CN102197115B - Systems and methods for producing a crude product - Google Patents

Abstract

A flexible once-through process for hydroprocessing heavy oil feedstock is disclosed. The process employs a plurality of contacting zones and at least a separation zone to convert at least a portion of the heavy oil feedstock to lower boiling hydrocarbons, forming upgraded products. The contacting zones operate under hydrocracking conditions, employing a slurry catalyst which comprises an active metal catalyst having an average particle size of at least 1 micron in a hydrocarbon oil diluent, at a concentration of greater than 500 wppm of active metal catalyst to heavy oil feedstock. The plurality of contacting zones and separation zones are configured in a permutable fashion allowing the once-through process to be flexible operating in various modes: a sequential mode; a parallel mode; a combination of parallel and sequential mode; all online; some online and some on stand-by; some online and some off-line; a parallel mode with the effluent stream from the contacting zone being sent to at least a separation zone in series with the contacting zone; a parallel mode with the effluent stream from the contacting zone being combined with an effluent stream from at least another contacting zone and sent to the separation zone; and combinations thereof. In one embodiment, the effluent from a contacting zone is sent to the next contacting zone in series for further upgrade, with the next contacting zone having a pressure drop of at most 100 psi, with the pressure drop is not due to a pressure reducing device as in the prior art. In one embodiment, at least an additive material selected from inhibitor additives, anti-foam agents, stabilizers, metal scavengers, metal contaminant removers, metal passivators, and sacrificial materials, in an amount of less than 1 wt. % of the heavy oil feedstock, is added to at least one of the contacting zones.

Description

For the production of the system and method for thick product

The cross reference of related application

The application requires the submission date to be the U.S. Patent application sequence No.12/233171,12/233 on September 18th, 2008,327,12/233393,12/233439,12/212796 and 12/212737 and the submission date be 12/506 of on July 21st, 2009,987,12/506,937 and 12/506,840 right of priority.The application requires right of priority and the rights and interests of aforementioned application, by reference their content is incorporated to herein.

Technical field

The present invention relates to for heavy oil feed being processed or the system and method for upgrading, and the thick product that uses such system and method to produce.

Background technology

Petroleum industry turns to gradually as heavy oil feed such as heavy crude, residual oil, coal, Tar sands etc. to material source.What these feeds were characterised in that high density is rich in bituminous matter residual oil and low API degree, and some of them are low to moderate and are less than 0 ° of API.

U.S. Patent No. 7390398,7431822,7431823 and 7431831 has been described method, system and the catalyzer for the treatment of heavy oil feed.In the various embodiments of prior art, waste slurry catalyzer and unconverted heavy oil feed recirculation are returned to process and merge with fresh heavy oil feed, therefore make heavy oil conversion rate maximize.

Still need technique heavy oil feed to carry out improved system and the method for upgrading/processing, particularly obtain the improved system of good prepared using with less catalyzer rate of utilization.

Summary of the invention

On the one hand, the present invention relates to heavy oil feed to carry out the method for hydrotreatment, the method is used multiple zone of action and at least one disengaging zone, and the method comprises: the gas feed that hydrogen is provided; The slurry catalyst that comprises the active catalyst in hydrocarbon oil diluent is provided; In the first zone of action by the gas feed of at least part of described hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst under the hydrocracking condition in sufficient temp and enough pressure, merge so that at least part of described heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form upgraded product; Using from comprising of described the first zone of action described upgraded product, described slurry catalyst, the gas of described hydrogen and the mixture of unconverted heavy oil feed first effluent material stream deliver to the first disengaging zone as charging, wherein volatility upgraded product is shifted out together with the first top stream with the gas of described hydrogen, and using described slurry catalyst, drift as the first non-volatile material compared with the hydrocracking product liquid of heavy and described unconverted heavy oil feed; Wherein in interchangeable mode, described multiple zone of action and disengaging zone are configured so that described multiple zone of action and disengaging zone operate with following pattern: ordered mode; Parallel model; The combination of parallel model and ordered mode; All on-line; Some are online and some are for subsequent use; Some online and some off-lines; Be sent to the parallel model of at least one disengaging zone of connecting with this zone of action from the described outflow streams of described zone of action; Merge and deliver to the parallel model of described disengaging zone from the described outflow streams of described zone of action and the outflow streams from another zone of action at least; And their combination.

On the other hand, the present invention relates to heavy oil feed to carry out the method for hydrotreatment, the method is used multiple zone of action and at least one disengaging zone, comprises the first zone of action and the zone of action except the first zone of action, and the method comprises: the gas feed that hydrogen is provided; Heavy oil feed is provided; With active metal catalyst with heavy oil feed than the concentration that is greater than 500wppm, the slurry catalyst charging that comprises the active metal catalyst that in hydrocarbon oil diluent, median size is at least 1 micron is provided; The gas feed of at least part of described hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst charging are merged in the first zone of action under hydrocracking condition at least part of described the first heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form upgraded product; By from comprising of described the first zone of action described upgraded product, described slurry catalyst, the gas of described hydrogen and the first effluent material stream of unconverted heavy oil feed deliver to the first disengaging zone, wherein volatility upgraded product is shifted out together with the first top stream with the gas of described hydrogen, and using described slurry catalyst, isolate and drift as the first non-volatile material compared with the hydrocracking product liquid of heavy and described unconverted heavy oil feed, wherein said the first non-volatile material stream contains the solid that is less than 30%; Collect described the first top stream for further processing in product purification unit; Collect described the first non-volatile material stream and separate and be recovered in interior further processing for comprising slurry catalyst, wherein described slurry catalyst is separated and recovery with the described hydrocracking product liquid compared with heavy with described unconverted heavy oil feed.

In the third aspect, the present invention relates to heavy oil feed to carry out the method for hydrotreatment, the method is used multiple zone of action and at least one disengaging zone, comprises the first zone of action and the zone of action except described the first zone of action, and the method comprises: the gas feed that hydrogen is provided; Heavy oil feed is provided; Amount with the 1wt% that is less than heavy oil feed provides at least one additive materials that is selected from inhibitor additive, defoamer, stablizer, metal scavenger, metal pollutant remover, metal passivator and expendable material; The slurry catalyst charging that comprises the active metal catalyst that in hydrocarbon oil diluent, median size is at least 1 micron is provided; The gas feed of at least part of described hydrogen, at least part of described heavy oil feed, at least part of described additive materials and at least part of described slurry catalyst charging are merged in the first zone of action under hydrocracking condition at least part of described the first heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form upgraded product; First effluent material stream from described the first zone of action is delivered to the first disengaging zone, wherein volatility upgraded product is shifted out together with the first top stream with the gas of described hydrogen, and using described slurry catalyst, separate and drift as the first non-volatile material compared with the hydrocracking product liquid of heavy and described unconverted heavy oil feed, wherein said the first non-volatile material stream contains the solid that is less than 30%; Collect described the first top stream for further processing in product purification unit; Collecting described the first non-volatile material flows for further processing in catalyst recovery unit.

Aspect another, the present invention relates to heavy oil feed to carry out the method for hydrotreatment, the method is used multiple zone of action and at least one disengaging zone, and the method comprises: the gas feed that hydrogen is provided; Heavy oil feed is provided; The slurry catalyst charging that comprises the active metal catalyst that in hydrocarbon oil diluent, median size is at least 1 micron is provided; The gas feed of at least part of described hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst charging are merged in the first zone of action operating under the first pressure under hydrocracking condition, so that at least part of described the first heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form upgraded product; First effluent material stream from described the first zone of action is delivered to inlet pressure than the first disengaging zone of the low maximum 100psi of the first pressure, wherein volatility upgraded product is shifted out together with the first top stream with the gas of described hydrogen, and using described slurry catalyst, drift as the first non-volatile material compared with the hydrocracking product liquid of heavy and unconverted heavy oil feed, wherein said the first non-volatile material stream contains the solid that is less than 30%; Collect described the first top stream for further processing in product purification unit; Collecting described the first non-volatile material flows for further processing in catalyst recovery unit.

Accompanying drawing is briefly described

Fig. 1 is the schema of schematically describing the embodiment of a through type upgrading system, and described upgrading system has two zone of action with ordered mode (series connection) operation.

Fig. 2 is the schema of the second embodiment of upgrading process, and described upgrading process has three zone of action with ordered mode operation, and wherein each zone of action has the disengaging zone of series connection (optionally with bypass).

Fig. 3 is the schema of another embodiment of a through type upgrading process, and described upgrading process has the zone of action of three tandems (walking abreast) operation, and wherein each zone of action has the disengaging zone of series connection (optionally with bypass).

Fig. 4 is the schema of the embodiment of a through type upgrading process of handiness, and described upgrading process has multiple zone of action and disengaging zone, and some of them zone of action moves with ordered mode, and the 3rd reactor is for subsequent use, or with incoming flow tandem operation separately.

Fig. 5 is the schema of another embodiment of a through type upgrading process of handiness, and described upgrading process has the unit of tandem (walking abreast) operation and has steam injection, and VGO and additive are fed to toward some zone of action.

Fig. 6 is the schema of another embodiment of a through type upgrading process of handiness, and described upgrading process has three tandems (walking abreast) operation and shares the zone of action of a disengaging zone.

Fig. 7 is the schema of another embodiment of a through type upgrading process, described upgrading process has two zone of action with ordered mode operation, its sequential operation is tandem, has with the heavy oil feed of himself, optional VGO charging and the single of catalyst charge and contact in upgrading operation.

Describe in detail

The heavy oil feed that the present invention relates to heavy oil feed, particularly has a high heavy metal content is processed or the improved system of upgrading.

Term below using in whole specification sheets, and except as otherwise noted, below term there is implication below.

As used herein, " heavy oil " charging or feed refer to heavy and overweight raw material, include but not limited to residual oil, coal, pitch, shale oil, Tar sands etc.Heavy oil feed can be liquid, semisolid and/or solid.The example of described heavy oil feed that can upgrading includes but not limited to Canadian Tar sands herein, from Brazilian Sang Tuosi and Campos basin, the Egyptian gulf in Suez, Chad lake, Venezuela Zulia, the Sumatran vacuum residuum of Malaysia and Indonesia.Other example of heavy oil feed comprises bucket substrate and the residual oil that oil refining processing is remaining, comprises " bucket substrate " and " residual oil "-atmospheric tower substrate, and its boiling point is at least 343 DEG C (650 °F); Or vacuum distillation tower substrate, its boiling point is at least 524 DEG C (975 °F); Or " slag oil asphalt " and " vacuum residuum "-its boiling point is more than 524 DEG C (975 °F).

The character of heavy oil feed includes but not limited to: at least 0.1, at least 0.3 or at least 1 TAN; At least viscosity of 10cSt; API degree is maximum 15 in one embodiment, and in another embodiment maximum 10.One gram of heavy oil feedstock typically contains the Ni/V/Fe of at least 0.0001 gram; The heteroatoms of at least 0.005 gram; The raffinate of at least 0.01 gram; The C5 bituminous matter of at least 0.04 gram; At least 0.002 gram of MCR; Every gram of crude oil; At least 0.00001 gram of one or more organic acid an alkali metal salt; The sulphur of at least 0.005 gram.In one embodiment, heavy oil feed has at least API degree of sulphur content and-5～+ 5 of 5wt%.

In one embodiment, heavy oil feed comprises Athabasca pitch (Canada) and has at least 50 volume % vacuum resid.In another embodiment, described feed is Boscan (Venezuela) charging with at least 64 volume % vacuum resid.In one embodiment, heavy oil feed contains at least 100ppm V (every grammes per square metre oil feed).In another embodiment, V level is 500-1000ppm.In the 3rd embodiment, be 2000ppm at least.

Term " processing ", " treated ", " upgrading ", " carrying out upgrading " and " through upgrading ", in the time being combined with heavy oil feed, describe and carried out or carried out the heavy oil feed of hydrotreatment or material or the crude product of gained, the concentration reduction of the molecular weight reduction of heavy oil feed, the boiling range reduction of heavy oil feed, the reduction of bitum concentration, hydrocarbon free radical and/or the amount of impurity for example sulphur, nitrogen, oxygen, halogenide and metal are reduced.

The upgrading of heavy oil feed or processing typically refer to " hydrotreatment " in this article.Hydrotreatment refers to any processing of carrying out under hydrogen exists, includes but not limited to hydrocracking, hydrocracking, hydrogenation, hydrotreatment, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), Hydrodearomatization, hydroisomerization, Hydrodewaxing and comprises the hydrocracking of selective hydrogenation cracking.The product of hydrotreatment can show viscosity, viscosity index, saturates content, low-temperature performance, volatility and the depolarize etc. of improvement.

As used herein, hydrogen refers to hydrogen and/or under heavy oil feed and catalyzer exist, reacts and one or more compounds of hydrogen are provided.

SCF/BBL (or scf/bbl) refers to the gas (N of every barrel of hydrocarbon charging ₂, H ₂deng) standard cubic foot unit.

Nm ³/ m ³refer to the gas nominal cubic meter of every cubic metre of heavy oil feed.

VGO or vacuum gas oil, refer to the hydrocarbon of the boiling Range Distribution Analysis under 0.101MPa with 343 DEG C of (650 °F)-538 DEG C (1000 °F).

" wppm " represents 1,000,000/weight.

As used herein, term " catalyst precursor " refers to the compound that contains one or more catalytically-active metals, finally forms catalyzer by described compound.It should be noted that catalyst precursor can have the catalytic activity as hydrotreating catalyst.As used herein, " catalyst precursor " can be called herein " catalyzer " in the time using in the linguistic context at catalyst charge.

As used herein, term " live catalyst " refers to not yet used catalyzer or catalyst precursor in the reactor of hydrotreatment operation.Term live catalyst also comprises the catalyzer of " regeneration " or " recovery " in this article, for example at least reactor of hydrotreatment operation, used (" used catalyzer ") but its catalytic activity level recovered or at least brought up to fully the catalyzer higher than the catalytic activity level of used catalyst.Term " live catalyst " can exchange and use with " fresh slurry catalyzer ".

As used herein, term " slurry catalyst " (or be sometimes called " slurry " or " dispersed catalyst ") refers to that catalyzer and/or catalyst precursor particle (aggregate, particulate or crystal grain) disperse liquid medium for example oil, water or its mixture therein.Term slurry catalyst refers to live catalyst, or in heavy oil upgrading, uses and reduced active catalyzer.

In one embodiment, slurry catalyst incoming flow contains live catalyst.In another embodiment, slurry catalyst charging contain can be in feed heater and/or zone of action original position form the catalyst precursor composition of the good distribution of active catalyst.Can be using granules of catalyst in one embodiment as powder, be incorporated into medium (thinner) as precursor or in the 3rd embodiment in another embodiment after pre-treatment step.In one embodiment, medium (or thinner) is hydrocarbon oil diluent.In another embodiment, liquid medium is heavy oil feed itself.In another embodiment, liquid medium is hydrocarbon ils for example VGO medium or the thinner except heavy oil feed.

As used herein, " catalyst charge " comprises any catalyzer that is suitable for heavy oil feedstock to carry out upgrading, for example, and one or more body catalysts and/or one or more are at supported catalyst.In one embodiment, catalyst charge is slurry catalyst form.

As used herein, term " body catalyst " can with " unsupported catalyst " exchange use, represent be not conventional catalyst form (for example its have preliminary shaping, preformed catalyst carrier then by dipping or deposited catalyst make this carrier be loaded with metal) catalyst composition.In one embodiment, body catalyst forms by precipitation.In another embodiment, body catalyst has the tackiness agent of bringing in catalyst composition.In another embodiment, body catalyst forms by metallic compound and without any tackiness agent in the situation that.In the 4th embodiment, body catalyst is the disperse type catalyzer for example, using as the dispersed catalyst particle in liquid (hydrocarbon ils) mixture.In one embodiment, catalyzer comprises one or more commercial known catalyzer, for example, from the Microcat of ExxonMobil company ^tM.

As used herein, term " zone of action " refers to wherein by contacting with slurry catalyst charging under existing at hydrogen and heavy oil feed is processed or the equipment of upgrading.In zone of action, at least the character of thick charging can be changed or upgrading.Zone of action can be a part for reactor, reactor, multiple parts of reactor or their combination.Term " zone of action " can exchange and use with " reaction zone ".

In one embodiment, upgrading process comprises multiple reactors as zone of action, and the structure of described reactor is identical or different.The example of spendable reactor comprises stacked bed reactor, fixed-bed reactor, ebullated bed reactor herein, continuous agitator tank reactor, fluidized-bed reactor, spray reactor, liquid/liquid contactor, slurry reactor, liquid recirculation reactor and their combination.In one embodiment, reactor is up-flow reactor.In another embodiment, be downflow reactor.In one embodiment, at least slurry bed hydrocracking reactor that zone of action refers to at least fixed bed hydrogenation treatment reactor is connected.In another embodiment, at least one zone of action also comprises built-in (in-line) hydrotreater, and this hydrotreater can be removed and in handled crude product, exceed 70% sulphur, exceedes 90% nitrogen and exceed 90% heteroatoms.

As used herein, term " disengaging zone " refers to and wherein the upgrading heavy oil feed from zone of action is directly added to separated region or at the equipment that carries out being directly added to after one or more intermediate treatment separated region, for example high pressure-temperature flash tank or flash separator, wherein separate with volatile liquid gas with non-volatile part.In one embodiment, the material stream of non-volatile part comprises unconverted heavy oil feed, a small amount of compared with the hydrocracking product liquid of heavy (synthetic or less volatility/nonvolatile upgraded product), slurry catalyst and any entrained solid (bituminous matter, coke etc.).In one embodiment, disengaging zone provides from a zone of action to the pressure drop of next zone of action of connecting.Pressure drop allows gas to separate and cause with non-volatile part with volatile liquid by disengaging zone.

In one embodiment, zone of action and disengaging zone are merged in an equipment, described equipment for example has reactor or the staged reactor-separator of inner separator.In reactor-separator structure of the type, vapor product slave unit top is left, and non-volatile part is left with slurry catalyst in sidepiece or the bottom of equipment together with entrained solids part (if any).

In one embodiment, to comprise be then the single reaction vessel of separator to upgrading system.In another embodiment, described system comprises at least two up-flow reactors of connecting with at least one separator, after at least one separator is set directly at the final reactor of series connection.In another embodiment, comprise by multiple tandem reactors of unique sequence (train) operation.In the 4th embodiment, comprise by the Parallel Sequence with multiple reactors.In the 5th embodiment, comprise to walk abreast and multiple reactors of the combining and configuring of serial operation.Have wherein and operate with regard to handiness other embodiment that upgrading system is configured, with the various combination of reactor/flash separator, from a kind of operator scheme to another kind of operator scheme, for example parallel (tandem) runs to series connection (along continuous) operation.

In one embodiment, upgrading system can comprise the reactor of connecting with staged reactor-separator and the combination of separator, before wherein solvent deasphalting (SDA) unit is arranged on the first reactor between the reactor of any two series connection or in series connection as inter-stage system for handling.

This upgrading system is characterised in that once operate by pattern, and itself and upgrading system difference of the prior art are that slurry catalyst and heavy oil feed flow through zone of action once, instead of as prior art around system recirculation or circulate again.In a through type upgrading system, in fact unconverted material and the recirculation of slurry catalyst compound are not got back to first in series connection (or front) zone of action or reactor.From the non-volatile material of last disengaging zone in upgrading system, comprise unconverted material, compared with the hydrocracking product liquid of heavy (synthetic product or non-volatile/less volatility upgraded product), slurry catalyst, a small amount of coke, bituminous matter etc., be sent in one embodiment the further processing/regeneration of elsewhere for catalyzer, or be sent to oil removing unit so that spent catalyst is separated with hydrocarbon, deliver to subsequently metals recovery units with from waste catalyst recovery precious metal.

Oil removing unit and/or metals recovery units can be with a through type upgrading system in identical places, or they can be from a through type upgrading system in different places, for example carry out oil removing by the other party in different areas or country (different party) and operate, and/or carry out metal recovery in strange land by the contractor in different areas or country.

processing condition: in one embodiment, upgrading system is for example maintained under hydrocracking condition under minimum temperature to realize the hydrocracking of heavy oil feed.In one embodiment, in the temperature of 400 DEG C of (752 °F)-600 DEG C (1112 °F) and the pressure of 10MPa (1450psi)-25MPa (3625psi) operating system of getting off.In one embodiment, process regulation is obtained and runs through approximately equably zone of action.In another embodiment, between zone of action, condition changes and has the upgraded product of various specific natures in order to obtain.

In one embodiment, zone of action technological temperature is approximately 400 DEG C of (752 °F)-Yue 600 DEG C (1112 °F), be less than in another embodiment 500 DEG C (932 °F), and be greater than in another embodiment 425 DEG C (797 °F).In the first embodiment, system °F operates taking the temperature difference between the zone of action of entrance and exit as 5-50.

Make in the first embodiment the temperature of disengaging zone maintain zone of action temperature ± 90 °F (approximately ± 50 DEG C) in, in the second embodiment in ± 70 °F (approximately ± 38.9 DEG C), in the 3rd embodiment in ± 15 °F (approximately ± 8.3 DEG C), in the 4th embodiment in ± 5 °F (approximately ± 2.8 DEG C).In one embodiment, last disengaging zone and immediately the temperature difference between last zone of action in ± 50 °F (approximately ± 28 DEG C).

Operation pressure in zone of action is about 10MPa (1 in one embodiment, 450psi)-Yue 25MPa (3,625psi), in the second embodiment, be about 15MPa (2,175psi)-Yue 20MPa (2,900psi), in the 3rd embodiment, be less than 22MPa (3,190psi), in the 4th embodiment, be greater than 14MPa (2,030psi).

A through type upgrading system is characterised in that logistics throughput is much higher compared with upgrading system of the prior art (with unconverted heavy oil feed recirculation).In each zone of action, the liquid hourly space velocity of heavy oil feed (LHSV) will be generally about 0.075h in the first embodiment ^-1-Yue 2h ^-1; In the second embodiment, be about 0.1h ^-1-Yue 1.5h ^-1, in the 3rd embodiment, be about 0.15h ^-1-Yue 1.75h ^-1, in the 4th embodiment, be about 0.2h ^-1-Yue 1h ^-1, in the 5th embodiment, be about 0.2h ^-1-Yue 0.5h ^-1.In one embodiment, LHSV is 0.1h at least ^-1.In another embodiment, LHSV is less than 0.3h ^-1.

In one embodiment, multiple reactors that zone of action comprises single reaction vessel or series connection, thus the total residence time of 0.1-15 hour is provided.In the second embodiment, the residence time is 0.5-5 hour.In the 3rd embodiment, the total residence time in zone of action is 0.2-2 hour.

pressure drop is minimized: in the prior art, disclose for pressure drop higher in heavy oil upgrading system, pressure drop 1000psi at the most in the time entering disengaging zone, is preferably 300-700psi, can relatively easily lower (lighter) boiling point material be separated/shift out from this upgrading system by disengaging zone.Can be because the introducing of reliever causes high pressure drop.But, discovery has the upgrading system fluctuation of service of higher pressure drop, particularly frequent jams, this is due to the settling in equipment and/or common valve operational issue, these problems comprise due to valve inlet or outlet is stopped up, valve corrosion or corrode and can not open under setting pressure.

In one embodiment, with regard to for example efficiency of optimum operation, a through type upgrading system is designed, compared with prior art stopped up along with pressure drop is less than 100psi the shut-down period much shorter causing by equipment.Obtain optimum efficiency with minimum pressure drop in system in one embodiment, wherein make the pressure of disengaging zone maintain in the first embodiment last zone of action ± 10 to ± 100psi in, in the second embodiment in ± 20 to ± 75psi, in the 3rd embodiment in ± 50 to ± 100psi.The pressure drop so using refers to the difference between top hole pressure X and the inlet pressure Y of disengaging zone of last zone of action, and wherein (X-Y) is less than 100psi.

System for sequential operation can also be to obtain optimum efficiency from a zone of action to the minimum pressure of next zone of action, make in the first embodiment pressure drop be maintained below 100psi, in the second embodiment, be below 75psi, in the 3rd embodiment, be less than 50psi.Pressure drop herein refers to the difference between the top hole pressure of a zone of action and the inlet pressure of next zone of action.

In one embodiment, zone of action is communicated with to obtain minimum pressure drop with the direct fluid in next disengaging zone or zone of action.The direct fluid connection using herein refers to from zone of action to next disengaging zone (or next zone of action) of series connection to have unrestricted flow, and there is no flow limitation.In one embodiment, obtain that direct fluid is communicated with and not by valve, orifice plate (or allied equipment), or pipe diameter changes the flow limitation causing.

In one embodiment, from zone of action to next disengaging zone or the minimum pressure drop of zone of action (in the time entering disengaging zone or zone of action) owing to pipe the relay part such as ell pipeline, bend pipe, Y-tube etc., and not owing to as used the reliever such as valve, the control valve etc. that cause pressure decreased in prior art.In the prior art, instructed disengaging zone to play stage head shield retaining.

In one embodiment, while flowing to next equipment of series connection from zone of action at effluent, minimum pressure drop is to be increased and Level Change causes by frictionloss, wall resistance, volume.If use valve in once by system, valve is selected/designs to make to remain on below 100psi to the pressure drop of next part equipment from for example zone of action of an equipment.

hydrogen feed: in one embodiment, provide sources of hydrogen to this process.Hydrogen also can join in heavy oil feed before entering preheater or after preheater.In one embodiment, hydrogen feed and heavy oil feed also enter zone of action in same pipeline stream.In another embodiment, sources of hydrogen can be joined to zone of action along the direction contrary with feed flow.In the 3rd embodiment, the heavy oil of hydrogen by gas pipeline and merging and slurry catalyst incoming flow separate and enter zone of action.In the 4th embodiment, hydrogen feed was introduced directly into catalyzer and the heavy oil feed of merging before introducing zone of action.In another embodiment, the heavy oil of hydrogen and merging and catalyst charge are introduced in the bottom of reactor as point other material stream.In another embodiment, hydrogen can be added to some regions (the section)/position of zone of action.

In one embodiment, provide sources of hydrogen (ratio based on gaseous hydrogen source of the gas with heavy oil feed): 0.1Nm with following flow rate to this process ³/ m ³-Yue 100,000Nm ³/ m ³(0.563-563,380SCF/bbl), about 0.5Nm ³/ m ³-Yue 10,000Nm ³/ m ³(2.82-56,338SCF/bbl), about 1Nm ³/ m ³-Yue 8,000Nm ³/ m ³(5.63-45,070SCF/bbl), about 2Nm ³/ m ³-Yue 5,000Nm ³/ m ³(11.27-28,169SCF/bbl), about 5Nm ³/ m ³-Yue 3,000Nm ³/ m ³(28.2-16,901SCF/bbl) or about 10Nm ³/ m ³-Yue 800Nm ³/ m ³(56.3-4,507SCF/bbl).

In one embodiment, some hydrogen (25-75%) are supplied to the first zone of action, and by rest part as a supplement hydrogen join other zone of action in system.

In some embodiments, sources of hydrogen and carrier gas are merged and make its recirculation pass through zone of action.Carrier gas can be for example nitrogen, helium and/or argon gas.Carrier gas can promote flowing of heavy oil feed and/or flowing of sources of hydrogen in zone of action.Carrier gas can also strengthen the mixing in zone of action.In some embodiments, can use sources of hydrogen (for example hydrogen, methane or ethane) as carrier gas and make its recirculation pass through zone of action.

catalyst charge: in an embodiment of the upgrading system moving in ordered mode, all slurry catalyst chargings are provided to the first zone of action.In other embodiment of ordered mode, at least part of catalyst charge " is separated " or redirect at least one other zone of action in system (except the first zone of action).In another embodiment of the zone of action moving in tandem (walking abreast), slurry catalyst charging (with heavy oil feed) is accepted in the zone of action in all operations.

In one embodiment, at least 10% of " at least partly " expression catalyzer.In another embodiment, be at least 20%.In the 3rd embodiment, be at least 40%.In the 4th embodiment, make at least one zone of action except first zone of action at least 50% live catalyst steering.

In an embodiment of sequential operation, the catalyst charge that is less than 60% is added to the first zone of action in system, make other zone of action in more than 40% live catalyst steering.In another embodiment, catalyst charge is divided equally between the zone of action in system.In one embodiment, at least part of live catalyst charging is delivered to at least one indirect contact area and/or the last zone of action in system.

In another embodiment, with regard to handiness catalyst charge scheme, this process design is made sometimes catalyst charge to be added to the first reactor the certain time section in system with full ratio (100% required catalyst ratio), then divide equally ground or be separately added to all reactors lasting scheduled time amount in system according to predetermined proportion, or for treating that the catalyst charge that is added to different reactor with different concns separates according to predetermined proportion.

Slurry catalyst charging used herein can comprise as single catalyst charge stream or one or more different slurry catalysts of point other incoming flow.In one embodiment, single live catalyst incoming flow is supplied to zone of action.In another embodiment, live catalyst charging comprises multiple different catalyst type, wherein some catalyst type toward one or more zone of action (for example flows to as independent material, the first zone of action in system), and different slurry catalysts as different catalyst stream to the zone of action except the first zone of action in system.

In one embodiment, different catalysts being delivered to zone of action, front-end and back-end can be used for alleviating vanadium intercepting and capturing problem and maintains overall upgrading performance.In one embodiment, Ni only or the NiMo sulfide slurry catalyst that is rich in Ni are delivered to front reaction device to contribute to the vanadium in minimizing system to intercept and capture, and simultaneously can be by different catalyzer, be for example rich in the Mo sulfide of Mo or NiMo sulfide catalyst be injected into rear end reactor maintaining overall high conversion, improve product quality and (in one embodiment) likely reduces gas yield.As used herein, the slurry catalyst that is rich in Ni refers to that Ni/Mo ratio is greater than 0.15 (in wt.%), and on the contrary, the slurry catalyst that is rich in Mo refers to that Ni/Mo ratio is less than 0.05 (in wt.%).

In one embodiment, first slurry catalyst charging carries out preconditioned (precondition) before contacting with heavy oil feed before one of entering in zone of action or before entering zone of action.In an example, described catalyzer enters preconditioned unit with hydrogen with the flow rate of 500-7500SCF/BBL (BBL refers to toward the cumulative volume of the heavy oil feed of system) herein.Do not make cold catalyzer contact with heavy oil feed, preconditioned step contributes to hydrogen adsorption in active catalyst position, and finally contributes to transformation efficiency.In an embodiment with pre-body conditioning unit, slurry catalyst/hydrogen mixture is heated to the temperature of 300 °F-1000 °F (149-538 DEG C).In another embodiment, in hydrogen at the temperature of 500-725 °F (260-385 DEG C) catalyzer described in preconditioned.In another embodiment, mixture is heated in the first embodiment under the pressure of 300-3200psi; In the second embodiment, pressure is 500-3000psi; In the 3rd embodiment, pressure is 600-2500psi.

the slurry catalyst using: slurry catalyst is included in the active catalyst in hydrocarbon oil diluent.In one embodiment, catalyzer is to comprise at least one group vib metal, or at least one VIII family metal, or the sulphurized catalyst of at least one IIB family metal, for example iron sulphide catalyzer, zinc sulphide, nickelous sulfide, moly-sulfide or iron sulphide zinc catalyst.In another embodiment, catalyzer is the multimetallic catalyst that comprises at least one group vib metal and at least one VIII family metal (as promotor), and wherein metal can be simple substance form or form of metal compound.In an example, catalyzer is the MoS with at least VIII family metallic compound promotes ₂catalyzer.

In one embodiment, catalyzer is the body multimetallic catalyst that comprises at least one VIII family base metal and at least two kinds of group vib metals, and wherein at least two kinds of group vib metals are approximately 10 with the ratio of VIII family base metal: 1-approximately 1: 10.In another embodiment, catalyzer has formula (M ^t) _a(X ^u) _b(S ^v) _d(C ^w) _e(H ^x) _f(O ^y) _g(N ^z) _h, wherein M represents at least one group vib metal, such as Mo, W etc., or their combination; X plays promoter metals effect, represents with lower at least one: VIII family base metal for example Ni, Co; Such as Fe of VIII family metal; Such as Cr of group vib metal; Such as Ti of IVB family metal; Such as Zn of IIB family metal, and their combination (hereinafter X is called " promoter metals ").In this formula, t, u, v, w, x, y, z represent the total charge of each component (being respectively M, X, S, C, H, O and N) in addition; Ta+ub+vd+we+xf+yg+zh=0.B with a subscript than the value with 0-5, and (0 <=b/a <=5).S represents that the value of subscript d is for the sulphur of (a+0.5b) to (5a+2b).C represents that subscript e has the carbon of the value of 0 to 11 (a+b).H is that f value is the hydrogen of 0 to 7 (a+b).O represents that g value is the oxygen of 0 to 5 (a+b); N represents that h has the nitrogen of the value of 0 to 0.5 (a+b).In one embodiment, for single metal component catalyzer, for example catalyzer of Mo (there is no promotor) only, it is 0 value that subscript b has.

In one embodiment, described catalyzer is prepared by catalyst precursor composition, and described composition includes organic metal complex or for example transition metal of compound and organic acid oil-soluble compounds or complex compound.The example of this compound comprises group vib and VIII family metal such as naphthenate, acetylacetonate (pentanedionate), octylate and the acetate of Mo, Co, W etc., for example molybdenum naphthenate, naphthenic acid vanadium, sad vanadium, hexacarbonylmolybdenum and Vanadium hexacarbonyl.

In one embodiment, slurry catalyst has the median size of at least 1 micron.In another embodiment, slurry catalyst has the median size of 1-20 micron.In the 3rd embodiment, slurry catalyst has the median size of 2-10 micron.In one embodiment, slurry catalyst particle comprises catalyst molecule and/or is of a size of the aggregate of the nano sized particles of colloid (be less than 100nm, be less than about 10nm, be less than about 5nm and be less than about 1nm).In another embodiment, it is for example the individual layer MoS of 5-10nm that described granules of catalyst comprises nano-scale on edge ₂bunch.In operation, the particle of colloid/nano-scale is assembled in hydrocarbon diluent, is the slurry catalyst of 1-20 micron thereby form median size.

In one embodiment, the slurry catalyst of q.s is added to zone of action so that each zone of action has slurry (solid) catalyst concn of the 500wppm-3wt.% at least ratio of heavy oil (catalyst metal with).

In one embodiment, for giving and expect that boiling point is less than at least 75% transformation efficiency of the material of 1000 °F (538 DEG C) from heavy oil under the high throughput of 0.15LHSV at least, the amount that is added to the catalyzer in zone of action is the 500-7500wppm of catalyst metal in heavy oil feed.In the second embodiment, the concentration of live catalyst charging is 750-5000wppm catalyst metal.In the 3rd embodiment, be 1000-3000wppm.In the 4th embodiment, concentration is less than 3000wppm.In the 5th embodiment, concentration is 1200ppm at least.Catalyst metal refers to the active metal in catalyzer, for example, just wherein use Ni as with regard to the NiMo sulfide slurry catalyst of promotor, and catalyst metal herein refers to Mo concentration.

Can expect using less catalyzer for upgrading system, for example, be less than 500ppm or be even less than 200ppm or 100ppm.But this is less than non-constant/less desirable transformation efficiency of 50% by causing in one embodiment, is even less than 10% in the second embodiment.Low levels of catalysts also causes unstable operation, for example unconverted heavy oil generation sedimentation (letdown), coking, obstruction etc. in equipment, particularly reactor.

optional system for handling-SDA: in one embodiment, before the first zone of action, use solvent deasphalting unit (SDA) with by the pre-treatment of heavy oil feed.In another embodiment, use SDA as the temporary location being arranged in behind one of middle disengaging zone.In refinery, typically use SDA unit to extract incrementally the more hydrocarbon of lightweight from heavy hydrocarbon streams, the oil wherein extracting is typically called deasphalted oil (DAO), and stay simultaneously and there is weight molecule and the larger oil of dreg of heteroatoms concentration stream, this oil of dreg stream is typically called SDA tar, SDA bottoms etc.SDA can be independent unit or be integrated into the unit in upgrading system.

In SDA, can use all kinds of SOLVENTS, from propane to hexane, this depends on diasphaltene level required before being fed to zone of action.In one embodiment, SDA is designed to produce deasphalted oil (DAO) for concocting or be directly added to zone of action to substitute or supplementary heavy oil feed with catalyst charge.Like this, can carry out optimization to type of solvent and operational condition makes to produce high volume and can accept the DAO of quality and be added to zone of action.In this embodiment, the suitable solvent using for low volume SDA tar and high volume DAO includes but not limited to hexane or similar C6+ solvent.This scheme can allow most heavy oil feed obtaining upgrading in zone of action subsequently, will otherwise use and can not produce a favourable very heavy bucket end bottom thing that increases progressively conversion economy because needs add a large amount of hydrogen.

In one embodiment, in SDA, by all heavy oil feed pre-treatment and DAO product is added in the first zone of action, or according to feed solutions feed separately, wherein at least a portion is gone to the zone of action the first zone of action in series connection.In another embodiment, first by some heavy oil feed (depending on source) pre-treatment and some feeds are directly added in zone of action in untreated situation in SDA.In another embodiment, DAO and untreated heavy oil feed are merged as an incoming flow arrival zone of action.In another embodiment, in point other feed pipe, DAO and untreated heavy oil feed are added in system, DAO goes to one or more zone of action and untreated heavy oil feed is gone to one or more identical or different zone of action.

Use therein in the embodiment of SDA as temporary location, by contain from the non-volatile part of the coke/bituminous matter of the slurry catalyst of at least one disengaging zone and optional minimum quantity etc. deliver to SDA for the treatment of.Using DAO itself as incoming flow, combine as charging with heavy oil feed, or combine as charging with the bottom stream from one of disengaging zone, deliver at least one zone of action from SDA unit.Send to any metal of taking out of in slurry catalyst of recovery by containing bitum DAO bottoms, or for the bitum application of needs, for example, with oil fuel blending, use with pitch, or utilized in some other application.

In one embodiment, by regulating solvent for use and with respect to the required DAO rate of recovery of heavy oil feed, the quality of DAO and DAO bottoms being changed.At optional pretreatment unit, for example in SDA, the DAO oil of recovery is more, and the overall qualities of DAO is poorer, and the overall qualities of DAO bottoms is also poorer.Select about solvent, typically, along with using lighter solvent for SDA, will produce fewer DAO, but quality is by better, if but the heavier solvent of use will produce more DAO, but quality will be lower.This is particularly caused by bituminous matter and the solvability of other weight molecule in solvent.

heavy oil feed: heavy oil feed can comprise herein as single incoming flow or as dividing other heavy oil feed stream one or more different heavy oil feed from different sources herein.In one embodiment, single heavy oil conduit (conduit pipe) is to past all zone of action.In another embodiment, use multiple heavy oil pipelines (conduit) that heavy oil feed is supplied to different zone of action, some of them heavy oil feed flows to toward one or more zone of action, and some other heavy oil feed flow to toward one or more different contact zone.

In some embodiments, at least part of heavy oil feed (treating upgrading) " separated " before being added in zone of action or redirect at least one other zone of action (except the first zone of action) or SDA unit.In an embodiment of sequential operation, the unconverted heavy oil feed that is less than 90% is added to the first reactor in system, wherein more than 10% unconverted heavy oil feed is redirect to other zone of action in system.In another embodiment of tandem operation, between the zone of action by heavy oil feed in system, divide equally.In another embodiment, the unconverted heavy oil feed that is less than 80% is added to the first zone of action in system, and all the other heavy oil feed are redirect to last zone of action in system.In the 4th embodiment, the heavy oil feed that is less than 60% is added to the first zone of action in system, and remaining unconverted heavy oil feed is divided equally between other zone of action in system.

In one embodiment, heavy oil feed was preheated before concocting with slurry catalyst incoming flow.In another embodiment, thus by the concoction of heavy oil feed and slurry catalyst charging preheat to produce viscosity enough low feed allow catalyzer to be mixed well in this feed.In one embodiment, at the low temperature at least about 100 DEG C (212 °F) of the hydrocracking temperature than in zone of action, preheat.In another embodiment, preheat at least about the temperature of 50 DEG C the hydrocracking temperature than in zone of action is low.In the 3rd embodiment, the mixture of heavy oil feed and/or heavy oil feed and slurry catalyst preheats at the temperature of 500-700 °F (260-371 DEG C).

optional additive-defoamer injects: as used herein, front end zone of action (or first zone of action) refers to first reactor of multiple zone of action with sequential operation.In an embodiment of system with at least three zone of action, the first front end zone of action can comprise the first and second reactors.In one embodiment, at least one defoamer is injected into at least one zone of action in system so that foam volume minimizes and can make reaction zone make full use of.As used herein, term defoamer comprises froth breaking material and de-soak material, in order to prevent that foam from producing and/or reduction foaming degree.In addition, some froth breaking materials can have two kinds of functions, for example, reduce under certain conditions/alleviate foaming, and under other operational condition, prevent that foam from producing.

Defoamer is optional to be purchased product such as silicoorganic compound is as polydimethylsiloxane (PDMS), polydiphenylsiloxane, fluorinated siloxane etc. from many, and its amount is the 1-500ppm of heavy oil feed.In one embodiment, use polymer PDMS, for example its viscosity exceedes 60,000cSt in one embodiment, exceedes in another embodiment 100,000cSt, in the 3rd embodiment, exceedes 600,000cSt.Think that the defoamer of viscosity higher (higher molecular weight) decomposes and more slowly and not too tend to pollute and cause poisoning of catalyst by Si.

In one embodiment, defoamer is joined to such as kerosene of hydrocarbon solvent, this has reduced the viscosity of defoamer and has made it can pumping.In one embodiment, defoamer is 1 with the ratio of solvent: 1-1: 1000.In another embodiment, be 1: 2-1: 100.In the 3rd embodiment, be 1: 3-1: 50.In one embodiment, make defoamer in the hydrocarbon solvent of q.s, dilute to make it have the viscosity that is less than 1000cSt, thereby can use standard equipment to process it.

In one embodiment, defoamer is directly joined to heavy oil feed.In another embodiment, mixture is injected along multiple positions of up-flow reactor.In another embodiment, defoamer solvent mixture is injected into the top of up-flow reactor.In the 4th embodiment, be injected in 30%Nei region, height for reactor top.In one embodiment defoamer is injected in the top of reactor and has improved the liquid back mixing in reactor.

optional additive-inhibitor/stablizer/expendable material: in one embodiment, supplementing or substituting as defoamer, to be selected from least one additive of inhibitor, stablizer, metal scavenger, metal pollutant remover, metal passivator and expendable material with the 1-20 of heavy oil feed, the amount of 000ppm joins zone of action (being referred to as " additive materials ").In the second embodiment, add additive materials with the amount that is less than 10,000ppm.In the 3rd embodiment, additive materials is 50-1000ppm.

Should notice that some additives can have several functions.In one embodiment, some metal scavengers can also be used as metal pollutant remover and/or metal passivator under suitable condition.In another embodiment, expendable material used can be used for as metal scavenger the heavy metal of Sorption of Heavy Oil charging.Some other expendable materials, except playing the effect of the metal scavenger for absorbing metal, also absorption or trapping comprise other material of deposit coke.

In one embodiment, additive materials is directly joined to heavy oil feed.In another embodiment, additive materials is joined to slurry catalyst charging.In the 3rd embodiment, join zone of action using additive materials as (separate) incoming flow independently.

In one embodiment, additive materials can add same as before or in suitable diluent or carrier solvent.Exemplary carrier solvent includes but not limited to aromatic hydrocarbon solvent for example toluene, dimethylbenzene and crude oil derived aromatics distillment.Exemplary thinner comprises vacuum gas oil, diesel oil, decanted oil, turning oil and/or lightweight gas oil.In some embodiments, can make additive materials be dispersed in the heavy oil feed of small part.

In one embodiment, additive materials is injected in the top area (section) of reactor.In another embodiment, additive materials is injected in multiple opening for feeds of up-flow reactor.

In one embodiment, additive materials is selected to realize well emulsify or the dispersion of heavy oil studies on asphaltene.In another embodiment, what additive materials was selected to improve the storage stability of heavy oil feed and/or improvement can pumping.In another embodiment, additive is stabilizer compounds for example acetone, metacetone and the oil of mirbane that contains polar link, adds with the amount of the 0.001-0.01wt% of heavy oil feed.

In one embodiment, additive materials is inhibitor additive, is selected from oil soluble polynuclear aromatic substance, Young's modulus depressant, for example organic and inorganic bronsted lowry acids and bases bronsted lowry and metalloporphyrin.In another embodiment, selected additive is aliphatic amide or aliphatic amine derivative and the such as metal fatty acid salt of Special Metal salt compound of alkoxide.

In one embodiment, additive materials is " expendable material " (or " material for trapping "), it is for trapping deposit coke and/or the metal (Ni, V, Fe, Na) of heavy oil feed, or for making deposit coke and/or metal (Ni, V, Fe, the Na) deposition and/or fixing of heavy oil feed, thereby alleviate the deleterious effect of these materials to catalyzer and/or equipment.In another embodiment, additive materials is used for the bituminous matter of fixing/Sorption of Heavy Oil feed, thereby alleviates catalyst deactivation.In one embodiment, expendable material has large hole, and the BET surface-area for example having is 1m at least in the first embodiment ²/ g is 10m at least in the second embodiment ²/ g is 25m at least in another embodiment ²/ g.In another embodiment, additive materials is to have at least 0.005cm ³the expendable material of the pore volume of/g.In the second embodiment, pore volume is 0.05cm at least ³/ g.In the 3rd embodiment, total pore volume is 0.1cm at least ³/ g.In the 4th embodiment, pore volume is 0.1cm at least ³/ g.In one embodiment, expendable material has at least 0.5cm ³the pore volume of/g.In another embodiment, there is at least 1cm ³/ g.

In one embodiment, the microballoon that expendable material comprises for example calcined kaolin of macropore inert material.In another embodiment, expendable material is characterised in that at least 20% of its pore volume is made up of the hole of at least 100 dusts; In the second embodiment, formed by the hole of 150-600 dust.

The example that is used for the additive materials that traps settling/removing metal includes but not limited to such as Mg of silicate compound ₂siO ₄and Fe ₂siO ₄; Inorganic oxide for example iron oxide compound as FeO.Fe ₂o ₃, FeO, Fe ₃o ₄, Fe ₂o ₃deng.Other example of additive materials comprises silicate compound for example fumed silica, Al ₂o ₃, MgO, MgAl ₂o ₄, zeolite, calcined kaolin microballoon, titanium dioxide, gac, carbon black and their combination.The example of metal passivator includes but not limited to alkaline earth metal compound, antimony and bismuth.

In one embodiment, additive materials is from the metal scavenger that for example Degussa, Albermale, Phosphonics and Polysciences buy of originating.In one embodiment, metal scavenger is with trade(brand)name DELOXANE ^tMfrom the macroporosity organic radical functional polysiloxane of Degussa.

In one embodiment, scavenging agent/trapping agent/scavenging agent material source is in slurry catalyst, the waste slurry catalyzer of dry powdered form specifically.In one embodiment, waste slurry catalyzer is from using means known in the art for example to be carried out oil removing and shifted out the heavy oil upgrading system of at least 75% heavy oil by membrane filtration, solvent extraction etc.There is at least 1m as the waste slurry catalyzer of expendable material in one embodiment ²the BET surface-area of/g originally can be along the coke/metal of reactor inner member deposition in order to trap.In the second embodiment, waste slurry catalyzer has at least 10m ²the BET surface-area of/g.In the 3rd embodiment, BET surface-area is greater than 100m ²/ g.

In one embodiment, additive is the scavenging agent/trapping agent/scavenging agent material that derives from the useless de-oiling slurry catalyst that has wherein shifted out some or most of metal.In one embodiment, additive is the waste slurry catalyst mode of drying, and at least some or most of metal such as nickel, molybdenum, cobalt etc. shift out from this spent catalyst.In one embodiment, expendable material is the solid residue form that comprises coke and for example ammonium meta-vanadate of some VB family metal complexs, and described residue obtains after most of metal for example molybdenum, nickel are shifted out by pressure leaching method.In another embodiment, expendable material is the solid residue form that mainly comprises coke, wherein leaves considerably less vanadium (ammonium meta-vanadate form).

In another embodiment, expendable material is carbon black, and to select it be due to its high surface-area, various aperture structure and be easy to be reclaimed/separated with heavy metal by burning.In addition, carbon material is relatively soft, therefore makes the infringement of reducing valve and miscellaneous equipment material minimize.In one embodiment, carbon material can be any general known to and commercially available material.Example includes but not limited to porous prilled carbon solid, it is characterized in that the distribution of sizes and 10 of 1-100 micron is to exceeding 2,000m ²the BET surface-area of/g.In one embodiment, carbon material has median size and the about 90-approximately 1 of 1-50 micron, 500m ²the BET surface-area of/g.In another embodiment, carbon material has the median size of 10-30 micron.Optionally, catalystic material for example can be calcined and/or first carried out pre-treatment with slurry catalyst dipping by one or more technology as generally known in the art being added to before mixing in upgrading system and/or with heavy oil feed.

In one embodiment, additive materials comprises and has for example 100m at least of large surface-area ²the gac in the aperture of the hole area of/g and 100-400 dust.In one embodiment, additive materials is to be the DARCO KB-G of 40 microns as D-90 ^tMfrom the powdered active carbon that is purchased of Norit.In another embodiment, being purchased carbon material is that D-90 is the DARCO INSUL of 23 microns ^tM.In another embodiment, additive materials comprises the carbon black obtaining by the coking of waste slurry catalyzer in heavy oil residue, and described heavy oil residue carrys out the metal recovery process since waste slurry catalyst recovery/separating metal.

In one embodiment, along with using surface treated expendable material, additive materials plays several functions, and the such as removing of settling trapping/metal and froth breaking, the removing of settling trapping/metal suppress mutually with centre etc.In one embodiment, expendable material is with at least for example inhibitor of additive materials and/or defoamer carry out surface treatment (or coating).

In one embodiment, additive materials is the carbon black of surface modification.In one embodiment, surface-treated carbon black contains the reactive functional groups that antifoam performance is provided from the teeth outwards, and has necessary surface-area and coke and/or the metal (Ni, V, Fe, Na) of aperture structure to deposit in trapping and/or fixing heavy oil feed.In one embodiment, additive is surface-treated carbon black, wherein makes carbon contact with for example following additive for heavy oil: silicoorganic compound are as dialkylsiloxane polymkeric substance, polydimethylsiloxane, polydiphenylsiloxane, poly-phenylbenzene dimethyl siloxane, fluorinated siloxane and their mixture.

In another embodiment, multifunction additive is the expendable material that for example carboxylic acid of topical oil solube metallic compound and carboxylate salt, oil soluble polynuclear aromatic substance, Young's modulus depressant and other additive materials known in the art are processed.

In another embodiment, defoamer such as silicoorganic compound, alkyl defoamer succeedingly are ejected into carrier such as carbon black, titanium dioxide etc. upper to produce the multifunction surface treatment additive for upgrading system.

optional water injects-controls heavy metal deposition: as used herein, front end zone of action (or first zone of action) refers to the first reactor in the system with multiple zone of action with ordered mode (continuously) operation.In an embodiment of system with at least three zone of action, the first front end zone of action can comprise the first and second reactors.In another embodiment, the first zone of action only refers to the first reactor.

As used herein, term " water " is for representing water and/or steam.

Controlling in an embodiment of heavy metal deposition, optionally water is injected in a through type upgrading system with the ratio of about 1-25wt.% (with respect to heavy oil feed).In one embodiment, the water that injects q.s is to obtain the water concentration of 2-15wt.% in system.In the 3rd embodiment, inject q.s to obtain the water concentration of 4-10wt.%.

If need to control heavy metal deposition and/or improve catalyst activity, water can be added continuously or off and on (injection).Water can be joined in heavy oil feed before or after preheating.In one embodiment, a large amount of water is joined and treats that pre-warmed heavy oil is in material mixture, and a large amount of water is directly joined in front end zone of action.In another embodiment, only by heavy oil feed, water is joined in front end zone of action.In another embodiment, at least 50% water is joined to heavy oil to be heated in material mixture, and remaining water is directly joined in front end zone of action.

In one embodiment, water is incorporated in system as a part for slurry catalyst charging.In one embodiment, with heavy oil feed, or before being added to system as point other incoming flow, water is joined to slurry catalyst charging and carries out pre-treatment with this slurry catalyst and hydrogen.

In one embodiment, water is incorporated in system with the amount of the about 25wt.% of approximately 1-of the heavy oil feed that enters preheating the stage (before heavy oil feed is preheated).In one embodiment, the part using water as heavy oil feed joins in all zone of action.In another embodiment, water is joined only in the heavy oil feed toward the first zone of action.In another embodiment, water is joined only in the charging toward the first two zone of action.

In one embodiment, in the multiple positions along zone of action, water is directly joined in zone of action with the ratio of the 1-25wt.% of heavy oil feed.In another embodiment, by water directly join in this process, tend to most to occur heavy metal deposition several zone of action at first in.

In one embodiment, some water are joined in this process with dilution steam generation form.In one embodiment, at least 30% water is added with vapor form.In the embodiment therein water being added as dilution steam generation, can add steam in any position in this process.For example, can be joined in the heavy oil feed before or after preheating, join in catalyzer/heavy oil mixture material stream, and/or directly join in the gas phase of zone of action, or add in the multiple positions along the first zone of action.Dilution steam stream can comprise process steam or clean steam.Steam can be heated before being added in upgrading process in stove or make it overheated.

In embodiments, water is joined at least one of the first zone of action and the second zone of action with the amount of 30 % by weight at the most of heavy oil feed.

Think that the existence of water has advantageously changed metallic compound sulfur molecule balance in this process, therefore reduced heavy metal deposition.Water/steam in the first zone of action is expected to the heavy metal deposition on minimizing equipment.In one embodiment, also think and contribute to control/maintain temperature distribution required in zone of action adding of water.In another embodiment, think and water is joined to front end zone of action and reduced the temperature of reactor.Can make the temperature of the first zone of action keep than the low at least 5-25 of the temperature degree (Fahrenheit temperature) of next zone of action of series connection.

Because reduced temperature of reactor, think the speed of reaction of reactive maximum vanadium material slow get off, thereby make vanadium deposit on slurry catalyst and make catalyzer take vanadium settling out of reactor therefore to have limited the deposition of solids in reactor apparatus with controllable manner more.

In one embodiment, compared with not adding the operation of water, with regard to suitable operating time section, for example at least with regard to February, the heavy metal deposition thing making in reactor apparatus that adds of water is reduced by least 25%.In another embodiment, compared with not adding the operation of water, water add the heavy metal deposition thing that is reduced by least 50%.In the 3rd embodiment, compared with not adding the operation of water, water add the heavy metal deposition that is reduced by least 75%.

optional other hydrocarbon charging: in one embodiment, can be optionally using such as VGO(vacuum gas oil of other hydrocarbon oil feed), matter turning oil in petroleum naphtha, MCO(), light cycle (LCO), heavy recycle stock (HCO), solvent join any zone of action in system as a part for heavy oil feed stream with the amount of the 2-40wt.% of heavy oil feed to body (solvent donor) or other aromatic solvent etc.In one embodiment, the effect of the thinner that reduces heavy oil feed viscosity is played in other hydrocarbon charging.

with temperature of reactor control heavy metal deposition: in one embodiment, as water being joined with the substituting and/or supplementing of the front end zone of action of sequential operation, reduce the temperature of tending to the front end zone of action that heavy metal deposition occurs most.

In one embodiment, be than next reactor low at least 10 °F (5.56 DEG C) of series connection by the Temperature Setting of the first reactor.In the second embodiment, the first temperature of reactor is set as than next reactor low at least 15 °F (8.33 DEG C) of series connection.In the 3rd embodiment, be low at least 20 °F (11.11 DEG C) by Temperature Setting.In the 4th embodiment, be than next reactor low at least 25 °F (13.89 DEG C) of series connection by Temperature Setting.

system performance: in an embodiment of a through type upgrading system and under the much lower catalyst concn of the art methods than thering is recycle stream, for example be less than under the concentration of 5000wppm catalyst metal, the heavy oil feed of 75wt% is at least converted into compared with lighter products in high throughput single pass method (only using a reactor or multiple reactor tandem/parallel running).In another embodiment, obtain at least 80% transformation efficiency with the slurry catalyst concentration within the scope of 750-4000wppm catalyst metal in the methods of the reactors of ordered mode operation thering are two.In the 3rd embodiment, obtain at least 80% transformation efficiency with the high heavy oil throughput of the catalyst concn within the scope of 750-2500wppm and 0.15LHSV.In the 4th embodiment, be to obtain with the concentration within the scope of 1000-1500wppm catalyst metal.In an embodiment with three tandem reactors, have been surprisingly found that, through type upgrading system for example, with little a lot of catalyst concn (2500ppm) with have that recirculation for example, compares with the prior art of greater catalytic agent concentration (4200ppm) that transformation efficiency equates or better.As used herein, transformation efficiency refer to heavy oil feed to boiling point the transformation efficiency lower than 1000 °F of (538 DEG C) materials.

In one embodiment, in the method for recirculation, to be less than 5000wppm catalyst metal, at least 98% heavy oil feed is converted into compared with lighter products thering are three tandem reactors and do not have.In another embodiment, for being less than 2500wppm catalyst metal, transformation efficiency is at least 98%.In another embodiment, for the slurry catalyst with 1500-5000wppm catalyst metal concentration, transformation efficiency is at least 80%.In the 4th embodiment, for the slurry catalyst with 1500-5000wppm catalyst metal concentration, transformation efficiency is at least 95%.

In one embodiment, one time through type upgrading system provides at least 60% sulphur transformation efficiency for the slurry catalyst concentration within the scope of 750-5000wppm catalyst metal, at least 20% conversion rate of nitrogen and at least 50% MCR transformation efficiency.

In one embodiment, because the hydrogen adding has expanded heavy oil cumulative volume, a through type upgrading system produces in upgraded product and exceedes 100% volume yield (than the heavy oil of input).Upgraded product, compared with low boiling hydrocarbon, comprises liquefied petroleum gas (LPG) (LPG) in one embodiment, gasoline, diesel oil, vacuum gas oil (VGO) and monopropellant oil.In the second embodiment, upgrading system provides at least 110% volume yield with the form of LPG, petroleum naphtha, monopropellant oil and VGO.In the 3rd embodiment, at least 115% volume yield.

In one embodiment, depend on condition and the position of disengaging zone, in non-volatile portion part-streams, be less than 50wt% (accounting for the gross weight of non-volatile material stream) compared with the amount of heavy isocrackate.In the second embodiment, in the non-volatile material stream from disengaging zone, be less than 25wt% compared with the amount of heavy isocrackate.In the 3rd embodiment, in the non-volatile material stream from disengaging zone, be less than 15wt% compared with the amount of heavy isocrackate.In oil of dreg stream, the amount of solid for example, changes according to level of conversion and optional additive materials (if any) expendable material used.In one embodiment, the solids content in oil of dreg stream is 1-10% solid in the first embodiment, is 2-5% solid in another embodiment, in the 3rd embodiment, is less than 30wt% solid, in the 4th embodiment, is less than 40wt% solid.

the embodiment of brief description of the drawings: with reference to accompanying drawing to further describe embodiment of the present invention.

Fig. 1 schematically describes to use slurry catalyst once heavy oil feed is carried out by pattern to the block diagram of the upgrading system 110 of upgrading.First, heavy oil feed 104 is incorporated into together with slurry catalyst charging 110 in the first zone of action 120 of system.In the figure, heavy oil feed 104 can be preheated before being added in zone of action in well heater (not shown).Hydrogen 121 can be introduced together with the charging of heavy oil/slurry catalyst in as directed same pipeline 122, or optionally be introduced as independent incoming flow.Although do not show, water and/or steam can be introduced together with slurry catalyst with charging in same pipeline, or be entered as point other incoming flow.In addition, the mixture of water, heavy oil feed and slurry catalyst can be preheated at well heater before being added in zone of action.Can optionally other hydrocarbon oil feed 105 for example VGO, petroleum naphtha be joined to any zone of action in system as a part for incoming flow with the amount of the 2-30wt.% of heavy oil feed.In one embodiment, in the first zone of action, make to be greater than the heavy oil feed conversion of half and the hydrogen feed of consumption at least 25% in the first zone of action.

The outflow streams 123 that comprises upgrading material, waste slurry catalyzer and unconverted heavy oil feed, hydrogen etc. is taken out and delivers to disengaging zone 130, for example heat separator from the first zone of action 120.

Disengaging zone 130 causes or allows gas to separate with non-volatile part with volatile liquid.In one embodiment, gaseous state and volatile liquid part 131 are taken out from top, disengaging zone and use it for oil-poor contactor or downstream process 160 and further process.By comprising slurry catalyst and entrained solid, coke, unconverted heavy oil feed, in heat separator etc., next zone of action 140 in series connection is taken out and be added to the tower bottoms stream 133 of newly-generated hydrocarbon, thereby produce for the other reaction of upgrading material more.(not shown) in another embodiment, flows out next zone of action 140 that streams 123 is walked around disengaging zone 130 and directly delivered to series connection.

In one embodiment, the live catalyst charging 110 of other part and heavy oil feed 104 are directly added in the zone of action 140 of series connection as the incoming flow of point other material stream or merging.In another embodiment, also for example VGO of optional hydrocarbon ils feed 105 (vacuum gas oil) is added in next zone of action 140.(not shown) in one embodiment, is also provided to zone of action 140 using water and/or steam as point other incoming flow, or in same pipeline, introduces together with slurry catalyst with charging.Hydrogen 141 can be introduced together with charging in same pipeline, or optionally be introduced as independent incoming flow.(not shown) in another embodiment, mixes at least part of or all hydrogen feed be added in reactor 140 with the liquid stream 133 from disengaging zone.Quenching hydrogen supply response hydrogen in one embodiment, because leave with vapor stream 131 from most of hydrogen of the first zone of action 120.

Comprise next disengaging zone 150 that flows to series connection with the outflow streams 142 of the upgrading material of slurry catalyst, hydrogen, coke, unconverted heavy oil etc. for gas is separated with non-volatile part 152 with volatile liquid 151.Take out gaseous state and volatile liquid part from top, disengaging zone, and itself and gaseous state and volatile liquid part from last disengaging zone are merged as material stream 161 for further processing in hydrotreatment system 160 or downstream product purification system.Non-volatile (or less volatility) portion part-streams is taken out and sent to for oil removing/metal recovery as oil of dreg stream 152.(not shown) in another embodiment, by for example LGO quench stream 161 in oil-poor contactor of hydrocarbon stream.

Hydrotreater 160 uses conventional hydrotreating catalyst in one embodiment, with the similar high pressure of upgrading system rest part (in 10psig) under operate, and can remove desulfuration, nitrogen and other impurity from upgraded product with the HDN level of conversion of > 99.99%, thereby the sulphur content higher than in 70 °F of boiling point parts that makes material stream 162 is reduced in the first embodiment and is less than 20ppm, in the second embodiment, is less than 10ppm.In another embodiment, at the temperature of built-in hydrotreater in 10 °F of zone of action temperature, operate.

Fig. 2 is the schema of another embodiment of a through type upgrading process, and this upgrading process has three zone of action with ordered mode operation, for example reactor 120,135 and 140, and wherein each zone of action has the disengaging zone with optional bypass pipe series connection.As shown, the outflow streams 123 that comprises upgrading material, waste slurry catalyzer and unconverted heavy oil feed, hydrogen etc. of taking out from the first zone of action 120 is delivered to disengaging zone 130, or the second zone of action 135 of directly delivering to series connection is for further upgrading.Or (as shown in dotted line), flows out streams 123 and can walk around disengaging zone 130 and directly enter next zone of action 135 of series connection.Also for example VGO of other catalyst charge, heavy oil feed and other feed hydrocarbon can be added to the second zone of action with other hydrogen feed 137.Flow out streams 136 and leave zone of action 135 and flow to disengaging zone 145, wherein the upgraded product of gas (comprising hydrogen) and volatile liquid form and non-volatile liquid part 147 are separated and set it as material stream 146 and shift out at tower top.Non-volatile material is flowed to 147 next zone of action 140 of delivering to series connection for further upgrading.

In some embodiments, contain with unconverted oil, proceed to as directed next reactor 140 compared with the non-volatile material stream 147 of the slurry catalyst of the hydrocracking product liquid of heavy, optional expendable material and a small amount of coking and bituminous matter combination.The other incoming flow that comprises the gas that contains hydrogen, optional VGO charging, optional (other) heavy oil feed and optional catalyst charge can be merged for reacting in the further upgrading of next reactor 140 with non-volatile material stream 147.The outflow streams 142 of carrying out autoreactor that comprises upgrading heavy oil feed flows to disengaging zone 150, wherein upgraded product and hydrogen is merged and sets it as overhead 151 and shift out.Using comprise non-volatile part such as catalyst pulp, contain coking and bitum unconverted oil, shift out for reclaim/regeneration of downstream catalyst as residual oil 152 compared with the tower bottoms stream of the hydrocracking product liquid of heavy, optional expendable material etc.

Fig. 3 is that three zone of action are by the schema of another embodiment of a through type upgrading process of Parallel Sequence, for example reactor 120,135 and 140 of described three zone of action, thus and there is optional bypass pipe and make a disengaging zone can be used for all three reactors.In one embodiment, system operates with all three reactor parallel work-flows under high logistics throughput, wherein each reactor has heavy oil feed, catalyst charge, the optional VGO charging etc. of himself, effluent is gone to an identical separator 150 or is gone to separately point other reactor, collects from the non-volatile part of separator as residual oil 152 for further processing.(not shown, or by shown in long and short dash line) in one embodiment, system is operating compared with under slow flow rates with the reactor of at least two serial operations, and wherein the non-volatile part of self-separation device is delivered to next reactor of series connection in the future.In one embodiment, the outflow streams of taking out from reactor can be delivered to the separation device being positioned at after each reactor, for example material stream 123 flows to separator 130, material stream 136 flows to separator 145, material stream 142 flows to separator 150, and the non-volatile material from any disengaging zone can be drifted/send to Residual Oil Tank 152 for reclaim/regeneration of downstream catalyst.

Share in an embodiment (as shown in long and short dash line) of separator at all reactors, all outflow streams are delivered to separator 150, wherein oil-poor contactor or downstream process 160 are taken out and delivered to overhead as material stream 151.

handiness operation: as the through type upgrading process with multiple zone of action and disengaging zone described in Fig. 3 constructs to provide handiness operation in interchangeable mode, thereby adapt to different operator schemes.Although do not show in Fig. 3, suitable valve can be arranged in process pipeline with opening/closing correspondingly, thereby a through type process system of permission be switched to another kind of operator scheme from a kind of operator scheme.

Different patterns includes but not limited to the combination of following pattern and they: a) operate with a reactor to two or three (or more) reactors; B) with operation be in a sequential manner multiple reactors of serial operation in low logistics throughput but operate under high transformation efficiency, next reactor of wherein delivering to series connection by the effluent from a reactor or from liquid stream at the bottom of the tower of separator is for further conversion; C), with the reactor of at least some tandems (walking abreast) operations with operate under high logistics throughput to the heavy oil feed toward each reactor, some of them reactor is in for subsequent use or off-line mode; D) by a hybrid operational mode with the reactor of reactor tandem (walking abreast) operation of other multiple series operations; E) operate with the reactor of tandem (walking abreast) operation, wherein the outflow streams from each reactor is delivered to the separator with described reactors in series; And f) operate with the reactor of tandem (walking abreast) operation, wherein the outflow streams of autoreactor merges and is delivered to separation and the recovery for upgraded product of or two separators in the future.

Although do not describe herein, but can there is other arrangement of aforesaid operations pattern, for example integrated mode, is wherein divided into the multiple incoming flows toward two or more tandem reactors by the effluent from a reactor or from liquid stream at the bottom of the tower of separator.In addition, because system is arranged by handiness operation, in can the process of the operation using any reactor as (or order by merging/tandem pattern) in a sequential manner, main or unique reactor, the first reactor (or the second reactor, the 3rd reactor etc.) operate, and can be using any disengaging zone the main or unique separator, first in successive processes (second or C grade) disengaging zone or unique disengaging zone.

In one embodiment, this process allows with the dissimilar handiness such as heavy oil feed, catalyst type operation, wherein reactor and their own feed system parallel runnings.Handiness parallel and/or series operation also allows a reactor to close down for sedimental purification, removal etc., and the rest part of this system operation simultaneously.This means and improved overall operation process efficiency with the minimum overall system shut-down period.

In one embodiment, this process allows the flexible conversion from an operator scheme to another operator scheme, and does not need unit close down and restart.In one embodiment, only making some zone of action keep operation for example when single reactor operation, other reactor maintains in hot standby mode, as in the reactor of operation under the pressure and temperature in rising.In one embodiment, maintain pressure and temperature in stand-by facilities, the hydrogen recycle of heat is by off-duty and keep one or more reactors for subsequent use.

In one embodiment, to be in the roughly the same temperature and pressure of operating reactor under reactor, q.s is supplied to each standby reactor through the gas feed of hydrogen of heating.As used herein, the temperature of roughly the same (or similar) refers in 50 °F of temperature of reactor that the temperature of standby reactor is in operation, in the 100psi of the reactor pressure that the pressure of standby reactor is in operation.

In one embodiment, the hydrogen of q.s is the 10-100% that is supplied to the hydrogen of operating reactor.In another embodiment, the hydrogen of this q.s is 10-30%.In the 4th embodiment, the hydrogen of q.s is to be supplied to the still 15-25% of the hydrogen total amount of the reactor in operation.Hot hydrogen material stream leaves one or more standby reactors and enters disengaging zone, in this, it is merged and delivers to oil-poor contactor or the downstream process for product purification with overhead subsequently.

Fig. 4 has described an embodiment (version of Fig. 3) of a through type upgrading process of handiness, and wherein in system, only two reactors 120 and 135 participate in heavy oil upgrading, and make the 3rd reactor assembly 140 in only having H ₂for subsequent use or reinforcement (back up) pattern of charging, or it can be as shown for heavy oil upgrading (using different catalyzer and/or heavy oil feed).The 3rd reactor 140 systems of also can closing down are for safeguard and make other two to keep online simultaneously.

As shown, reactor 120 and 135 series operations, wherein deliver to reactor 135 for further upgrading by liquid stream 133 at the bottom of the tower from high pressure-temperature (HPHT) separator 130.Volatile products material stream from tower top HPHT separator and hot hydrogen 151 from stand-by unit (if or reactor 140 be the overhead with upgraded product while moving) are merged and deliver to oil-poor contactor or downstream purification process.Collect from separator for example 147 the tower bottoms stream that comprises unconverted heavy oil, spent catalyst slurry, bituminous matter etc. as residual oil 152 and delivered to downstream process and reclaim metal for oil removing and/or in metals recovery units.

Fig. 5 has described another embodiment (version of Fig. 3) of a through type upgrading system of handiness, wherein all unit participate in heavy oil upgrading so that turnout maximizes, heavy oil feed 104, slurry catalyst charging 110, the optional steam that is injected into some reactors, for example defoamer of optional additive materials that is injected into some reactors and/or expendable material be to some in the reactor toward parallel running, and optional VGO is added to some in the reactor of tandem operation.Although do not show, should be noted that and can make to turn to an independent HPHT separator from the effluent of any or all reactor, instead of advance by with the separator of reactors in series, for example can flow out streams 123 and 136 and merge with the outflow streams 142 that is reactor 140 from final reactor in sequence carrying out respectively autoreactor 120 and 140, as the charging to past HPHT separator 150.If the unit that reactor separates as the separator of HPHT separately carrying with them operation, can accumulate a kind of oil of dreg stream 152 and be delivered to downstream process and reclaim metal for oil removing and/or in metals recovery units comprising for example 133,147 tower bottoms stream of unconverted heavy oil, spent catalyst.

The oil of dreg stream 152 waste slurry catalyzer that contain the amount of 5-30wt% in a small amount of coking and bituminous matter, optional expendable material (if any) and unconverted oil.Volatile products material from tower top HPHT separator is flowed to merging and delivers to oil-poor contactor or downstream product purge process.

Fig. 6 is the schema of another embodiment of a through type upgrading process, and this upgrading process has three zone of action of tandem (walking abreast) operation and the disengaging zone sharing.As shown, each reactor 120,135 and 140 and they carry difference heavy oil, catalyzer, optional VGO, optional steam injection (not shown) and the operation of optional additive charging (not shown) tandem.In the future the outflow streams 123,136 and 142 of autoreactor merge and deliver to an independent disengaging zone 150 for by upgraded product with comprise waste slurry catalyzer, compared with the oil of dreg flow point of heavy hydrocarbon and unconverted heavy oil feed from.Because reactor is as the upgrading reactor tandem operation separating, in each reactor, heavy oil feed and catalyst charge can be identical or different.

Fig. 7 is that the another kind of handiness upgrading system is arranged, and wherein two reactors 120 and 135 move with ordered mode at first.Although do not show, also other heavy oil feed and catalyzer, optional additive, VGO charging etc. can be joined to the second reactor 135 with the outflow streams 123 from the first reactor.Can make final reactor keep standby mode, the H of heat ₂this reactor of flowing through, or also can use it for as shown heavy oil upgrading, wherein final reactor 140 and the operation of sequential operation (reactor 120 and 135) tandem.Can be with identical or different to the charging operating toward sequential to heavy oil feed, catalyst charge and VGO charging toward final reactor 140.As shown, the outflow streams from two kinds of operations 136 and 142 merged and deliver to disengaging zone 150.

Although do not show in all figure, but through type upgrading system can comprise circulate/recirculation channel and pump (not shown) for promoting the dispersion of zone of action reactant, catalyzer and heavy oil feed again, particularly arrive the first zone of action with high recirculation flow and mix with turbulent flow in the device that induces reaction, thereby reduce heavy metal deposition.In one embodiment, recirculating pump circulates in loop reactor, and the temperature head therefore maintaining between reactor feed position and outlet position is 1-50 °F, preferably 2-25 °F.In another embodiment, recirculation will limit the temperature difference that runs through zone of action being caused by thermopositive reaction and guarantee hydrogen and the good contact of reactant.

In the zone of action under hydrocracking condition, at least part of heavy oil feed (higher hydrocarbon) is converted into compared with low boiling hydrocarbon, thereby forms upgraded product.Should note, along with upgrading material takes out from zone of action and is added to disengaging zone, slurry catalyst keeps together with upgrading feed as waste slurry catalyzer at least partly, and waste slurry catalyzer exists and leaves disengaging zone with non-volatile liquid part in disengaging zone.

Following examples provide as the non-limitative illustration of each side of the present invention.

embodiment: in the system with 3 solution-air paste state bed reactors, carry out heavy oil upgrading experiment, described reactor and 2 heat separators (each respectively with second and the 3rd reactors in series be connected) be connected in series.

For all embodiment, fresh slurry catalyzer is prepared according to the instruction of U.S. Patent No. 2006/0058174, for example first Mo compound and ammoniacal liquor are mixed to form to moisture Mo compound, vulcanize with sulfocompound, promote with Ni compound, then the temperature of at least 350 °F with at least under the pressure of 200psig, this mixture is for example changed in VGO at hydrocarbon ils, thereby form active slurry catalyzer to deliver to the first reactor.The ratio that Mo concentration in VGO is 5%, Ni/Mo is 10wt%.

Heavy oil feed in embodiment has performance as shown in table 1.

Charging explanation	VR-1	VR-H	VR-2
				Charging API	2.5	1.35	2.70
Charging proportion	1.06	1.07	1.06
				Viscosity (100C), cst	14548	-	-
Viscosity (130C), cst	1547	51847	8710
				Viscosity (150C), cst	NA	5647	2102
Feed sulfur, wt%	5.53	4.3675	5.12
				Feed nitrogen, ppm	5688	9907	7900
Charging MCR, wt%	25.4	27.9	29.9
				Charging vanadium, ppm	517.7	759.8	671.6
Charging nickel, ppm	102.2	174.3	141.9
				Hot heptane bituminous matter, wt%	16.3	19.2	25.7
Charging VR (1000F+) content, wt%	86.4	95.5	95.7
				Charging HVGO (800F+) content, wt%	97.8	98.9	100
Charging VGO (650F+) content, wt%	99.6	100	100
				Charging C, wt%	83.71	84.30	83.24
Charging H, wt%	9.88	9.75	9.53
				H/C ratio	0.118	0.116	0.114

To operate upgrading system under two kinds of patterns: recirculation and a through type.In as the recirculation mode of prior art, return a part for non-volatile material stream (STB or " at the bottom of stripper column " product) from final reactor recirculation to the first reactor and will shift out a part as releasing material stream.STB material stream adds up to toward approximately 30% of the heavy oil feed of this system.Releasing material stream adds up to toward the approximately 15wt% of the heavy oil feed of this system.STB material stream is containing having an appointment 10-15wt% slurry catalyst.

In all experiments, the effluent taking out from the first reactor is delivered to the second reactor to proceed upgrading reaction.By from second and the outflow streams of the 3rd reactor deliver to respectively and second and the separator of the 3rd reactors in series, and be separated into hot vapor stream and non-volatile material stream.Vapor stream (" HPO " or high pressure overhead) is shifted out and collected for further analysis from high-pressure separator top.The non-volatile material stream that comprises slurry catalyst and unconverted heavy oil feed from the first separator is delivered to the 3rd reactor.Be STB material stream from the non-volatile material stream that comprises slurry catalyst and unconverted heavy oil feed of second (finally) separator, be recycled to the first reactor (for " recirculation " experiment) or send to as oil of dreg stream (for " through type " experiment).

Hydrogenation technique condition is as follows: temperature of reactor (in 3 reactors) is 805-820 °F, and wherein average reactor temperature as shown in Table; Total pressure is 2400-2600psig; LHSV as shown in Table, is 0.1-0.30h ^-1; H ₂rate of air flow (SCF/BBL) is 7500-20000.For some experiments, make some reactors take off-line to improve combined feed total feed throughput (as shown in using the quantity of the reactor in operation in table).

As shown in table 3 and under suitable LHSV, be comparable to the transformation efficiency obtaining in the comparative example 3 with the upgrading process of recirculation mode and much higher catalyst concn (4200ppm) operation with the transformation efficiency once providing by pattern and the embodiment 8 under low catalyst concn (2500ppm Mo/VR).Together with HDM transformation efficiency, HVGO and VGO transformation efficiency are respectively 93% and 78% with high HDS, HDN, HD MCR.All product A PI degree obtains and approaches 31 degree, is similar to recirculation operation.Described experiment shows can remove recycle stream and not affect overall performance, reduces or improves catalyst content (2500 or 4200ppm) and obviously do not change performance.

In comparative example 4, attempt the not success of suitable (low) catalyst concn operation upgrading system with recirculation mode and 2500ppm Mo/VR, this is because system is never stablized and had a plant issue (forming coking and deposition of solids in reactor) being caused by the low-conversion of recirculation mode.

The result of Evaluation operation example 1, comparative example 1 and comparative example 2 is the transformation efficiency under different logistics throughputs and high catalyst ratio (2.1%Mo) with contrast.Reduce as desired at higher building circulation excessive lower vacuum residuum (VR) transformation efficiency, but still there is the transformation efficiency of > 70% (71.74%).In addition, from product, shift out the V and the Ni that in charging, are greater than 95%, and all product A PI degree increases by approximately 17 degree compared with VR charging.

Embodiment 2-7 will evaluate a through type upgrading system under various logistics throughputs and low catalyst concentration (1500-2500ppm).As shown in Example 2, under 0.3VR LHSV and 4200ppm Mo, realized the VR transformation efficiency of > 75%.HVGO and VGO transformation efficiency are respectively 62% and 50%, show most VR to be converted into light hydrocarbon/oil.In the time making catalyst content be reduced to 2500ppm (embodiment 3) or 1500ppm (embodiment 4), VR transformation efficiency improves slightly due to total LHSV slight reduction.In the time that temperature of reactor is brought up to 825 °F from 818-819 °F, make VR transformation efficiency be increased to 79% with the low catalyst levels of 2500ppm Mo, compared with usage quantity in recirculation mode (comparative example 3), make its catalyzer rate of utilization reduce by 40%.As shown in embodiment 6-7, the VR transformation efficiency the simultaneously whole product A PI increase that under 2500ppmMo, obtain 92-94% are greater than 26 degree.

As noted, by once by pattern under the ratio (1500-4200ppm) of low catalyzer and oil, under high VR throughput (0.3LHSV) and the high temperature of reactor at 818-825 °F, obtain at least 75% VR (1000 °F) transformation efficiencys (75-79%).Under 0.15LHSV, VR transformation efficiency is brought up to 92-94% and under the high temperature of reactor of 0.1LHSV and 818-825 °F, is almost transformed transformation efficiency > 98% completely.Also as noted, the catalyst concn in reactor improves from a reactor to next reactor (series connection), and no matter upgrading system is with recirculation mode or once operates by pattern.

comparative example 10.Expection with low-down catalyst concn (250ppm Mo/VR) by once not succeeding by mode operation upgrading system because system can be due to blockage problem, that the chances are is unstable due to the caused low-conversion of low catalyst concentration.

embodiment 13.In this embodiment, test upgrading system studies on asphaltene and other sedimental specific absorption with expendable material.Use for the material that optionally adsorbs bothersome bituminous matter and have heavy body.Therefore described material adsorptive pitch matter prevent that bituminous matter from making catalyst deactivation, thereby make this system with less catalyzer operation and still maintain high transformation efficiency simultaneously.

In embodiment 13 (in table 4), two kinds of different sacrifice sorbent materials are evaluated.C-2 is the commercial carbon blacks material with 2-12 micron mean sizes from STREM Chemicals.C-1 is the carbon black that the coking of waste slurry catalyzer in the heavy oil residue by deriving from previous upgrading operation obtains, and has D-90 (particle diameter is 2-12 micron) and the 400m of 10 microns ²the BET surface-area of/g.In the rhythmic reaction experiment with heavy oil VR-1/ turning oil (3: the 2 ratios) concoction of 112.5g and the levels of catalysts of 1.25% Mo/VR-1 heavy oil feed, this carbonaceous material is added with 3000ppm carbon/VR wt/wt.Reaction is carried out and 825 °F of lower soaking (soak) 2 or 5 hours under 1600psig hydrogen pressure.Contrast with the rhythmic reaction experiment of sacrifice property sorbent material not thering is the operation of carbonaceous material.Table 4 has gathered catalytic performance.

Table 4

HDN represents hydrodenitrification; HDS represents hydrogenating desulfurization; HDMCR represents that hydrogenation takes off Micro Carbon Residue; VR represents vacuum residuum; H/C is than the atomic ratio that represents hydrogen and carbon; Measure dry solid values according to methods known in the art.HDN is the general measurement for catalyst hydrogenation activity.As shown, with do not have carbon with reference to compared with, use the firm raising that soaking time demonstrated HDN activity in 2 and 5 hours that operates in of carbonaceous expendable material.

For the object of this specification sheets and claims, except as otherwise noted, represent all numbers of quantity, percentage ratio or ratio and other numerical value for this specification sheets and claim, be under any circumstance all interpreted as being modified by term " about ".Therefore, unless indicated to the contrary, the numerical parameter providing in following specification sheets and appended claims be can according to the desirable properties that obtains of attempt and/or for measuring the precision of instrument of this value about value of changing, therefore comprise directional error or determine the standard deviation of this value method used.The term "or" using in claim, unless clearly indicated for referring to "and/or", only refers to surrogate or alternative for mutually repelling, although the definition of disclosure support is only to refer to surrogate and "and/or".Word " one " or " one " is when " comprising " while being used in combination and can mean " one " with term in claims and/or specification sheets, but it also meets " one or more ", " at least one " and " a kind of's or more than one " implication.In addition, all scopes disclosed herein comprise end points and can independently combine.Generally speaking, except as otherwise noted, singular elements can for plural meaning and vice versa, and do not lose generality.As used herein, term " comprises " and grammatical variants plan is nonrestrictive, makes description every in list can not get rid of other similar terms, and described similar terms can replace the item of listing or be added in listed.

Can imagine and of the present invention any aspect of discussing in the context of one embodiment of the invention be implemented in or be applicable to any other embodiment of the present invention.Similarly, any composition of the present invention can be the result of any method of the present invention or technique or can be used for any method of the present invention or technique.The specification sheets of writing discloses the present invention with embodiment, comprises preferred forms, and also can make any those skilled in the art implement and use the present invention.The scope of the claims is defined by the claims, and can comprise other embodiment that those skilled in the art can expect.These other embodiment intend to comprise within the scope of the claims, if the word language of their Constitution Elements and claim does not have discrepant words, if or they comprise and the of equal value Constitution Elements of claim word language without essential difference.By reference to all references mentioned in this article is included in herein clearly.

Table 3

Claims (19)

1. for heavy oil feed being carried out to hydrotreatment and the described heavy oil feed of 75wt% at least being transformed to form the method for upgraded product, the method is used multiple zone of action and at least one disengaging zone, comprises the first zone of action, and the method comprises:

The gas feed of hydrogen is provided;

Heavy oil feed is provided;

The concentration between 500wppm and 5000wppm with active metal catalyst and heavy oil feed ratio, provides the slurry catalyst charging that comprises the active metal catalyst that in hydrocarbon oil diluent, median size is at least 1 micron;

The water of the amount of 30 % by weight at the most of described heavy oil feed is joined to described the first zone of action;

The gas feed of at least part of described hydrogen, at least part of described heavy oil feed, water and at least part of described slurry catalyst charging are merged in the first zone of action under hydrocracking condition at least part of described heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form upgraded product;

By from comprising of described the first zone of action described upgraded product, described slurry catalyst, the gas of described hydrogen and the first effluent material stream of unconverted heavy oil feed deliver to the first disengaging zone, wherein volatility upgraded product is shifted out together with the first top stream with the gas of described hydrogen, and described slurry catalyst and described unconverted heavy oil feed are drifted as the first non-volatile material, and wherein said the first non-volatile material stream contains the solid that is less than 30%;

Collect described the first top stream for further processing; And

Collecting described the first non-volatile material flows for further processing.

2. according to the method for claim 1, the method also comprises:

Amount with the 1wt% that is less than described heavy oil feed provides the additive materials that is selected from inhibitor additive, defoamer, stablizer, metal scavenger, metal pollutant remover, metal passivator, expendable material or their mixture;

And wherein,, in described combining step, at least part of described additive materials and gas feed, described heavy oil feed, water and described slurry catalyst charging containing described hydrogen are merged in described the first zone of action.

3. multiple zone of action and disengaging zone are configured so that described multiple zone of action and disengaging zone operate with following pattern in interchangeable mode according to the process of claim 1 wherein: ordered mode; Parallel model; The combination of parallel model and ordered mode; All on-line; At least one is online and at least one is for subsequent use; Some online and some off-lines; Be sent to the parallel model of at least one disengaging zone of connecting with this zone of action from the described outflow streams of described zone of action; Merge and deliver to the parallel model of described disengaging zone from the described outflow streams of described zone of action and the outflow streams from different contact zone; And their combination.

4. according to the method for claim 1, wherein said the first zone of action operates and has a top hole pressure for X under the first pressure, wherein said the first disengaging zone has the inlet pressure for Y, and wherein between the described top hole pressure X of described the first zone of action and the described inlet pressure Y of described the first disengaging zone, have pressure drop Z, and Z is less than 100psi.

5. the method for claim 4, wherein said pressure drop Z is less than 75psi, and wherein said pressure drop Z is caused by reliever.

6. the process of claim 1 wherein that described active metal catalyst has the median size of 1-20 micron.

7. basis the process of claim 1 wherein that described slurry catalyst comprises the nanocluster that size is less than the colloid size particles of 100nm, and wherein said nanocluster has the median size of 1-20 micron.

8. the method for claim 1, the method also comprises:

Other hydrocarbon oil feed except described heavy oil feed is joined to described the first zone of action with the amount of the 2-30wt% of heavy oil feed.

9. the method for claim 1, wherein the gas feed of the hydrogen of q.s is offered to the method and be greater than 100% volume yield to make it have with upgraded product, described upgraded product comprises liquefied petroleum gas (LPG), gasoline, diesel oil, vacuum gas oil and monopropellant oil.

10. the method for claim 2, wherein said additive materials is the expendable material of the metal for trapping heavy oil feed and coke, this expendable material has at least 1m ²the BET surface-area of/g and at least 0.005cm ³the total pore volume of/g.

The method of 11. claims 2, wherein said additive materials is waste slurry catalyzer.

12. the process of claim 1 wherein and make described at least one zone of action in standby mode, and the method also comprises:

Making to maintain temperature and pressure in the described zone of action of standby mode is similar under the temperature and pressure under the hydrocracking condition in described the first zone of action;

And wherein the gas feed of the hydrogen of the heating of q.s is provided to described zone of action in standby mode to maintain the temperature and pressure that is similar to described the first zone of action.

13. the process of claim 1 wherein that described multiple zone of action operates with parallel model, and the method also comprises:

By the gas feed of at least part of hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst charging are provided to the second zone of action also operating under hydrocracking condition;

The gas feed of described at least part of hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst charging are merged in described the second zone of action at least part of described heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form other upgraded product;

By described first effluent material stream with from gas and second the flowing out streams and deliver to described the first disengaging zone of unconverted heavy oil feed of comprising of the second zone of action described other upgraded product, described slurry catalyst, described hydrogen, wherein described the first top stream and described the first non-volatile material are drifted for further processing;

And wherein other heavy oil feed is added to described the second zone of action.

14. the process of claim 1 wherein that described multiple zone of action operates with ordered mode, and the method also comprises, before described first effluent material stream is delivered to described the first disengaging zone:

Also maintain the second zone of action under hydrocracking condition so that at least part of described unconverted heavy oil feed in described outflow streams is converted into compared with low boiling hydrocarbon by delivering to from the described first effluent material stream of described the first zone of action with the gas feed of other hydrogen, thereby form other upgraded product; And

Collect from the gas of the described upgraded product of described the second zone of action, described slurry catalyst, described hydrogen and the mixture of unconverted heavy oil feed as the charging that enters described the first disengaging zone.

15. the process of claim 1 wherein that described multiple zone of action operates with parallel model, wherein at least two zone of action run parallel, the method also comprises:

The gas feed of at least part of described hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst are merged in the second zone of action under hydrocracking condition at least part of described heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form other upgraded product, wherein said the second zone of action and described the first zone of action run parallel; And

By the described first effluent material stream from described the first zone of action and from comprising of described the second zone of action described other upgraded product, described slurry catalyst, described hydrogen the outflow streams of mixture of gas deliver to described the first disengaging zone.

16. the process of claim 1 wherein that described multiple zone of action operates with parallel model, wherein at least two zone of action run parallel, the method also comprises:

The second slurry catalyst is provided, and wherein said the second slurry catalyst is different from the described slurry catalyst that offers described the first zone of action;

The gas feed of at least part of described hydrogen, at least part of described heavy oil feed and at least part of described the second slurry catalyst are merged in the second zone of action under hydrocracking condition at least part of described heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form other upgraded product, wherein said the second zone of action and described the first zone of action run parallel; And

To deliver to the second disengaging zone as charging from the second outflow streams that comprises the gas of other upgraded product, described slurry catalyst, described hydrogen and the mixture of unconverted heavy oil feed described in described the second zone of action, wherein the gas of other volatility upgraded product and described hydrogen is shifted out as the second top stream, and described slurry catalyst and described unconverted heavy oil feed are drifted as the second non-volatile material.

17. the process of claim 1 wherein that described multiple zone of action operates with parallel model, and the method also comprises:

By the gas feed of at least part of hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst charging offer the second zone of action also operating under hydrocracking condition;

The gas feed of at least part of hydrogen, at least part of described heavy oil feed and at least part of described slurry catalyst charging are merged in described the second zone of action at least part of described heavy oil feed is converted into compared with low boiling hydrocarbon, thereby form other upgraded product;

By gas and second the flowing out streams and deliver to described the first disengaging zone with described first effluent material stream of unconverted heavy oil feed from comprising of described the second zone of action described other upgraded product, described slurry catalyst, described hydrogen, wherein described the first top stream and described the first non-volatile material are drifted for further processing;

And optionally, wherein to toward the described slurry catalyst charging of described the second zone of action with to the described slurry catalyst charging of past described the first zone of action be different slurry catalyst.

The method of any one in 18. claim 13-17, the method also comprises:

Water is joined to described the second zone of action with the amount of 30 % by weight at the most of described heavy oil feed.

The method of any one in 19. claim 13-17, being wherein the slurry catalyst of only Ni or the slurry catalyst that is rich in Ni to the described slurry catalyst charging toward the first zone of action, is the slurry catalyst of only Mo or the slurry catalyst that is rich in Mo to the catalyst charge toward described the second zone of action.