CN103764800B

CN103764800B - The preheating of charging in the hydrotreatment of hydrocarbon pyrolysis product

Info

Publication number: CN103764800B
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: 2016-04-27
Anticipated expiration: 2032-08-31
Also published as: CA2845002C; WO2013033582A1; EP2751235A1; SG2014011100A; CA2845002A1; CN103764800A; EP2751235B1

Abstract

The present invention relates to the pyrolysis product of upgrading, from hydrocarbon pyrolysis obtain the method for the hydrocracking of upgraded product, the equipment for aforesaid method.Especially the invention provides the method reducing coking and fouling in aforesaid device.

Description

The preheating of charging in the hydrotreatment of hydrocarbon pyrolysis product

The cross reference of related application

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

Technical field

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

Background technology

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

The SCT method for upgrading comprising Conventional catalytic hydrotreatment perplexs by significant catalyst deactivation.The method can operate under temperature 250 DEG C to 380 DEG C, pressure 5400kPa to 20,500kPa, and the catalyzer of use comprises Co, Ni, or one or more in Mo; But observe significant catalyzer coking.Although can be operated at 200 DEG C to 350 DEG C by rising hydrogen dividing potential drop, reduction space velocity and temperature and reduce catalyzer coking; But, SCT hydrotreatment is undesirable under these conditions, increase hydrogen and cost of equipment because raising hydrogen dividing potential drop and cause method to be deteriorated economically, and having encouraged undesired hydrogenation because raise hydrogen dividing potential drop, reduce space velocity and reduce temperature.

Summary of the invention

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

A () provides the first mixture, it comprises >=10.0wt.% hydrocarbon, based on the weight of the first mixture;

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

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

D () provides effectiveness fluid (utilityfluid), this effectiveness fluid comprises >=1.0wt.% aromatic hydrocarbons, based on the weight of effectiveness fluid;

E () providing package is containing the hydrogen stream of molecular hydrogen;

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

(g) in hydrotreating zone under the effectiveness fluid of the hydrogen stream of (i) this hydrogen stream and/or heating and (ii) this effectiveness fluid and/or heating exists by effectiveness fluid: tar stream weight ratio is that the tar stream that heats at least partially of catalytic hydroprocessing condition hydrotreatment of 0.05 to 3.0 is to produce the product of hydrotreatment, the product assay of hydrotreatment that wherein this effectiveness fluid comprises is >=10.0 % by weight, based on the weight of effectiveness fluid.

The present invention relates to hydrocarbon conversion processes in another embodiment, it comprises: (a) provides the first mixture, and it comprises>=50.0wt.% hydrocarbon, based on the weight of the first mixture; B () pyrolysis first mixture is to produce the second mixture in the presence of water vapor, it comprises>=C of 1.0wt.% ₂unsaturates and>=1.0wt.% tar, this weight percentage is based on the weight of the second mixture; C (), from the second mixture separation tar stream, wherein this tar stream comprises the>=molecule of atmospheric boiling point>=290 of 90wt.% second mixture DEG C; D () provides effectiveness fluid, and this effectiveness fluid comprises>=and 1.0wt.% aromatic hydrocarbons is based on the weight of effectiveness fluid; E () providing package is containing the hydrogen stream of molecular hydrogen; F () guides this tar stream through at least one well heater by (i); (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) heats this effectiveness fluid to temperature>=425.0 DEG C and one or more modes in being merged by the effectiveness fluid of this tar stream and heating; G () is under this hydrogen stream and this effectiveness fluid exist, by catalytic hydroprocessing condition hydrotreatment this tar stream at least partially in hydrotreating zone, this hydroprocessing condition comprises temperature range 300 DEG C to 500 DEG C, pressure range 15 bar (absolute pressure) is to 135 bar (absolute pressure), and effectiveness fluid: tar weight ratio 0.05-3.0, wherein the product assay of this hydrotreatment that comprises of (i) this effectiveness fluid is>=50.0wt.%, based on the weight of effectiveness fluid; And the product assay of this hydrotreatment that comprises of (ii) this heat-transfer fluid is>=50.0wt%, based on the weight of heat-transfer fluid.

Accompanying drawing explanation

Fig. 1 schematic diagram illustrates the process layout for hydrotreating reactor part, and this reactor part uses effectiveness fluid with auxiliary SCT hydrotreatment.Marked potential high coking region.Fig. 2-4 illustrates the process layout's example in the scope of the invention with schematic diagram.The present invention is not limited to these embodiments, and this specification sheets is not to get rid of the embodiment of other the present invention more in broad range.Fig. 2 illustrates hydrotreating reactor part, and it uses the first reactor region of lesser temps to reduce to minimum to make reactor preheat sequence coking and fouling danger.Fig. 3 illustrates hydrotreater reactor part, and it makes tar charging reduce to minimum around this reactor feed/effluent interchanger and charging adjustment well heater to make coking and fouling risk.Fig. 4 illustrates hydrotreater reactor part, and the catalyst bed heating of its reactor head makes coking and fouling risk reduce to minimum.Under Fig. 5 is presented at 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, and such as, high temperature pyrolysis, such as applies the high temperature pyrolysis method of water.Above-mentioned a kind of method for pyrolysis, steam cracking is following open more in detail.The present invention is not limited to steam cracking, and describes some embodiment according to steam cracking, is not to get rid of the method for pyrolysis of other the present invention more in broad range.

Part of the present invention can reduce catalyzer coking by hydrotreatment SCT under the existence of effectiveness fluid based on discovery, and this effectiveness fluid comprises a large amount of aromatic hydrocarbons, such as, and list or polycyclic aromatic hydrocarbons.Preliminary heating device coking while requiring heating SCT and effectiveness fluid mixture to required hydroprocessing temperature simultaneously to avoid doing like this.

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

Hydrotreatment SCT improves the suitability of tar as oil fuel, and this be by reduce it viscosity and improve with the consistency of other oil fuel, reduce it boiling point distribution, improve it hydrogen richness and transform the thermostability that bituminous matter and bituminous matter precursor improve tar thus.The fuel oil product obtained can be, such as have than untreated tar the alternative product of the significantly more global business of high value.

Fig. 1 schematic diagram illustrates the hydrotreating reactor part for hydrotreatment SCT.As shown in Figure 1, in charging stock tank 30, SCT stream 10 and effectiveness fluid merge 20, be pumped across pipeline 50, then mix with hydrogeneous stream 60 by pump 40.Then this mixture 61 preheats succeeded by supplementing the reactor inlet temperature be preheated in technique arrangement (processtrim) well heater 90 in facing to the interchanger 70 of this reactor effluent 120.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, same catalyst is used.This catalyzer can be such as conventional hydrotreating catalyst, and such as RT-621, obtains from Albermarle.

Then this hydrotreater effluent stream is introduced to via pipeline 122 and leaves interchanger 70 to one or more segregation section 130, (comprise via the directed sweeping gas stream left of pipeline 132 for being separated (i) from this hydrotreater effluent stream, such as, excessive or with cross process gas), (ii) product via the directed hydrotreatment left of pipeline 134 (comprises, such as, hydrotreatment SCT), and (iii) guides the lighter-than-air gas stream left (to comprise such as via pipeline 133, methane and hydrogen sulfide) for upgrading and/or use, such as combustion gas.Separation in addition can be implemented in separation phase, such as, for going out light-weight fuel oil and/or heavy oil from the product separation of hydrotreatment.Supplementary Division process gases (such as, molecular hydrogen) can guide via pipeline 131 and enter segregation section 130.Fu Qing process gas guides via pipeline 60 and leaves 130 sections, to be recycled to hydrotreater 110.Any H ₂s and NH ₃removed before this process gas enters pipeline 60 in 130 sections at least partially.

Although improve thermostability in SCT hydrotreatment, there is thermally labile SCT to required reactor inlet temperature and form fouling risk, such as coking in preheating SCT.Above-mentioned coking can be tended to make this preliminary heating device, Reactor inlet and this catalyst bed top fouling.

Can find out and use quartz filling reactor, such as, not produce any catalyzer dirt when heating this effectiveness fluid/tar/hydrogen mixture.This quartz is inertia, to simulate any equipment being exposed to heated mixt.This reactor runs 400 DEG C and 425 DEG C and measures and runs through this reactor pressure and fall.It is the signal indicating coking and fouling that Pressure Drop increases in time.Condition is as follows:

Reactor: 3/8OD manages, and 18in. (45.72cm) is long, and 12in. (30.48) cm heats

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 is by contrasting expression of results of plotting working time at various temperatures to the Pressure Drop running through this reactor observed.Notice that Pressure Drop and time scale are different in two graphic representations.At 400 DEG C under these conditions, this Pressure Drop is later almost negligible more than 80 hours in operation.But at 425 DEG C, after operation only 5 or 6 hours, Pressure Drop increases fast, causes reactor to run and just stops less than 27 hours.In 425 DEG C of graphic representations, observed Pressure Drop vibration shows the flowing of coking and fouling and blocking charging and hydrogen.

Above-mentioned coking and fouling can limit the time span that conversion process is run continuously.Once coking makes key equipment incrustation, then conversion process needs to interrupt to remove coking.Should be able to run continuously and at least 1 day, (8.6 × 10 to can be used for this conversion process of industry park plan ⁴second), preferably at least 1 week (6.0 × 10 ⁵second), more preferably at least January (2.6 × 10 ⁶second), most preferably at least 1 year (3.2 × 10 ⁷second) do not make the excessive fouling of hydrotreating apparatus or hydrotreating catalyst excessive coke formation.

Such as, in order to industrial operation, the Pressure Drop running through hydrotreating reactor or miscellaneous equipment should be no more than about 3.0,4.0 or 5.0 times of initial (SOR) Pressure Drop under design current velocity.

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

Specifically, in the embodiment that Fig. 1 describes, determine that feeding side reactor feed under certain condition/effluent interchanger 70 and Reactor inlet charging arrange well heater (trimheater) 90 and there is coking and fouling risk, if SCT, optionally merge with effectiveness fluid and/or molecular hydrogen, preheating at the temperature exceeding about 572 °F (300 DEG C) in this device.Therefore, in certain embodiments, this tar stream 10 enters this hydrotreater and is then heated to hydrotreater reactor inlet temperature 700 °F-800 °F (370 DEG C-425 DEG C) between 200 °F-572 °F (90 DEG C-300 DEG C).Fig. 1 shows hydrotreatment layout and has tar stream (or the tar merged with effectiveness fluid and/or the molecular hydrogen) device location of coking possibility before its hydrogen treatment.In certain embodiments, this effectiveness fluid comprises, such as, 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 under general reactor preheating temperature 700 °F-800 °F (370 DEG C-425 DEG C), in preliminary heating device, be not inclined to coking.The risk of the coal-tar middle oil component of charging coking and fouling when being heated beyond about 572 °F (300 DEG C) is there is in FIG with the device location that dashed circle highlights.

Certain embodiments of the invention are to a certain extent based on the exploitation untreated tar stream (such as SCT) being preheated to the method for hydrotreating reactor temperature in.It alleviates and even eliminates preliminary heating device fouling (or reducing catalyzer coking formation) to allow that flow reactor runs.Other embodiment of the present invention is based on the exploitation of hydrogenation of tar treatment process utilizing high-active catalyst.In this embodiment, hydrotreatment tar upstream preheat requirements is reduced or eliminated because this hydrotreating catalyst is active enough at a lower temperature.These methods can be used alone or in combination.The application of method as described below further, can allow conversion process to run at least 1 day continuously (8.6 × 10 ⁴second), preferably at least 1 week (6.0 × 10 ⁵second), more preferably at least January (2.6 × 10 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 DEG C and comprising >=5.0wt.% has the molecule of multiple fragrant core, based on products weight.TH is generally solid at 25.0 DEG C and generally includes SCT fraction it to be insoluble to the Skellysolve A of 5:1 (vol.:vol.) ratio at 25.0 DEG C: SCT (" conventional extraction into heptane method ").TH can comprise high molecular weight molecules (such as, MW >=600) such as bituminous matter and other height-molecular weight hydrocarbon.This term " bituminous matter " is defined as heptane insolubles, and tolerance is according to ASTMD3279.For example, TH comprises>=10.0wt.% have by (i) low relative molecular amount alkane and/or alkene, such as, C ₁-C ₃alkane and/or alkene, (ii) C ₅and/or C ₆ring paraffinic hydrocarbon (cycloparaffinic) ring, or the high molecular weight molecules of the fragrant core that one or more link together in (iii) thiophene (thiophenic) ring.Usually, the carbon atom of the TH of >=60.0wt.% is included in based on TH carbon atom weight in one or more fragrant core, and such as, scope is 68.0wt.%-78.0wt.%.Do not wish to retrain by any particular theory or model simultaneously, it is believed that due to van der waals force between TH molecule in addition, the aggregation that TH is formed has relative two dimensional form.TH aggregation large size, scope is such as, their overall dimension ten nanometer to hundreds of nanometer (" nm "), to cause under catalytic hydroprocessing condition aggregation mobility and diffusivity low.In other words, conventional TH transforms by harsh quality-transport restriction puzzlement, and it causes TH to be converted into the highly selective of coking.Have been found that this aggregation is decomposed into each molecule by the SCT merging effectiveness fluid, such as, their overall dimension≤5.0nm and molecular weight ranges are between about 200 grams every mole to 2500 grams every mole.This causes mobility that TH in SCT is larger and diffusivity, causes catalyzer-duration of contact shorter under hydroprocessing conditions and be converted into coking less.Therefore, SCT transforms and can carry out at low pressures, and such as, 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 such as, 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, that the such as thick dregs of fat (" residual oil ") had not only comprised normal pressure but also the residual oil comprising vacuum and other such as, the stream usually run in oil and petroleum chemistry processing.The aromatic carbon content of this SCT's passes through ¹³cNMR measures substantially higher than residual oil.For example, in SCT, the quantity of aromatic carbon is generally greater than 70wt% and is usually 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 DEG C, for example, SCT1 studies on asphaltene only 32.5wt% atmospheric boiling point very higher than 565 DEG C.Vacuum resid is not just like this.Even if solvent extraction is the method do not completed, result shows that the bituminous matter major part in vacuum resid is heavy molecules, and its atmospheric boiling point is higher than 565 DEG C.When with the condition substantially the same for vacuum resid under carry out heptane solvent extraction time, compared with vacuum resid situation, the bituminous matter obtained from SCT comprises the molecule of (based on the weight) atmospheric boiling point <565 DEG C of much higher per-cent.SCT is different from residual oil is in addition metal and nitrogenous compound relative content.In SCT, total metal content≤1000.0ppmw (1,000,000/, weight) based on SCT weight, such as ,≤100.0ppmw, such as≤10.0ppmw.The nitrogen total amount be present in SCT is less than the nitrogen content of thick oily vacuum resid usually.

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

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, the metal of SCT, hydrogen and nitrogen content (based on wt.) scope are very low.50 DEG C of SCT kinematic viscosity (cSt) normally >=1000, or >=100, even if SCT atmospheric boiling point >=565 of relative populations are DEG C much lower compared with vacuum resid situation.

SCT obtains usually used as hydrocarbon pyrolysis product.This pyrolytic process can comprise, such as high temperature pyrolysis, such as utilize 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 will get rid of to utilize other method for pyrolysis within the present invention widely scope.

SCT is obtained by pyrolysis

Conventional steam cracking uses pyrolyzer, and it has two major sections: convection zone and radiation section.The hydrocarbon component of the convection zone that this feedstock (the first mixture) generally enters stove wherein the first mixture is heated by the steam component of indirect contact from this radiation section hot flue gas and direct this first mixture of contact and is vaporized.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 any unreacted component of product and the first mixture produced by the first mixture pyrolysis.Usual at least one segregation section is positioned at this pyrolyzer downstream, and this segregation section is used 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 such as primary fractionator.Usually, cooling section, general direct quenching or indirect heat exchange are between this pyrolyzer and this segregation section.

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

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

In addition, the first mixture can comprise thinner, such as, in nitrogen, water etc. one or more.Such as, >=1.0wt.% thinner, based on the first mixture weight, such as >=25.0wt.%.When this pyrolysis is steam cracking, the first mixture can by this hydrocarbon with comprise steam diluent and combine and prepare, such as, 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 embodiment; the hydrocarbon of the first mixture comprises >=10.0wt.%; such as; one or more in >=50.0wt.%, such as >=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 comprise >=about 0.1wt.% bitum those.Suitable crude oil comprises, and such as, height-sulphur original oil, is such as rich in those of polynuclear aromatics.Optionally, the hydrocarbon of the first mixture comprises sulphur, and such as, >=0.1wt.% sulfenyl is in the hydrocarbon composition weight of the first mixture, and such as, >=1.0wt.%, such as scope is about 1.0wt.% to about 5.0wt.%.Optionally, the sulfur-containing molecules of the first mixture at least partially, such as, the sulfur-containing molecules of first mixture of >=10.0wt.%, comprises at least one aromatic ring (" aromatic hydrocarbons sulphur ").When (i) first the hydrocarbon of mixture be crude oil or comprise >=the crude oil fraction of 0.1wt.% aromatic hydrocarbons sulphur and (ii) this pyrolysis be steam cracking time, then SCT comprises a large amount of sulphur derived from the first mixture aromatic hydrocarbons sulphur.Such as, based on weight, in SCT, SCT sulphur content can than the hydrocarbon component height about 3-4 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 obtain from normal pressure pipe still (" APS ") and/or vps vacuum pipe-still (" VPS ") 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 first mixture uses is by producing the APS bottoms from crude separation and the combination of the APS bottoms succeeded by VPS process.

Optionally, this pyrolyzer has at least one vapour/liquefaction tripping device (being sometimes referred to as flash vaporization kettle or flash tank) integrated with it, for upgrading first mixture.When the hydrocarbon component of the first mixture comprise >=about 0.1wt.% bituminous matter based on the hydrocarbon composition weight of the first mixture, such as, during >=about 5.0wt.%, above-mentioned vapour/liquefaction tripping device is specially suitable.Conventional vapour/liquefaction tripping device can be used to complete these, but the present invention is also not limited thereto.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, disclosed in 235,705 United States Patent (USP)s those, it all introduces the application as a reference.Suitable vapour/liquefaction tripping device is also disclosed in US Patent No. 6,632, and 351 and US7,578, in 929, it all introduces the application as a reference.Usually, when using vapour/liquefaction tripping device, the gas phase composition leaving this device forms identical with the gas phase entering this device substantially, and similarly leave this flash tank liquid phase composition substantially form identical with the liquid phase entering this device, that is, gas/liquid tripping device is separated and is substantially made up of the two-phase physical sepn entering this tank.

In the embodiment using the gas/liquid tripping device combined with pyrolyzer, the hydrocarbon component of the first mixture is provided to the import of pyrolysis unit convection zone at least partially, and wherein heat hydrocarbon is in gas phase to make this hydrocarbon at least partially.When (such as steam) uses thinner, the thinner composition optional (but preferred) of the first mixture adds this section and mixes with this hydrocarbon component to produce the first mixture that the first mixture is gas phase at least partially,, then at least one gas/liquid tripping device flash distillation to leave molecule, the such as bituminous matter of the high molecular of the first mixture at least partially from the first mixture separation and guiding.Fraction at the bottom of tower can guide from this steam-liquid separation device and leave, and at the bottom of this tower, fraction comprises, such as, and >=10.0% (based on weight) first bituminous matter of 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 about 600 °F (315 DEG C) to about 950 °F (510 DEG C) and pressure range is about 275kPa to about 1400kPa, such as, temperature range is about 430 DEG C to about 480 DEG C and pressure range is about 700kPa to 760kPa.Overhead fraction from gas/liquid tripping device can heat further in convection zone, and then introduce within radiation section via crossover pipe (crossoverpiping), wherein overhead fraction is exposed to temperature >=760 DEG C under pressure >=0.5 bar (g), such as, temperature range is about 790 DEG C to about 850 DEG C and pressure range is about 0.6 bar (g) extremely about 2.0 bar (g), to implement the hydrocarbon component pyrolysis (such as cracking and/or reformation) of the first mixture.

Convection zone import downstream and there is to the crossover pipe upper reaches of radiation section one of advantage of gas/liquid tripping device be that it makes the category of hydrocarbon that just can directly use as the first mixture hydrocarbon component without the need to pre-treatment increase such as, the hydrocarbon component of the first mixture can comprise >=50.0wt.%, such as, one or more crude oil of >=75.0wt.%, such as >=90.0wt.% (the hydrocarbon composition weight based on the first mixture), the crude oil of even higher naphthenic acid content and fraction thereof.The charging with high naphthenic acid content be a large amount of tar of preparation those one of and be specially suitable when at least one gas/liquid tripping device and pyrolyzer combine.If requirement, the composition of the first mixture can change in time, such as, by application during the cycle very first time, there is the first mixture of the first hydrocarbon component, then application has the first mixture of the second hydrocarbon component during the second time cycle, and the first and second hydrocarbon is in fact different hydrocarbon or substantially different hydrocarbon mixtures.First and the substantially equal time can be had second cycle, but this is dispensable.First and second periods alternately can continuously or semi-continuously implement (such as, in " closing " operation), if asked.This embodiment can be used for the order pyrolysis of inconsistent 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 at ambient conditions).Such as, comprise original oil the first hydrocarbon component can during the cycle very first time in order to prepare the first mixture and during the second time cycle steam cracked tar in order to prepare the first mixture.

In other embodiment, do not use gas/liquid tripping device.For example when the hydrocarbon of the first mixture comprises one or more grade of timesharing of crude oil and/or crude oil, this pyrolytical condition can be conventional steam cracking conditions.Suitable steam cracking conditions comprises, such as, the first mixture be exposed to temperature (in heating outlet measure) >=400 DEG C, such as, scope is 400 DEG C-900 DEG C, and pressure >=0.1 bar, cracking residence time scope about 0.01 second to 5.0 seconds.In one or more embodiment, first mixture comprises hydrocarbon and thinner, wherein based on the weight of the hydrocarbon of the first mixture, the hydrocarbon of the first mixture comprises >=the wax-like residual oil of 50.0wt.%, long residuum, petroleum naphtha, mixtures of residua or crude oil in one or more.This thinner comprises, and such as, >=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 (i) temperature range 760 DEG C-880 DEG C; (ii) pressure range 1.0-5.0 bar (absolute pressure), or (iii) cracking residence time ranges is one or more in 0.10-2.0 second.

Guide the second mixture to leave from pyrolyzer, the second mixture is derived from the first mixture by pyrolysis.When using regulation pyrolytical condition, the second mixture generally comprises>=C of 1.0wt.% ₂the TH of unsaturates and>=0.1wt.%, this weight percentage is based on the weight of the second mixture.Optionally, the second mixture comprises the>=C of 5.0wt.% ₂the TH of unsaturates and/or>=0.5wt.%, the TH of such as>=1.0wt.%.Although the second mixture generally comprises light olefin required for mixture, SCN, SCGO, SCT and the unreacted component of the first mixture (water such as in steam cracking situation, and unreacted hydrocarbon sometimes), in these, respective relative quantity generally depends on, such as, the composition of the first mixture, pyrolyzer layout, processing condition etc. during pyrolysis.Usual guiding leaves the second mixture for pyrolysis section, such as, for cooling and segregation section.

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

Although do not require, the present invention is applicable to pyrolyzer downstream side second mixture cooling, such as, can use system cools second mixture comprising transfer line interchanger.Such as, this process stream can be cooled to temperature and be about 700 DEG C-350 DEG C by this transfer line interchanger, and in order to efficiently produce hyperpressure steam, it can be used by the method or directedly to leave.If asked, generally position between this furnace outlet and this segregation section, the second mixture can carry out direct quenching.Second mixture contact liq quench stream replaces or can complete this quenching with transfer line exchanger process in addition.If used in conjunction with at least one transfer line exchanger, this quench liquid preferably introduces transfer line exchanger downstream side position.Suitable quench liquid comprises liquid quench oil, as by downstream side quenching oil gas-liquid separator (knock-outdrum), pyrolysis fuel oil and water obtain those, it can obtain from the dilution steam generation of the source of routine, such as condensation.

Segregation section swims 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 lower pyrolyzer usually.Can use conventional separating device in segregation section, such as, one or more flash tanks, fractionator, water quick cooling tower, indirect condenser etc., be such as disclosed in US Patent No. 8,083, those in 931.In segregation section, the 3rd mixture as tar stream can from the second mixture separation, makes the 3rd mixture tar stream comprise the >=TH of 10.0wt.% second mixture, based on the TH weight of the second mixture.When this pyrolysis is steam cracking, this tar stream generally comprises SCT, it obtains certainly, such as, the tower bottoms stream of the steam crackers of SCGO stream and/or primary fractionator, flash tank bottoms (such as, 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 embodiment, this tar stream comprises >=TH of 50.0wt.% second mixture, based on the TH weight of the second mixture.Such as, this tar stream can comprise >=TH of 90.0wt.% second mixture, based on the TH weight of the second mixture.This tar stream can have, such as, (i) sulphur content scope 0.5wt.-7.0wt.%, (ii) TH content range is 5.0wt.%-40.0wt.%, this weight percentage is based on tar stream weight, and (iii) is 1.01g/cm 15 DEG C of density ranges ³-1.15g/cm ³, such as, 1.07g/cm ³-1.15g/cm ³, and (iv) 50 DEG C of range of viscosities 200cSt-1.0x10 ⁷cSt.

This tar stream can comprise TH aggregation.In one or more embodiment, this tar stream comprises >=the TH aggregation of 50.0wt.% second mixture, based on the TH aggregation weight of the second mixture.Such as, this tar stream can comprise >=the TH aggregation of 90.0wt.% second mixture, based on the TH aggregation weight of the second mixture.

This tar stream usually guides from this segregation section and leaves for tar stream hydrotreatment effectiveness fluid exists.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 will got rid of in broad range of the present invention.

Effectiveness fluid

This effectiveness fluid is used, such as, for duration of runs during effectively increasing hydrotreatment and the product property improving hydrotreatment in this tar stream of hydrotreatment.Effective effectiveness fluid aromatic hydrocarbons, that is, comprise the molecule with at least one fragrant core.In one or more embodiment, this effectiveness fluid comprises >=40.0wt.% aromatic carbon, such as >=60.0wt.% aromatic carbon, is measured by NMR.Hydrotreater is got back in liquid phase, effectively recirculation that in one or more embodiment, this effectiveness fluid comprises the product of a part of hydrotreatment.All the other hydroprocessed product liquid phases can guide from this process to be left and is optionally used as low sulphur fuel oil blend component.The product of this hydrotreatment can optionally 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 of the liquid phase as effectiveness fluid.The liquid phase of the product of hydrotreatment can comprise >=and 90.0wt.% has the weight of molecule based on the product of hydrotreatment of the product of the hydrotreatment of at least four carbon atom.In other embodiment, this liquid phase comprises >=product of 90.0wt.% hydrotreatment in there are atmospheric boiling point >=65.0 DEG C, >=150.0 DEG C, the molecule of >=260.0 DEG C, based on the weight of the product of hydrotreatment.

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

In other embodiment, this effectiveness fluid comprises aromatic hydrocarbons (that is, comprising the molecule with at least one fragrant core) and ASTMD8610% and distills point >=60 DEG C and 90% distillation point≤350 DEG C.Optionally, this effectiveness fluid (it can be solvent or solvent mixture) ASTMD8610% distills point >=120 DEG C, such as, >=140 DEG C, such as >=150 DEG C and/or ASTMD8690% distillation point≤300 DEG C.

In one or more embodiment, this effectiveness fluid (i) critical temperature is that 285 DEG C-400 DEG C and (ii) comprise >=the 1-Polycyclic aromatic hydrocarbons of 80.0wt.% and/or 2-Polycyclic aromatic hydrocarbons, comprise its alkyl functionalized derivative, based on the weight of effectiveness fluid.Such as, this effectiveness fluid can comprise, and such as, >=90.0wt.% is mono--Polycyclic aromatic hydrocarbons, comprises those with one or more hydrocarbon substituent, such as 1-3 or 1-2 hydrocarbon substituent.Above-mentioned substituting group can be any hydrocarbyl group, and it is consistent with this effectiveness total fluid distillation characteristics.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, this effectiveness fluid comprise in >=90.0wt.% ethylbenzene, Three methyl Benzene, dimethylbenzene, toluene, naphthalene, alkylnaphthalene (such as methylnaphthalene), tetralin or alkyl tetralin (such as methyl tetralin) one or more.Usually need this effectiveness fluid to be substantially free of the molecule with alkenyl functionality, applying hydrotreating catalyst in the embodiment especially under above-mentioned molecule exists has the trend forming coking.In embodiments, based on the weight of effectiveness fluid, this effectiveness fluid comprises≤10.0wt.% ring compound, and this ring compound has C ₁-C ₆side chain, this side chain has alkenyl functionality.

In certain embodiments, from SCN and/or SCGO of the second mixture separation in the downstream side primary fractionator of the pyrolyzer run under this effectiveness fluid is included in steam cracking conditions, such as, SCN and/or SCGO.This SCN or SCGO can in the hydrotreater of different routines hydrogen treatment (such as not hydrogen treatment together with this tar).This effectiveness fluid can comprise, and such as >=50.0wt.% is separated gas oil, based on the weight of effectiveness fluid.In certain embodiments, effectiveness fluid obtains from the product of hydrotreatment at least partially, such as, by being separated and the product of hydrotreatment of recirculation part atmospheric boiling point≤300 DEG C.

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

This effectiveness fluid is used, such as, for the cycle of operation during being effectively increased in hydrotreatment in this tar stream of hydrotreatment.During hydrotreatment, effectiveness fluid and tar stream relative populations normally about 20.0wt.% extremely about 95.0wt.% tar stream and about 5.0wt.% extremely about 80.0wt.% effectiveness fluid, adds tar stream gross weight based on effectiveness fluid.Such as, effectiveness fluid and tar stream relative populations normally (i) about 20.0wt.% extremely about 90.0wt.% tar stream and about 10.0wt.% extremely about 80.0wt.% effectiveness fluid during hydrotreatment, or (ii) about 40.0wt.% is to about 90.0wt.% tar stream and about 10.0wt.% extremely 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 can merge within this hydroprocessing vessel or hydrotreating zone with this tar stream at least partially at least partially, but this is dispensable, and in one or more embodiment at least partially this effectiveness fluid and at least partially this tar stream as separate material flow supply and (such as) this hydroprocessing vessel or upstream, hydrotreating zone before entering) be merged into a feed steam.In certain embodiments, the feed steam to this hydrotreater comprises 40.0wt.%-90.0wt.%SCT and 10.0wt.%-60.0wt.% effectiveness fluid, and this weight percentage is based on the weight of feed steam.

Hydrotreatment

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

Conventional hydro process catalyzer may be used for this tar stream of hydrotreatment under effectiveness fluid exists, and such as specify those being used for residual oil and/or heavy-oil hydrogenation process, but the present invention is not restricted to this.Suitable hydrotreating catalyst comprises those and comprises (i) one or more base metals (bulkmetals) and/or (ii) one or more supported metal.This metal can be element form or compound form.In one or more embodiment, the element that this hydrotreating catalyst comprises at least one metal periodictable 5-10 race (is announced as thePeriodicChartoftheElements, TheMerckIndex, 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 embodiment, this race of catalyzer 5 race to 10 total metal content is the catalyzer at least 0.0001 gram of every gram, or at least 0.001 gram or at least 0.01 gram, wherein grams calculates based on element.Such as, it is 0.0001 gram-0.6 gram that this catalyzer comprises 5-10 race 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 particular embodiments, this catalyzer comprises at least one 15 race's elements further.Preferably 15 race's element instance are phosphorus.When use 15 race's element, the total amount that this catalyzer comprises 15 race'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 calculates based on element.

In embodiments, this catalyzer comprises at least one 6 race metal.Preferably 6 race's Material examples comprise chromium, molybdenum and tungsten.The total amount of 6 race's metals that this catalyzer can comprise is every gram of catalyzer at least 0.00001 gram, or at least 0.01 gram, or at least 0.02 gram, wherein grams calculates based on element.Such as, 6 race's total metal contents that this catalyzer can comprise are every gram of catalyzer 0.0001 gram-0.6 gram, 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 related embodiment, this catalyzer comprises at least one 6 metal and comprises at least one 5 race, 7 races, 8 races, 9 races or 10 race's metals further.Above-mentioned catalyzer can comprise such as 6 race's metallographic phase to 5 race's metals in molar ratio 0.1 to 20,1 to 10 or 2 to 5 metallic combination, wherein this ratio calculates based on element.Alternatively, this catalyzer comprise such as 6 race's metallographic phase to 7-10 race metal in molar ratio 0.1 to 20,1 to 10 or 2 to 5 metallic combination, wherein this ratio calculates based on element.

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

The present invention comprises and is incorporated into a kind of or catalyst metal of carrier (or thereon deposit), and such as one or more races of 5 race-10 and/or 15 race's metals are to form hydrotreating catalyst.This carrier is a kind of porous material.Such as, this carrier can comprise one or more refractory oxides, porous carbon-sill, zeolite or its combination.Suitable refractory oxides comprises, such as, 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, such as, 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, gamma-alumina, δ aluminum oxide, α-aluminum oxide or its quantity combined 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, measured by X-ray diffraction.In particular embodiments, this hydrotreating catalyst is CatalystT, and this carrier comprises at least one aluminum oxide, such as, 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 use, and such as X-ray diffraction measures.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 a carrier is used, this carrier can infiltrate required metal to form this hydrotreating catalyst.Before impregnating metal, this carrier can be through 400 DEG C-1200 DEG C or 450 DEG C-1000 DEG C or 600 DEG C of-900 DEG C of heat treated.In certain embodiments, this hydrotreating catalyst can be formed by add to the in type carrier mixture through heat treated or in conjunction with 5 race of race-10 metals.This kind of formation 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 such as at 150 DEG C-750 DEG C or 200 DEG C-740 DEG C or 400 DEG C of these catalyzer of-730 DEG C of heat treated.Optionally, this catalyzer at 400 DEG C-1000 DEG C under the air of warm air and/or oxygen enrichment exists heat treated make 5-10 race metallic transition at least partially be their corresponding metal oxides to remove volatile matter.In other embodiment, this catalyzer can (such as, air) in 35 DEG C-500 DEG C or 100 DEG C-400 DEG C or 150 DEG C-300 DEG C heat treated in the presence of oxygen.The time that thermal treatment can be carried out 1-3 hour does not make to remove most of volatile constituent the metal oxide form that 5 race of race-10 convert metals are them.The catalyzer prepared by aforesaid method is commonly referred to " calcining " or " dry " catalyzer.Can combine with formation sulphide process and prepare above-mentioned catalyzer, 5 race of race-10 metals are dispersed among carrier substantially.When this catalyzer comprises θ alumina supporter and one or more 5 race-10 race's metals, this catalyzer generally at >=400 DEG C thermal treatment to form this hydrotreating catalyst.Generally, at≤1200 DEG C, above-mentioned thermal treatment is implemented.

This catalyst shape can be, such as, 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 about 0.79mm to about 3.2mm (1/32-1/8 inch), about 1.3mm to about 2.5mm (1/20-1/10 inch), or about 1.3mm 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, such as, the shape, quaterfoil shape etc. of three leaves.Optionally, this catalyzer flat plate crush strength (flatplatecrushstrength) is 50-500N/cm, or 60-400N/cm, or 100-350N/cm, or 200-300N/cm, or 220-280N/cm.

The catalyzer of porous, comprises those with conventional stomata characteristics, within the scope of the invention.When using porous catalyst, the vesicular structure, aperture, pore volume, hole shape, aperture surface area etc. of this catalyzer, within the scope of conventional hydro process catalyst characterization, although the present invention is not limited thereto.Such as, this catalyzer aperture intermediate value is effective for hydrotreatment SCT molecule, and above-mentioned catalyzer aperture intermediate range is 30 dust-1000 dusts, or 50 dust-500 dusts, or 60 dust-300 dusts.Aperture can measure according to ASTM method D4284-07 mercury penetration method.

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

Usually, hydrotreating catalyst pore size distribution is not wide, so that reduces catalyst activity or selection rate indistinctively.Such as, 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, this catalyzer aperture intermediate value 50 dust-180 dust 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, such as>=0.3cm ³/ g, as>=0.7cm ³/ g, or>=0.9cm ³/ g.In certain embodiments, pore volume is, such as, 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 example, 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, such as, 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 need to substituting the catalyzer in hydrotreatment or zone of action.Catalyst life, usually than the multiple >10 not using the situation of effectiveness fluid to grow, such as, grows >=100 times, such as length >=1000 times.

Carry out hydrotreatment in presence of hydrogen, such as, merge molecular hydrogen and this tar stream and/or effectiveness fluid and/or (ii) by (i) hydrotreatment upstream guides molecular hydrogen to this hydrotreatment section in one or more pipeline or pipeline.Although purified molecule hydrogen may be used for this hydrotreatment relatively, but usually desirable is application " process gas ", it comprises enough molecular hydrogens for this hydrotreatment and optional other mass (such as, nitrogen and lighter hydrocarbons such as methane), it generally can not adversely hinder or affect this reaction or this product.Generally at the unwanted such as H of removing ₂s and NH ₃and so on impurity after, no process gas can with the product separation of hydrotreatment be used for apply again.This process gas optionally comprises >=about 50vol.% molecular hydrogen, and such as, >=about 75vol.%, based on guiding the process volume of gas entering this hydrotreatment section.

Optionally, the quantity of the molecular hydrogen of this hydrotreatment section is supplied to for about 300SCF/B (standard cubic foot every barrel) (53Sm ³/ m ³) to 5000SCF/B (890Sm ³/ m ³), wherein B refers to tar stream bucket.Such as, the molecular hydrogen that provides is 1000SCF/B (178Sm ³/ m ³) to 3000SCF/B (534Sm ³/ m ³).Under specifying the appointment hydrotreating catalyst of effectiveness fluid, molecular hydrogen and effective catalytic amount to exist, the product of hydrotreatment prepared by hydrotreatment tar stream under catalytic hydroprocessing condition comprises, such as, 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 will got rid of in broad range of the present invention.

This hydrotreatment is implemented usually under hydroconversion process condition, such as, under one or more the condition in the hydrocracking (comprising selec-tive hydrogenation cracking) for implementing appointment tar stream, 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, such as, 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 exist.Operable catalytic hydroprocessing condition can comprise, and such as, the thinner-tar stream of merging is exposed to 50 DEG C-500 DEG C or 200 DEG C-450 DEG C or 220 DEG C-430 DEG C or 350 DEG C-420 DEG C close to molecular hydrogen and hydrotreating catalyst.Such as, temperature range is 300 DEG C-500 DEG C, or 350 DEG C-430 DEG C, or 360 DEG C-420 DEG C.Effectiveness fluid tar stream weight hourly space velocity (WHSV) general range merged 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 at least 10h ^-1, or at least 15h ^-1.During hydrotreatment, the usual scope of molecular hydrogen partial pressure is 0.1MPa-8MPa, or 1MPa-7MPa, or 2MPa-6MPa, or 3MPa-5MPa.In some embodiments, molecular hydrogen partial pressure is≤7MPa, or≤6MPa, or≤5MPa, or≤4MPa, or≤3MPa, or≤2.5MPa, or≤2MPa.This hydroprocessing condition can comprise, such as temperature 300 DEG C-500 DEG C, and pressure 15 bar (absolute pressure)-135 clings to, space velocity 0.1-5.0WHSV, and molecular hydrogen rate of consumption is every volume tar about 53 standard cubic meter/cubic meter (Sm ³/ m ³) to about 445Sm ³/ m ³(300SCF/B-2500SCF/B).In one or more embodiment, this hydroprocessing condition generally comprises temperature 380 DEG C-430 DEG C, pressure 21 bar (absolute pressure)=81 bar (absolute pressure), space velocity 0.2-1.0, and rate of consumption of hydrogen is about 71Sm ³/ m ³to about 267Sm ³/ m ³(400SCF/B-1500SCF/B) one or more in.When using this appointment catalyzer to operate under these conditions, TH hydrogenation conversion usually >=25.0% based on weight, such as, >=50.0%.

Alleviate preliminary heating device fouling/coking

Preliminary heating device coking and fouling problem can be reduced or eliminated by such as certain embodiments of the present invention, refers now to some embodiment that Fig. 2-4 discloses the invention described above more in detail.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 the method for other the minimizing incrustation will got rid of in broad range of the present invention.

In Fig. 2-4, the device that enforcement effect and Fig. 1 are substantially identical is identified by same reference numerals.

Fig. 2 describes lesser temps first reactor region in embodiment and is used for making reactor preheat sequence coking and fouling risk reduce to minimum.This embodiment uses additional heating source: pre-heaters 51 and 53.Thermal source 51 can be, such as, preheat the interchanger of this hydrotreater charging in order to the heat by shedding from this hydrotreater effluent further, this effluent guides via pipeline 121 in interchanger 70 downstream side.Thermal source 53 can be, such as, and second cover pipeline in adjustment well heater 90.This embodiment also uses the first lesser temps section 110 hydrotreating reactor, and wherein the first reactor region stream 54 is only heated to 500 °F-600 °F (260 DEG C-315 DEG C) and can not makes reactor feed preheater 51 and 53 incrustation in this temperature.In fact, the first reactor region (or region) operates at temperature at least than low 100 DEG C of the second hydrotreater section (or region) 111.Optionally, the first reactor region can operate at the temperature of at least 50 DEG C or 25 DEG C lower than second segment effluent 55 expection from first paragraph reactor 110 be heat-staple and optional after to be preheated further and without the risk of coking and fouling.

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

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

A.Nebula20 obtains from Albemarle

b.CriterionDN3651,DN3551

c.AlbermarleKF860

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

Fig. 3 depicts embodiment, and wherein SCT charging adjusts well heater to avoid tar coking risk around this reactor feed/effluent interchanger and charging.In this embodiment, this SCT10 this reactor feed/effluent interchanger 70 or reactor feed adjustment well heater 90 in do not heat but make temperature close to this Reactor inlet or this reactor feed divider within when it mixes with effectiveness fluid and hydrogen 91 hydrogen adjusted in well heater 90 at reactor feed/effluent interchanger 70 and reactor feed fully overheated.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 to reactor feed and be heated to above required reactor inlet temperature.Then hot mixt 91 mixes with SCT50 and entire mixture 100 enters the reactor 110 being now in required reactor inlet temperature.Alleviate or eliminated at reactor feed/effluent interchanger 70 and the coal-tar middle oil coking and fouling risk of reactor feed adjustment well heater 90, because SCT charging does not preheat.Optionally, in the embodiment that another Fig. 3 does not show, only this effectiveness fluid is through this charging/effluent interchanger.Tar charging, effectiveness fluid, and then recycle hydrogen can heat in reactor feed adjustment well heater.

This embodiment ultimate principle is that this tar stream of not preheating is to the temperature higher than generation coking problem.On the contrary, by to heat on this effectiveness fluid and hydrogen to required reactor inlet temperature and then or be in close proximity to this Reactor inlet place and mix this tar stream effectiveness fluid higher with temperature and hydrogen and this preheating energy is provided, be wherein mixed to and want required reactor inlet temperature and contact catalyst and start hydrotreatment and react immediately.

This reactor feed/effluent interchanger and charging adjustment well heater are for subsequent use in another embodiment.This selects the impact alleviating the generation of any tar coking and fouling.This careful way can be allowed online or off-line decoking and more etc. importantly be allowed that flow reactor operates.Feed heater downstream side can comprise tank to reclaim the coking of peeling off during de-coking operations.This ultimate principle is also used to any method layout with supplementary alleviation anti-coking risk.

Application charging adjustment heater structure with by design than in Conventional heaters (until 4394kg/secm ²vs. general 1465kg/secm ²) more high quality flux, be less than 31,500W/m ²coking minimizes by lower heat flux and the highest film temperature being less than 910 °F (488 DEG C).

Fig. 4 describes an embodiment and wherein applies heat coking and fouling risk to be minimized to the catalyst bed of this reactor head.SCT not preheating in this reactor feed/effluent interchanger 70 or reactor feed adjustment well heater 90, but carry out gradually with reacting within reactor 110 itself and progressively reach temperature by supply external heat 102 at least the first catalyst bed 118.Such as 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 charging stream 102 and 101 in heat-transfer fluid provide.

In other embodiment, stream 102 and 101 can represent the process fluid of steam or heat or other thermal source any, such as, and outside electrical equipment wall well heater.Observe this method and reduce or eliminate incrustation in bench-scale testing factory research.It is found that to there is simultaneously this tar of preheating at this catalyzer, effectiveness fluid and hydrogen than with catalyst exposure before preheating cause a lot of more successfully, the operation of non-coking.Should be appreciated that the catalyst bed configurations of tubular reactor is the inner structure of 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 optionally in this reactor feed/effluent interchanger 70 and reactor feed adjustment well heater 90 on request preheating to make energy more efficient and be reduced in heat source requirement in hydrotreater reactor.This SCT not preheating in this reactor feed/effluent interchanger 70 or reactor feed adjustment well heater 90.At Fig. 4, another does not show this SCT in embodiment and can be preheated to enough low temperatures to avoid coking or incrustation.

In the embodiment of application hydrotreated liquid products recycled matter as this effectiveness fluid, this recycled matter can by obtaining this recycled matter and degassed from stabilizer tower distillation tower (stabilizerdistillationcolumn) bottoms.This liquid recycle thing can also obtain from flash separator bottoms.

Embodiment

Here is in Fig. 2-4, describe embodiment example, calculates and uses process simulation software, obtains from InvensysInc. process simulation software is a kind of simulator of stable state, can improve Process Design and operational analysis.It is designed to implement the strict quality for many chemical processes and energy balance calculating.For analogue reactor charging and Characterization of The Products are based on boiling point curve (simulation distil GC, ASTMD2887) and the density from experimental data.

For all embodiments, 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, acid gas removal, and utility appliance such as interchanger and recycle gas compressors.Optionally, provide light fuel and low-volatility fuel separating of oil with the product preparing two kinds of hydrotreatments.In this selects, this light-weight fuel oil is used as effectiveness fluid 20.

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

Comparative example 1

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

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 reduce to minimum.This embodiment uses the first lesser temps section 110 hydrotreating reactor more highly active catalyzer of application such as Nebula20CriterionDN3651, DN3551 or AlbermarleKF860 so that the first reactor region charging 54 to be only heated to 600 °F (375 DEG C).First paragraph reactor effluent 55 reaches 611 °F (322 DEG C).But at this, the highest coking active precursor (bituminous matter, cyclic diolefine, aromatic vinyl, alkene, diene, oxygen carrier) hydrotreatment.Then first paragraph reactor effluent 55 is heated to 742 °F (394 DEG C) and is heated to second segment reactor inlet temperature 750 °F (400 DEG C) 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 around this reactor feed/effluent interchanger 70 and reactor feed adjustment well heater 90.This SCT feed steam 50 is in 534 °F (279 DEG C) in this embodiment.Hydrogen 60 and effectiveness fluid 20 mix and guide to reactor feed/effluent interchanger 70 feeding side and be heated to 780 °F (415 DEG C) relative to 804 °F (429 DEG C) reactor effluent 120.Then heats stream 80 guides to reactor feed adjustment well heater 90 and is heated to 940 °F (504 DEG C).Then these 940 °F (504 DEG C) hot mixts 91 mix and this entire mixture 100 with 534 °F of (279 DEG C) SCT50, are now in required reactor inlet temperature 750 °F (400 DEG C), enter reactor 110.

Embodiment 4

Fig. 4 describes an embodiment, and the catalyst bed wherein to this reactor head applies heat coking and fouling risk to be minimized.SCT not preheating in this reactor feed/effluent interchanger 70 or reactor feed adjustment well heater 90, but progressively reaches 750 °F of (400 DEG C) temperature of reaction and carries out with reacting 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 to reactor feed and be heated to 750 °F (400 DEG C).Then this mixture 100 enters reactor 110.The SCT feed steam 50 of 534 °F (279 DEG C) also enters reactor 110.First catalyst bed 118 is designed to RT-621 catalyzer in pipe and the tubular reactor of heat-transfer fluid in shell.To be mixed with SCT feed steam by the mixture 100 adding hot hydrogen and effectiveness fluid and enter comprise this catalyzer 118 pipe and start to react.Heat-transfer fluid stream 102 enters 118 shell side heat supplies at 800 °F-850 °F (427 DEG C-454 DEG C) and leaves to this reactor with as stream 101, its then can in adjustment preheating oven 90 external heat (not shown) in another coil pipe.SCT charging, effectiveness fluid and hydrogen mixture leave this tubular reactor 118 in required temperature of reaction 750 °F (400 DEG C) and enter the catalyst bed 116 and 117 comprising RT-621 catalyzer.

Other document that all patents, test method and the application quote as proof, comprises priority document, is incorporated herein by reference completely, and its degree makes the above-mentioned openly and above-mentioned authority quoted consistent with the application be all allow.

Although illustrative forms disclosed in the present application is careful description, very clear other various improvement it will be apparent to those skilled in the art that and can easily by completing, and condition does 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 regards the patentable novel features comprising these open existence all as, comprises all features that can disclose one of ordinary skill in the art thus and be used as its equivalent.

When the lower limit of numeral and the upper limit of numeral list in the application, the scope that it is expected to is from any lower limit to any upper limit.

Claims

1. a hydroconversion process, comprising:

C (), from the second mixture separation tar stream, wherein this tar stream comprises the >=molecule of the second mixture of atmospheric boiling point >=290 of 90wt.% DEG C, and wherein this tar stream has the >=aromatics carbon content of 70wt.%;

D () provides effectiveness fluid, this effectiveness fluid comprises >=1.0wt.% aromatic hydrocarbons, based on the weight of effectiveness fluid;

E () providing package is containing the hydrogen stream of molecular hydrogen;

F this tar stream to be exposed to the temperature of 200.0 DEG C-400.0 DEG C by (i) by () under, (ii) under this effectiveness fluid being exposed to the temperature of temperature >=400.0 DEG C and then the effectiveness fluid of this tar stream and heating is merged, and/or (iii) this hydrogen stream is exposed to >=temperature of 400.0 DEG C under and one or more modes in then the hydrogen stream of this tar stream and heating being merged heat this tar stream;

(g) in hydrotreating zone under the effectiveness fluid of the hydrogen stream of (i) this hydrogen stream and/or heating and (ii) this effectiveness fluid and/or heating exists by effectiveness fluid: tar stream weight ratio is that the tar stream that heats at least partially of catalytic hydroprocessing condition hydrotreatment of 0.05 to 3.0 is to produce the product of hydrotreatment, the content of the product of hydrotreatment that wherein this effectiveness fluid comprises is >=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 at least 2.6x10 ⁶the product of this hydrotreatment of continuous production second.

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

5. the process of claim 1 wherein that the hydrocarbon of the first mixture comprises in petroleum naphtha, gas oil, wax-like residual oil, long residuum or crude oil one or more.

6. the process of claim 1 wherein that the hydrocarbon of the first mixture comprises mixtures of residua.

7. the method for claim 5, wherein gas oil is vacuum gas oil.

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

9. the process of claim 1 wherein that this hydrotreatment is implemented at the temperature of 200.0 DEG C-450.0 DEG C under at least one hydrotreating catalyst exists.

10. the process of claim 1 wherein the temperature of this tar heating to 200.0 DEG C-300.0 DEG C in step (f) (i).

The method of 11. claims 1, wherein step (f) (i) comprises (A) and guides this tar stream through at least one well heater, wherein this tar stream extracts heat, (B) guide this tar stream through the first channel of at least one interchanger and guide the product of hydrotreatment at least partially through the second passage of interchanger to extract heat from the product of this hydrotreatment to this tar stream, or (C) this tar stream thermopositive reaction at least partially.

The method of 12. claims 1, wherein whole for the product of hydrotreatment liquid phase separation is light weight fluid and heavy liquid by (i), wherein heavy liquid is included in this liquid phase the molecule that there are 90wt.% atmospheric boiling point >=300 DEG C, (ii) this effectiveness fluid comprises this light weight fluid of a part, and (iii) this effectiveness fluid has ASTMD8610% and distills point >=60.0 DEG C and 90% and distill point≤350.0 DEG C.

13. the process of claim 1 wherein that step (f) (i) comprises guides this tar stream through 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 14. claims 1, wherein step (f) (i) comprises this hydrogen stream of guiding, this tar stream together with this effectiveness fluid through at least one well heater, and wherein this tar stream, this effectiveness fluid and this hydrogen stream extract heat from this well heater.

15. the process of claim 1 wherein that step (f) comprises the temperature of this effectiveness fluid of heating to >=425.0 DEG C and merges the effectiveness fluid of this tar stream and heating.

16. 1 kinds of hydroconversion process, comprising:

A () provides the first mixture, it comprises >=50.0wt.% hydrocarbon, based on the weight of the first mixture;

B () pyrolysis first mixture is to produce the second mixture in the presence of steam, it comprises>=C of 1.0wt.% ₂unsaturates and>=1.0wt.% tar, this weight percentage is based on the weight of the second mixture;

E () providing package is containing the hydrogen stream of molecular hydrogen;

F () guides this tar stream through at least one well heater by (i), (ii) guide this tar stream through the first channel of at least one interchanger and the second passage guiding heat-transfer fluid to pass interchanger to extract heat from this heat-transfer fluid to this tar stream, or (iii) heats the temperature T that this tar stream is heated to 200.0 DEG C-400.0 DEG C by the temperature of this effectiveness fluid to>=425.0 DEG C and one or more modes in being merged by the effectiveness fluid of this tar stream and heating ₁;

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

The method of 17. claims 16, wherein this hydrotreating zone comprises at least two catalyst beds, is wherein supplied to the first catalyst bed to major general's indirect heating.

The method of 18. claims 17, wherein to the first catalyst bed supply outside heat, this first catalyst bed comprises many and comprises the pipe of at least one hydrotreating catalyst and guide this tar stream, this hydrogen stream and this effectiveness fluid at least partially to pass these many pipes under catalytic hydroprocessing condition, and this outside heat is supplied to the outside surface of these many pipes.

The method of 19. claims 16, the Pressure Drop wherein running through this hydrotreating zone is less than the initial pressure drop running through this hydrotreating zone 3.0 times.

The method of 20. claims 16, the hydrogen consumption of the per unit volume tar stream of wherein this hydrotreatment is 71 to 267Sm ³/ m ³.

The method of 21. claims 16, wherein this hydrotreating zone be at least divided into the first and second hydrotreating zone and wherein the first hydrotreating zone operate at 100 DEG C of temperature at least lower than the second hydrotreating zone.

The method of 22. claims 16, wherein this hydrotreating zone comprises at least one high-activity hydrogenation catalyst bed.

The method of 23. claims 22, wherein this catalyzer is selected from Nebula20, CriterionDN3651, CriterionDN3551, or AlbermarleKF860, and combination.