, light-weight fuel oil and heavy fuel oil (HFO)s.Hydrogen make-up enters segregation section 130 as material stream 131.Material stream 60 is recirculation hydrogen rich gass.In all situations, H before material stream 60 is sent hydrotreater back to ₂s and NH ₃and remove in segregation section 130.

Comparative example 1

In the comparative example who describes at Fig. 1, as indicated, the feeding side of this reactor feed/effluent interchanger 70 and this Reactor inlet charging are adjusted well heater 90 and are had coking and fouling risk.In whole embodiment, except as otherwise noted, this catalyzer is considered to conventional hydrotreating catalyst, such as RT-621, from Albermarle, obtains.Required hydrotreatment or Reactor inlet 100 for this catalyzer are considered to 750 °F (400 ℃) and 995psig (67 bar).

Embodiment 2

Fig. 2 describes an embodiment, and wherein the first reactor region of lesser temps is used for making reactor preheat sequence coking and fouling risk to reduce to minimum.This embodiment is used the more highly active catalyzer of the first lesser temps section 110 hydrotreating reactor application such as Nebula20Criterion DN3651, and DN3551 or Albermarle KF860 so that the first reactor region charging 54 are only heated to 600 °F (375 ℃).First paragraph reactor effluent 55 reaches 611 °F (322 ℃).But at this, hydrotreatment of the highest coking active precursor (bituminous matter, cyclic diolefine, aromatic vinyl, alkene, diene, oxygen carrier).Then first paragraph reactor effluent 55 is heated to 742 °F (394 ℃) and is heated to 750 °F of second segment reactor inlet temperatures (400 ℃) through preheater 90 in feeding preheating interchanger 70.Second segment reactor 111 comprises two RT-621 catalyst beds 116,117.

Embodiment 3

Fig. 3 describes an embodiment, and wherein this SCT charging is adjusted well heater 90 around this reactor feed/effluent interchanger 70 and reactor feed.This SCT feed steam 50 is in 534 °F (279 ℃) in this embodiment.Hydrogen 60 and effectiveness fluid 20 mix and guide to the feeding side of reactor feed/effluent interchanger 70 and be heated to 780 °F (415 ℃) with respect to 804 °F of (429 ℃) reactor effluents 120.Then heats stream 80 guides to reactor feed adjustment well heater 90 and is heated to 940 °F (504 ℃).Then these 940 °F (504 ℃) hot mixts 91 mix and this entire mixture 100 with 534 °F of (279 ℃) SCT50, existing in 750 °F of required reactor inlet temperatures (400 ℃), enter reactor 110.

Embodiment 4

Fig. 4 describes an embodiment, wherein to the catalyst bed of this reactor head, applies heat so that coking and fouling risk is minimized.Not preheating of SCT in this reactor feed/effluent interchanger 70 or reactor feed adjust well heater 90, but progressively reach 750 °F of (400 ℃) temperature of reaction with reacting and carry out within reactor 110 first catalyst area 118.Hydrogen 60 and effectiveness fluid 20 mix and guide to the feeding side of reactor feed/effluent interchanger 70 and then adjust well heater 90 and be heated to 750 °F (400 ℃) to reactor feed.Then this mixture 100 enters reactor 110.The SCT feed steam 50 of 534 °F (279 ℃) also enters reactor 110.The first catalyst bed 118 is designed to RT-621 catalyzer in pipe and the tubular reactor of heat-transfer fluid in shell.The mixture 100 of heated hydrogen and effectiveness fluid mixes with SCT feed steam and enters 118 the pipe that comprises this catalyzer and start to react.Heat-transfer fluid material stream 102 enters 118 shell side heat supplies at 800 °F-850 °F (427 ℃-454 ℃) and leaves to this reactor with as material stream 101, and it then can be adjusting in preheating oven 90 external heat (not shown) in another coil pipe.SCT charging, effectiveness fluid and hydrogen mixture leave this tubular reactor 118 and enter the catalyst bed 116 and 117 that comprises RT-621 catalyzer in 750 °F of required temperature of reaction (400 ℃).

Other document that all patent, test method and the application quote as proof, including priority document, is incorporated herein by reference completely, and its degree all allows the above-mentioned openly and above-mentioned authority quoted consistent with the application.

Although the careful description of the disclosed illustrative forms of the application, the improvement of very clear various other it will be apparent to those skilled in the art that and can be easily by completing, and condition is not deviate from disclosed spirit and scope.Therefore, it not the explanation that the application's claims scope will be restricted to embodiment and the application's statement, but this claim is regarded the patentable novel features that comprise all these open existence as, comprises and can disclose thus all features that one of ordinary skill in the art are used as its equivalent.

When digital lower limit and the digital upper limit are listed in the application, can desired extent be from any lower limit to the upper limit arbitrarily.

Claims

1. a hydroconversion process, comprising:

(c) from the second mixture separation tar stream, the wherein molecule of the second mixture of atmospheric boiling point >=290 of comprise >=90wt.% of this tar stream ℃;

(d) provide effectiveness fluid, comprise >=1.0wt.% of this effectiveness fluid aromatic hydrocarbons, based on the weight of effectiveness fluid;

(e) provide the hydrogen stream that comprises molecular hydrogen;

(f) by (i), this tar stream is exposed at the temperature of 200.0 ℃-400.0 ℃; (ii) this effectiveness fluid be exposed at the temperature of temperature >=400.0 ℃ and then the effectiveness fluid of this tar stream and heating merged, and/or (iii) this hydrogen stream being exposed to >=temperature of 400.0 ℃ under and then one or more modes in the hydrogen stream merging of this tar stream and heating are heated to this tar stream;

(g) in hydrotreatment region the hydrogen stream of (i) this hydrogen stream and/or heating and (ii) the effectiveness fluid of this effectiveness fluid and/or heating exist lower to effectiveness fluid: tar stream weight ratio is the product of the tar stream that heats of catalytic hydroprocessing condition hydrotreatment at least a portion of 0.05 to 3.0 with generation hydrotreatment, the content of product that wherein this effectiveness fluid accounts for hydrotreatment is for >=10.0 % by weight, based on the weight of effectiveness fluid.

2. the process of claim 1 wherein at least 6.0x10 ⁵the product of this hydrotreatment of continuous production second.

3. the method for claim 1 or 2, wherein 2.6x10 at least ⁶the product of this hydrotreatment of continuous production second.

4. the method for claim 1 or 2, wherein 3.2x10 at least ⁷the product of this hydrotreatment of continuous production second.

5. the method for any one in claim 1-4, wherein the hydrocarbon of the first mixture comprises one or more in petroleum naphtha, gas oil, vacuum gas oil, wax-like residual oil, long residuum, mixtures of residua or crude oil.

6. the method for any one in claim 1-5, what wherein the tar of the second mixture comprised (i) >=10.0wt.% atmospheric boiling point >=565 ℃ is not bitum molecule and (ii)≤1000.0ppmw metal, the weight of the tar of this weight percentage based on the second mixture.

7. the method for any one in claim 1-6, wherein, under at least one hydrotreating catalyst exists, this hydrotreatment is implemented at the temperature of 200.0 ℃-450.0 ℃.

8. the method for any one in claim 1-7, wherein step (f) (i) in by the temperature of this tar heating to 200.0 ℃-300.0 ℃.

9. the method for any one in claim 1-8, wherein step (f) (i) comprises that (A) guides this tar stream through at least one well heater, wherein this tar stream is extracted heat, (B) guide this tar stream through the first channel of at least one interchanger and guide the product of at least a portion hydrotreatment with the product from this hydrotreatment, to this tar stream, to extract heat through the second passage of interchanger, or (C) this tar stream thermopositive reaction of at least a portion.

10. the method for any one in claim 1-9, wherein comprise >=10.0wt.% of the product light Fuel oil ingredient of (i) this hydrotreatment and >=10.0wt.% low-volatility fuel oil ingredient, the weight of the product based on hydrotreatment, (ii) content that this effectiveness fluid accounts for oil fuel component is >=90.0wt.%, based on the quantity of this effectiveness fluid, and (iii) this light Fuel oil ingredient has ASTM D8610% distillation point >=60.0 ℃ and 90% and distills point≤350.0 ℃.

The method of any one in 11. claim 1-8, wherein step (f) (i) comprises and guides this tar stream to pass at least one well heater together with this effectiveness fluid, and wherein this tar stream and this effectiveness fluid absorb heat from well heater.

The method of any one in 12. claim 1-8, wherein step (f) (i) comprises and guides this hydrogen stream, this tar stream to pass at least one well heater together with this effectiveness fluid, and wherein this tar stream, this effectiveness fluid and this hydrogen stream extract heat from this well heater.

The method of any one in 13. claim 1-8, wherein step (f) comprises this effectiveness fluid of heating to the temperature of >=425.0 ℃ and merges the effectiveness fluid of this tar stream and heating.

14. 1 kinds of hydroconversion process, comprising:

(a) provide the first mixture, its comprise >=50.0wt.% hydrocarbon, based on the weight of the first mixture;

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

(d) provide effectiveness fluid, the weight of comprise >=1.0wt.% of this effectiveness fluid aromatic hydrocarbons based on effectiveness fluid;

(e) provide the hydrogen stream that comprises molecular hydrogen;

(f) by (i), guide this tar stream through at least one well heater; (ii) guide this tar stream through the first channel of at least one interchanger and guide second passage that heat-transfer fluid passes interchanger to extract heat from this heat-transfer fluid to this tar stream, or (iii) heating this effectiveness fluid and this tar stream is heated to the temperature of 200.0 ℃-400.0 ℃ to the temperature of >=425.0 ℃ and by one or more modes in the effectiveness fluid merging of this tar stream and heating;

(g) in hydrotreatment region under this hydrogen stream and this effectiveness fluid exist, by this tar stream of catalytic hydroprocessing condition hydrotreatment at least a portion, this hydroprocessing condition comprises 300 ℃ to 500 ℃ of temperature ranges, pressure range 15 bar (absolute pressure) are to 135 bar (absolute pressure), and effectiveness fluid: tar weight ratio 0.05-3.0, the product content of this hydrotreatment that wherein (i) this effectiveness fluid comprises is >=50.0wt.%, based on the weight of effectiveness fluid; And (ii) the product content of this hydrotreatment that this heat-transfer fluid comprises is >=50.0wt%, based on the weight of heat-transfer fluid.

The method of 15. claims 14, wherein at least two catalyst beds of this hydrotreatment district inclusion, wherein offer the first catalyst bed to major general's indirect heating.

The method of 16. claims 15, wherein to the first catalyst bed, supply with outside heat, this first catalyst bed comprises that the many pipes that comprise at least one hydrotreating catalyst and this tar stream of guiding at least a portion, this hydrogen stream and this effectiveness fluid pass these many pipes under catalytic hydroprocessing condition, and this outside heat is offered to the outside surface of these many pipes.

The method of 17. claim 14-16, the Pressure Drop that wherein runs through this hydrotreatment region is less 3.0 times than the initial pressure drop that runs through this hydrotreatment region.

The method of 18. claim 14-17, wherein the hydrogen consumption of the per unit volume tar stream of this hydrotreatment is no more than 267S m ³/ m ³.

The method of 19. claim 14-18, wherein this hydrotreatment region be at least divided into the first and second hydrotreatment regions and wherein the first hydrotreatment region at than at least low 100 ℃ of temperature in the second hydrotreatment region, operate.

The method of 20. claim 14-19, wherein at least one high-activity hydrogenation catalyst bed of this hydrotreatment district inclusion.

The method of 21. claims 20, wherein this catalyzer is selected from Nebula20, Criterion DN3651, Criterion DN3551, or Albermarle KF860, and combination.