CN1702147A - Presulfiding ocr catalyst replacement batches - Google Patents

Abstract

Catalyst particles are presulfided in a treatment zone separate from a hydroconversion reaction zone. The presulfided catalyst is then added to a substantially packed bed of catalyst in the hydroconversion reaction zone at reaction pressure, so that the reactor is not shut down to replace catalyst. The presulfiding process is particularly beneficial for use in moving bed reactors for heavy oil conversion.

Description

Presulfiding hydroprocessing catalyst replacement batches

The application is to be November 13, application number in 2000 the dividing an application for the application of " Presulfiding hydroprocessing catalyst replacement batches " that be 00818433.X, invention and created name the applying date.

Technical field

The present invention relates to the method for catalytic life that a kind of prolongation is used for the catalyzer of hydrocarbon feed stream hydrotreatment.More particularly, the invention provides a kind of prevulcanized hydrotreating catalyst, and prolong the catalytic life that is used for the catalyst bed in hydroconversion reactions district during the hydrotreatment so that improve suitability, reduce fouling rate.The present invention more specifically further provides a kind of method, and this method was used for before the hydrotreating catalyst with prevulcanized is transferred to the hydrotreatment reaction system externally prevulcanized hydrotreating catalyst.This method is intended to improve suitability and reduces fouling rate, and prolongs the catalytic life of common " catalyst filling bed " (it preferably can replace catalyzer in operation) that be used for the hydrotreating reactor system.Method of the present invention also can be advantageously utilize " the swelling catalyst bed ' ' (and for example, U.S. Patent No. 4,571,326 and U.S. Patent No. 4,744,887 in the ebullated bed described) the hydrocarbon reactor system in implement.

Background technology

Following three kinds of acceptable response device technology are suitable methods of hydrogen upgrading (upgrading) of industrial at present " weight " hydrocarbon liquid flow: (i) fixed bed reactor system; (ii) boiling or expanded polystyrene veneer reactor assembly, they can replace catalyzer in operation, and are H-Oil at industrial known their trade mark at present _RAnd LC-Fining _RAnd roughly packed bed type (substantially packed-bedtype) reactor assembly that (iii) has a replacement catalyst system in operation, as more specifically being described in U.S. Patent No. 5,076, in 908 (the authorizing Stangeland etc.), it and current invention and discovery have the common transferee.Fixed bed reactor system can be defined as such reactor assembly,, has the reaction zone of one or more static catalyzer that is, and the feedstream of liquid hydrocarbon and hydrogen are by its parallel flowing downward.Ebullated bed or expanded bed system can be defined as such reactor assembly, promptly, it has a upwards flow model single reaction district reactor, fill the catalyzer that is the random motion of expansible catalytic bed state in the reactor, be the expansible catalytic bed usually expand be higher than " caving in " bed level (it be do not expand or the boiling reactor system of non-boiling state in the volume of catalytic bed, do not have hydrocarbon stream upwards to flow through) 10vol%～about 35vol% or more.As U.S. Patent No. 5,076, specifically described in 908 (the authorizing Stangeland etc.), roughly packed bed type reactor assembly is a upwards flow-type reactor system, it comprises and much fills catalyst filling particulate reaction zone, granules of catalyst catalyzer add or the condition of taking out under little motion or do not move in the normal use.In the roughly packed bed type reactor assembly of Stangeland etc., when in the conventional catalyst replacement process when reactor takes out catalyzer, catalyzer is downward direction and flows with plug flow or with basic piston stream mode basically, and the catalyzer minimum degree ground in the adjacent layers of the catalyzer in the layer above or below the catalyst layer of observation mixes.

For what these those skilled in the art of hydrogen upgrading of heavy hydrocarbon liquid flow knew be, be used for heavy oil etc. hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking etc. catalyzer usually (for example by the carrier of basic material, aluminum oxide, silicon-dioxide, silicon-dioxide one aluminum oxide perhaps may be the crystalline silicon aluminates) and the metal (or compound) of one or more promotors or catalytic activity add trace substance and constitute.The typical catalytically-active metals that utilizes is a cobalt, molybdenum, nickel and tungsten; Yet, can be according to other metal of application choice or compound.What know for these those skilled in the art of upgrading of heavy oil is may roughly be prepared the mode of live catalyst in potential catalyst activity and work-ing life and/or be exposed to the influence of the method for aging catalyst before of popular response device operational condition.More particularly, promotor or the catalytically-active metals that is contained in the live catalyst is oxidation state.In the application of hydrotreatment sulfur-bearing raw material, metal oxide is converted into metallic sulfide.When before being exposed to reactor operating condition, the oxygenate conversion in the live catalyst being sulfide, use the catalysis characteristics that the method that is called presulfiding of catalyst is improved these metallic sulfides usually.For a long time, the industrial live catalyst of having developed concrete method for pre-sulphuration and when every batch operation begins, having loaded in the scene prevulcanized fixed-bed type reactor system.These methods generally include, the gas heating of catalyst in reactor and catalyzer drying means, then, with start oil (startup oil) wetting/soak catalyzer, subsequently, the raw material (having added the raw material of sulphur compound) of using the raw material of spike (raw material that contains the natural sulphur compound) not and mixing sulphur carries out vulcanisation step.Sulfuration (or prevulcanized) step also can alternatively be used H ₂/ H ₂S carries out the vapor phase sulfuration.These technology and several other method by HarmanHallie in May nineteen eighty-two, propose in the technical article of the catalyzer meeting of holding in Amsterdam (the oil and natural gas magazine (Oil and GasJournal) of printing distribution on December 20 nineteen eighty-two) and discuss, also by William J.Tuzynski be set forth in 1989NPRAMeeting, title is in the paper of " performance and the application of commodity prevulcanized agent ".

Usually, the raw material method for pre-sulphuration of spike does not comprise, under the temperature of reactor condition of about 300 ℃ (572)～about 350 ℃ (662), sulphur compound (they natural selected startup (startup) hydrocarbon feeds that is present in) resolves into H ₂S.The raw material pre-curing technology of spike is performed such: organic compounds containing sulfur is injected into selected startup hydrocarbon feed, so that the sulfurous organic compound of injection can be decomposed into H being lower than decompose to start under the temperature required temperature of the natural sulphur compound that exist in the oily raw material ₂S.Industrial preferred spike agent at present is dimethyl sulfide (DMS) and dimethyl disulfide (DMDS), and they can make vulcanisation operation finish under about 250 ℃～about 275 ℃ temperature usually.The vapor phase prevulcanized is restive, and does not reach optimum usually in industrial application, and this is because several reasons (comprising poor distribution and uneven sulfuration, thermopositive reaction weak heat-dissipating etc.).

Developed such technology: wherein, be fed to before reactor carries out so-called outside prevulcanized, by with sulphur compound (for example, polysulfide) dipping with catalyst pretreatment; Yet catalyzer must still experience drying, and is wetting, and is converted into the metallic sulfide attitude from the burning states of matter on the spot in the start-up operation process in reactor.The major advantage of claiming in this case, is to shorten start time and may improve activity.U.S. Patent No. 4,576,710 have enlightened the prevulcanized regenerated catalyst that is used for ebullated bed reactor, but openly do not carry out the mechanical detail or the operating practice of such prevulcanized step effect.

Design conventional prevulcanized and start-up operation to keep starting oily raw materials quality and temperature of reactor condition, consequently sulfuration and hydrogenation do not produce the harmful temperature condition that causes carbon laydown or metal sintering (they all reduce catalyst activity) in catalyzer ball inside.Briefly, the severity of hydrogenation is started the restriction of oil quality (for example, sulphur content) and temperature of reaction condition between aging and curing time in primary catalyst, weakens or stops basically until vulcanization reaction.State-of-the art can cause prevulcanized on the spot under the temperature that is lower than about 200 ℃ (392), be higher than about 300 ℃ (572 °F) and finish before and be elevated in temperature.Harman Hallie has indicated at the technical article that be published on the oil and natural gas magazine December 20 nineteen eighty-two, if vulcanize under higher temperature, can realize that the poor catalyst activity XOR reduces 7%～about 33%.Be enclosed in reactor on the line of operating under the temperature that is higher than 300 ℃ if will contain the fresh or regenerated batch of catalyst of the promoter metal that is oxidation state, just such loss of activity may occur suddenly.Therefore, required, what also be that we invented is a kind of suitable, that can reasonably realize and method economy, that is, the live catalyst batch of material in the reactor on the line of operating is added in prevulcanized under temperature that raises and hydrogen pressure.Can from preliminary ageing fresh or the regenerated catalyzer obtain substantial benefit, in order to be the metallic sulfide attitude before in the reactor on the line of under temperature that it is enclosed in rising and hydrogen pressure, operating with the promoter metal oxygenate conversion of major portion.

Summary of the invention

The present invention relates to the method that a kind of prevulcanized is used for the hydrocarbon conversion catalyst of moving-burden bed reactor (it comprises that at least one fills the reaction zone of granules of catalyst).Comprise in the moving-burden bed reactor from reaction zone and take out the device of granules of catalyst and add the device of granules of catalyst, reaction zone is remained on be hydrocracking refinery stream chosen temperature and pressure simultaneously toward reaction zone.In hydroconversion process, remove the pollutent (comprise nitrogen, sulphur, aromatic substance and metal one or more) of refinery stream with contacting on the granules of catalyst of hydrogen blended refinery stream in reaction zone that adds.So,, reduced one or more pollutents in the effluent of reaction zone with respect to the raw material of reaction zone.

One of moving-burden bed reactor is characterised in that, in hydroconversion process, can take out at least a portion granules of catalyst from reaction zone, and in the reaction zone of other granules of catalyst can be added to hydrotreatment the time.Can add and take out granules of catalyst and do not need the stopped reaction operation, just make operator set rapidly a bed catalyst particle to reach required product plate (productslate) or catalyst activity fully the stopped reaction device replace catalyzer.Moving-burden bed reactor also allow the logistics of operator's conversion refinery (for example, metallic logistics, they otherwise can rapid deactivation catalyzer).Frequent shutdown is removed the capital cost that the catalyzer that is subjected to metallic pollution is conventional fixed bed hydrogenation conversion process operating mechanism.

Its most widely aspect, the present invention relates to the method that the hydrocarbon feed stream in hydroconversion reactions district is upwards flow through in a kind of hydrotreatment, this method comprises:

In the presence of the hydrogen of reaction pressure, hydrocarbon feed stream fed fill the hydroconversion reactions district of particulate state hydrotreating catalyst and make described hydrocarbon feed stream begin upwards to flow through described catalyzer and therefrom reclaim reaction effluent;

A certain amount of hydrotreating catalyst is to produce the sulfurized catalyzer in the sulfidizing district; And

In the hydroconversion reactions district, add at least a portion sulfurized catalyzer, under reaction pressure, keep reaction zone simultaneously.

The preferably treatment district of catalyst vulcanization system comprises one or more processing vessels, they be contained in hydroconversion reactions in the reactor separate from.Typical sulfurizing temperature range is 90 ℃～370 ℃.The preferred temperature of sulphurized catalyst particulate is in 125 ℃～325 ℃ scopes.Preferred pressure 200KPa (15psig) to or the scope of a little higher than (for example, less than 450KPa or more than the 50psig) reaction zone pressure in.

Preparation method and the application in the moving bed reaction system that an importance of the present invention is a pre-sulfide catalyst.In conventional fixed-bed process, the live catalyst particle cures in reactor before reacting in being added to refinery stream usually.Allowing to add in the hydrotreatment process in the reaction system of catalyzer, live catalyst is usually not that sulphided state is added to reaction zone, the sulphur compound sulfuration by existing in the fluid that flows through granules of catalyst between the reaction period again.Yet, actively to higher hydrocracking when handling heavy feed stock need cause benefiting from careful sulfurized Application of Catalyst before contact heavy feed stock under the reaction conditions.By the present invention, the embodiment of a certain amount of hydrotreating catalyst comprises the steps: in sulfidizing district

Add a certain amount of hydrotreating catalyst in treatment zone, described amount comprises fresh hydrotreating catalyst;

Heat the hydrotreating catalyst of described amount, until catalyst temperature in 90 ℃～370 ℃ scopes; And

In treatment zone, add vulcanizing agent with preparation sulfurized catalyzer.

In preferable methods of the present invention, the method for adding a certain amount of hydrotreating catalyst in the treatment zone comprises the steps:

Prepare a kind of slurry that comprises hydrocarbon liquid and a certain amount of hydrotreating catalyst;

The slurry that will comprise hydrocarbon liquid and hydrotreating catalyst is added in the treatment zone; And

Take out at least a portion hydrocarbon liquid from treatment zone.

The method of adding vulcanizing agent in the treatment zone then comprises:

Under the temperature of the pressure of 0.2～24.2MPa and 90 ℃～370 ℃, the treatment zone that fills hydrotreating catalyst and vulcanizing agent pressurizeed and produce the catalyzer of partial vulcanization at least; And

Take out at least a portion vulcanizing agent from treatment zone.

In another embodiment of the present invention, the method for the catalyzer in the sulfidizing district comprises, makes the fluid of Containing Sulfur agent flow through the interior catalyzer of treatment zone, and this method comprises the steps:

Add a certain amount of hydrotreating catalyst in treatment zone, described amount comprises fresh hydrotreating catalyst;

Make the hydrocarbon liquid flow of being heated cross the hydrotreating catalyst of described amount in the treatment zone, until catalyst temperature in 90 ℃～145 ℃ scopes;

Subsequently, (under 15～3500psig) the pressure treatment zone is pressurizeed at 0.2MPa～24.2MPa;

Continue to make the hydrocarbon liquid flow of being heated to cross catalyzer in the described treatment zone, until catalyst temperature in 90 ℃～370 ℃ scopes;

Make cured blend flow through the catalyzer in the described treatment zone and prepare the catalyzer of partial vulcanization at least.

The preferred temperature of sulphurized catalyst particulate is in 125 ℃～325 ℃ scopes.Preferred pressure 200KPa (15psig) to or the scope of a little higher than (for example, less than 450KPa or more than the 50psig) reaction zone pressure in.

The catalyzer of the prevulcanized of producing in present method is added in the hydroconversion reactions district, under suitable reaction pressure, keeps reaction zone by following method simultaneously:

In the interior sulfurized catalyzer of treatment zone, add hydrocarbon liquid;

Formation comprises the slurry of hydrocarbon liquid and at least a portion sulfurized catalyzer; And

The slurry of described hydrocarbon liquid and sulfurized catalyzer is added to the hydroconversion reactions district, under reaction pressure, keeps reaction zone simultaneously.

In a more preferred embodiment, the present invention relates to have the moving bed reaction district of the roughly packed bed of catalyzer.A kind of method to hydrocarbon feed stream (it upwards flows through the hydroconversion reactions district of the roughly packed bed with catalyzer) hydrotreatment comprises the steps:

Hydrocarbon feed stream is imported the hydroconversion reactions district of the roughly packed bed with particulate state hydrotreating catalyst and makes described hydrocarbon feed stream begin upwards to flow through with certain flow velocity the roughly packed bed of described catalyzer, so that the roughly packed bed of described hydrotreating catalyst expand into roughly packed bed that length exceeds the described hydrotreating catalyst that is the packed bed state roughly holoaxial to below 10% of length, and from wherein reclaiming reaction effluent;

Take out the hydrotreating catalyst of first deal and make the roughly packed bed of described hydrotreating catalyst in described hydroconversion reactions district, begin downwards plug flow basically from the hydroconversion reactions district;

Add the particulate state hydrotreating catalyst of second deal in the treatment zone, described second deal comprises fresh hydrotreating catalyst;

The second deal hydrotreating catalyst in the sulfidizing district and prepare the sulfurized catalyzer; And

Add at least a portion sulfurized catalyzer in the past hydroconversion reactions district and replace the catalyzer of first deal of taking-up.

The present invention relates to prevulcanized hydrotreating catalyst before in the hydroconversion reactions district, adding catalyzer.The method vulcanization in situ hydrotreating catalyst that enlightens in this area,, unvulcanized catalyzer fresh by adding in catalyst bed used by this sulfur-bearing reactant fresh, unvulcanized catalyzer and vulcanized described catalyzer.Usually, these prior art vulcanization process range operation of application of temperature in being higher than present method also.In other factors, the present invention is based on this unexpected discovery, that is, when being used for hydrocracking, show higher substantially characteristic by the catalyzer of present method prevulcanized.Present method has guaranteed sulphurized catalyst, promptly, the sulphur compound that exists in the product flow of application from hydroconversion process is under the low sulfuration temperature of preparation catalyzer (it has higher characteristic in the desulphurization reaction of catalytic conversion reaction, particularly heavy feed stock).This discovery is for the following reactor particularly important of operation, that is, moving-burden bed reactor, particularly with packed bed up-flow reactor roughly catalyzer add and the taking-up process in the reactor operated under the plug flow conditions.

Description of drawings

Fig. 1 has set forth embodiment of the present invention, and it has one and only is used for the high pressure catalyzer translator to presulfiding of catalyst by the present invention.

Fig. 2 has set forth embodiment of the present invention, and it has and is used for a low pressure catalyzer translator and high pressure catalyzer translator to presulfiding of catalyst by the present invention.

Fig. 3 shows the desulfurization characteristic by the improvement of the catalyzer of prevulcanized of the present invention.

Detailed Description Of The Invention

Now in detail with reference to Fig. 1,2 about the preferred embodiment of the invention, a visible presulfiding of catalyst system is communicated with the catalyst bed 10 of reactor 11.The effect of catalyst vulcanization system is with catalyst vulcanization (that is, the metal oxide in the catalyzer being converted into metallic sulfide) before catalyzer is imported into reactor 11.In the present invention, in treatment zone 50, vulcanize (that is prevulcanized) catalyzer in one or more containers.

Be contained in the reaction zone 10 upper reaches reaction system preferably in the reactor 11, reaction solution enters reaction zone 10 by feed(raw material)inlet 14, and above stream mode is upwards by reaction zone 10 moving-burden bed reactors, and reaction effluent flows out from pipeline 16.This presulfiding of catalyst technology is for being effective as the ebullating bed reactor system or as the reaction zone of the roughly packed bed type reactor assembly operation with replacement catalyst system in operation (that is, can be under reaction pressure basically catalyzer be transferred to reaction zone and take out from reaction zone).For reactor system is kept as packed bed type reactor assembly roughly, replacing catalyst system in operation is a counter-current operation system, wherein, catalyzer and fluid velocity in conjunction with restriction bed expand into length exceed be the packed bed state bed roughly holoaxial to below 10% of length.More preferably, described bed is expanded remain on be the packed bed state bed roughly holoaxial to below 5% of length, more preferably below 1%.Preferably roughly packed bed type reactor assembly enlightens in U.S. Patent No. 5,076,908 (it is for referencial use to incorporate its disclosure into this paper).

In embodiment of the present invention of describing in Fig. 1, the catalyst vulcanization system comprises catalyzer transfer vessel 304, it be used for accepting and distribute the catalyst addition hopper 312 of hydrotreating catalyst to be communicated with.Catalyst hooper 312 has a sagging pipeline 314 that it is communicated with high pressure catalyst charge container 304, and container 304 carries out hydrotreatment for the catalyzer from catalyst addition hopper 312 to catalyst charge container 304.Conveniently be that sagging pipeline 314 is equipped with a valve 318, be used for regulating the catalyzer that flows through it.Catalyzer preferably is transferred to catalyst charge container 304 as the slurry in the hydrocarbon ils from catalyst addition hopper 312.

In one embodiment of the invention, with needing the sulfurized hydrotreating catalyst in the vulcanizing agent processing catalyzer transfer vessel 304." spike " agent or vulcanizing agent can be the spike agent or the vulcanizing agents (for example, mercaptan compound, thiophenes, organic sulfide etc.) of any appropriate, but the recirculation stream that is rich in sulphur that preferably reclaims from reaction effluent.Also can use S-contained substance (for example, dimethyl disulfide or dimethyl sulfide).A vulcanizing agent example is to be rich in hydrogen sulfide (H ₂S) the hydrocarbon gas (for example, methane, ethane etc.) preferably contains the H of about 5wt%～about 80wt% ₂S.Work as H ₂When S is used as vulcanizing agent in present method, preferred H ₂S comes the recirculation stream (not shown) since reaction effluent 16 recovery.For example, can utilize boiling point that reaction effluent 16 is separated into two or more components.Further separation can produce and be rich in H ₂The logistics of S, it can be recycled for use as vulcanizing agent by pipeline 328.

Such as has been described, can transfer to catalyzer transfer vessel 304 from the catalyzer that catalyst hooper 312 will be slurry, wherein, the liquid ingredient of slurry can be the product stream (for example, washing oil) from operation.After catalyzer is transferred to the catalyzer transfer vessel from catalyst hooper, preferentially before importing vulcanizing agent, remain in oil the catalyzer transfer vessel from catalyzer transfer vessel discharge at least a portion by pipeline 310 (cooperating) with valve 311.In the embodiment shown in Fig. 1, can vulcanizing agent be imported the catalyzer transfer vessel by pipeline 212 (cooperating) or by pipeline 328 (cooperating) with valve 330 with valve 213.

Before sulfuration, catalyzer is heated to the temperature of rising, for example, from 50 ℃ to 370 ℃, more preferably from 125 ℃ to 325 ℃, further preferably from 150 ℃ to 285 ℃.Can provide heat by using the catalyzer transfer vessel that indirect heating source (for example, steam jacket) is heated to comparatively high temps (for example, 90 ℃～370 ℃).Also can be before catalyzer be added to transfer vessel heatable catalyst, perhaps flow through catalyzer in the transfer vessel by using heated liquid.In the embodiment of Fig. 1, can provide the hydrocarbon ils that is heated from washing oil drum (being illustrated as 356 usually) by pipeline 340, wherein, provide the hydrocarbon ils that is heated to the washing oil drum by pipeline 354 (cooperating) with valve 356.

" hydrocarbon " (for example, gas oil or washing oil) of hydrocarbon and cold hydrocarbon ils of being used to be heated can be any suitable hydrocarbon, but preferably in the last running of boiling (more preferably in 315 ℃～525 ℃ scopes, seething with excitement) more than 315 ℃.Yet, those skilled in the art should understand, to be suitable in preferred embodiments just, as long as under cure conditions, do not evaporate in the sulfidizing process of this oil in high pressure catalyzer transfer vessel 304 with any significance degree at the following ebullient hydrocarbon ils of described temperature.

In this embodiment preferred, with containing H ₂The logistics of S is to catalyzer transfer vessel 304 (adding catalyzer is used for from the liquid oils of catalyst hooper 312 transmission catalyzer from wherein removing at least a portion) pressurization.Contain H ₂The logistics of S can be in from the normal pressure to the reactor any pressure of pressure in 11 [for example, from 0.2MPa to 24.2MPa (15～3500psig)] scope.Be contained in the H in the recirculation stream ₂S will have 0.2MPa～3.4MPa (pressure of 15～500psig) usually.By pipeline 212 or pipeline 328 valve (cause catalysis transfer vessel block sealing, comprise valve 307,311,323,318 and 386) relevant vulcanizing agent is imported the catalyzer transfer vessel with pipeline.Valve 213 is held open, and application hydrogen or hydrogenous gaseous mixture are pressurized to required pressure (comprising the pressure up to reactor) by pipeline 212 with the catalyzer transfer vessel.Under required pressure, valve 213 cuts out for some time that is enough to vulcanize the catalyzer in the transfer vessel.In sulfidation, with catalyzer remain in 90 ℃～370 ℃ scopes, in preferred 125 ℃～325 ℃ scopes, in more preferably 150 ℃～285 ℃ scopes, the temperature in preferred 175 ℃～240 ℃ scopes further.Usually, be less than 24 hours, preferably be less than 10 hours, more preferably less than being enough to vulcanize at least in part described catalyzer in 5 hours.Method for pre-sulphuration cause available metal oxide site on the sulphurized catalyst stoichiometric quantity at least 35% and more preferably at least 50%.

May wish to come further sulphurized catalyst with the other processing of vulcanizing agent.Other processing beyond for the first time is to be undertaken by handling roughly the same method with the first time.Like this, when the processing first time finishes,, add other vulcanizing agent toward this transfer vessel 304 again with 304 decompressions (for example) of catalyzer transfer vessel by pipeline 212.Such as described above, use H ₂Container is pressurized to required pressure, again catalyzer is vulcanized under pressure generally be less than 24 hours, preferably be less than 10 hours, more preferably less than 5 hours.Skilled professional is clear, active S-contained substance (for example, the H in vulcanizing agent ₂S) will there be compromise proposal between interior applied pressure of curing time that concentration, permission sulfuration are carried out and the curing cycle number of taking.In the S-contained substance of high density, vulcanisation step, more under the high pressure, perhaps carry out the operation of longer time, the sulfuration amount that hope is bigger for vulcanisation step.The selection of concentration, pressure and time roughly is the thing of local condition; All combinations should be regarded as and belong to scope of the presently claimed invention, as long as when vulcanisation operation finishes, the sulfurized catalyzer keeps detectable sulphur content to get final product.

The slurry that sulfurized catalyzer (it is sulfureted in catalyzer transfer vessel 304) is usually with hydrocarbon ils is transferred to reactor 10.Such oil can provide from washing oil drum 356 by pipeline 340.Wish that catalyzer is the state (for example, 125 ℃～325 ℃) that is heated and leads to reactor, so, the oil that is heated used usually from washing oil drum 356.Such oil can by deep fat supply line 354 with the amount that is enough at least a portion catalyzer in the impregnation oils equal or a little higher than reactor in provide under the pressure of pressure.Then, open valve 307 feeds reactor with catalyzer to pass through adding oil to the definite speed of the speed of catalyzer transfer vessel 304 via pipeline 324.

In an independent embodiment, use the catalyzer in vulcanizing agent (it flows through the catalyzer in the transfer vessel 304 in sulfidation) the sulfuration transfer vessel 304.Can use gaseous state or liquid vulcanizing agent.As previously mentioned, preparation catalyst addition hopper 312 is accepted and is distributed hydrotreating catalyst (it preferably includes catalyzer of the present invention).Catalyst addition hopper 312 has a sagging pipeline 314 that it is communicated with high pressure catalyst charge container 304, and container 304 carries out hydrotreatment for the catalyzer from catalyst addition hopper 312 to catalyst charge container 304.Conveniently, sagging pipeline 314 is used for regulating the catalyzer that flows through it for being equipped with a valve 318.For high pressure catalyst charge container 304 has been equipped with high pressure charging pipeline 324 and valve 323, be used for feedstream is imported high pressure catalyst charge container 304.

High pressure charging pipeline 324 be communicated with from the effusive various feedstreams of each bar pipeline.Pipeline 328 imports high pressure charging pipeline 324 with " spike " agent or vulcanizing agent." spike " agent or vulcanizing agent flows in the flowrate control valve 330 control curing systems.Pipeline 340 transmits the hydrocarbon (for example, hot gas oil) that is heated, can also be to high pressure charging pipeline 324 feed.Pipeline 340 is equipped with flowrate control valve 348, be used for controlling on request with from " spike " agent of pipeline 328 or the flow of vulcanizing agent hydrocarbon that is heated of fusion in feed pipe 324.Pipeline 350 is equipped with flow/level control valve 360, and its effect is that the cold hydrocarbon of transmission (for example, cold gas oil) is to washing oil drum, generally shown in 356.

Pipeline 362 is equipped with flowrate control valve 358 and interconnects with curing system and pipeline 350, be used for being dispensed into vulcanizing agent feed pipe 324 from the cold hydrocarbon of pipeline 350 and with " spike " agent or vulcanizing agent and the hydrocarbon fusion of being heated, thereby reduce the bulk temperature of the vulcanizing agent/hydrocarbon mixture that is heated, perhaps after pre-sulfide catalyst, wash or wash by the catalytic bed (not shown) in the high pressure catalyst charge container 304.In a preferred embodiment, to hydrotreating catalyst heating, that is, make the hydrocarbon liquid flow of being heated cross a certain amount of hydrotreating catalyst in the treatment zone 50 like this, until catalyst temperature in 90 ℃～145 ℃ scopes.Subsequently, 0.2MPa～24.2MPa (to treatment zone pressurization, the hydrocarbon liquid that is heated then continues to flow through the catalyzer in the treatment zone under 15～3500psig) the pressure, until catalyst temperature in 125 ℃～325 ℃ scopes.Then, make the sulfur agent mixture that transports via pipeline 324 flow through the catalyzer in the treatment zone and prepare the sulfurized catalyzer.

High pressure catalyst charge container 304 is made of net 382 (being communicated with pipeline 384).Any mixture that be heated hydrocarbon and/or cold hydrocarbon and remnants (unreacted) " spike " agent or the vulcanizing agent of high pressure catalyst charge container 304 are flow through in overflow is passed net 382 and is entered pipeline 384 for transmission be dispensed into washing oil separator 376.Pipeline 384 has been equipped with flow/pressure control valve 386, is used for the mixture of controlling flow piping 384 and working pressure or the operating pressure in the control high pressure catalyst charge container 304.

To the be heated any mixture of hydrocarbon and/or cold hydrocarbon and remnants (unreacted) " spike " agent or vulcanizing agent of washing oil separator 376 is separated into various components.(wherein, " spike " agent or vulcanizing agent are to be rich in H in embodiment preferred of the present invention ₂The hydrocarbon gas of S), will be heated hydrocarbon and/or cold hydrocarbon and be rich in H of washing oil separator 376 ₂The mixture separation of the hydrocarbon gas of S becomes overhead gas (for example, methane, ethane, nitrogen etc. and composition thereof), it comes out by discharge line 396 (having flow/pressure control valve 398), and the liquid hydrocarbon that reclaims, it comes out from washing oil separator 376 by discharge line 390 (it extends to pipeline 352 from washing oil separator 376), herein, the liquid hydrocarbon of recovery be imported into washing oil drum 356 after be heated hydrocarbon and/or cold hydrocarbon mix.The liquid hydrocarbon that liquid/flowrate control valve 392 controls in the discharge line 390 are reclaimed flows through the flow that flows out pipeline 390 from washing oil separator 376.

Liquid hydrocarbon from the recovery of washing oil separator 376 contains remaining overhead gas (it does not separate) usually in washing oil separator 376.Under those typical situations, when the mixture of the liquid hydrocarbon that reclaims and be heated hydrocarbon and/or cold hydrocarbon when pipeline 352 is imported into washing oil drum 356, remaining overhead gas is separation and be assigned with by pipeline 414 from mixture in washing oil drum 356.Pipeline 414 is equipped with flow/pressure control valve 420, is used for regulating remaining overhead gas stream and regulates operating pressure or the working pressure that washs in the oil drum 356.

Shown in figure 2 in the embodiment, the treatment zone of catalyst vulcanization system comprise two containers (they be contained in hydroconversion reactions in the reactor distinguish from), a low pressure catalyst charge container (generally shown in 302) is communicated with high pressure catalyzer transfer vessel (generally shown in 304) by the pipeline 306 with valve 308 (it is used to be controlled to small part sulfurized catalyzer and transfers to high pressure catalyzer transfer vessel 304 from low pressure catalyst charge container 302).In this embodiment of the present invention, provide low pressure catalyst charge container 302 as at the hydrotreating catalyst that is transferred to the small part prevulcanized by pipeline 306 from low pressure catalyst charge container 302 before the high pressure catalyzer transfer vessel 304, wetting, preheating and to the initial installation of small part prevulcanized hydrotreating catalyst.To understand easily from following description, high pressure catalyzer transfer vessel 304 is equipped with and is used for continuing wetting, preheating and further vulcanizes to the source of the hydrotreating catalyst of small part prevulcanized, but carries out under higher temperature and/or pressure (near the reaction conditions in the reactor 11).The prevulcanized of hydrotreating catalyst is more to carry out under low temperature and the pressure than directly the catalyzer of prevulcanized being transferred to the required temperature and pressure in hydroconversion reactions district (for example, existing in the reactor 11).Cure conditions in the low pressure catalyzer transfer vessel 302 for example comprises: greater than 200KPa (15psig), preferably at 200KPa～7000KPa (pressure between the 15psig～1000psig), and 90 ℃～370 ℃ temperature.Should understand, comprise as the spirit and scope of the present invention of describing among Fig. 1, be equipped with fresh (needing sulfurized) hydrotreating catalyst at low pressure catalyst charge container 302 and high pressure catalyzer transfer vessel 304 in the two, vulcanize two parts of hydrotreating catalyst batch of materials arranging in two containers 302 and 304 subsequently simultaneously.

Entering reactor 11 by pipeline 305 after the sulfurized catalyzer comes out from high pressure catalyzer transfer vessel 304 stores.Pipeline 305 has been equipped with stopping valve 307.Catalyst addition hopper 312 is provided, has been used for accepting and distributing hydrotreating catalyst (it preferably includes catalyzer of the present invention).Catalyst addition hopper 312 has one with it and low pressure catalyst charge container 302 or the sagging pipeline 314 that is communicated with high pressure catalyst charge container 304, is used for the hydrotreating catalyst in the catalyst addition hopper 312 is led to catalyst charge container 302 or 304.Conveniently be that sagging pipeline 314 is equipped with a valve 318, be used for regulating the catalyzer that flows through it.For low pressure catalyst charge container 302 has disposed a low pressure feed pipeline 320 and corresponding valve 321, be used for feedstream is imported low pressure catalyst charge container 302.High pressure charging pipeline 324 is communicated with high pressure catalyzer transfer vessel 304, is used for supplying with the feedstream that upwards flows through it.

Low pressure feed pipeline 320 and high pressure charging pipeline 324 be communicated with from the effusive various feedstreams of each bar pipeline.Pipeline 328 imports low pressure feed pipeline 320 and high pressure charging pipeline 324 with " spike " agent or vulcanizing agent through pipeline 329.The flow of " spike " agent or vulcanizing agent in the flowrate control valve 330 control curing systems.Be heated hydrocarbon (for example, hot gas oil) and feeding in raw material of pipeline 340 transmission by 329 pairs of low pressure feed pipelines 320 of pipeline and high pressure charging pipeline 324.Pipeline 340 has been equipped with flowrate control valve 348, is used for controlling the flow of hydrocarbon of being heated, the hydrocarbon that is heated on demand in feed pipe 320 and 324 respectively with " spike " agent or vulcanizing agent fusion from pipeline 328.Pipeline 350 has been equipped with flow/level control valve 360, and effect is that the cold hydrocarbon of transmission (for example, cold gas oil) is to washing oil drum (generally with 356 diagrams).

Pipeline 362 be equipped with flowrate control valve 358 and with curing system and pipeline 350 intercommunications, be used for cold hydrocarbon from pipeline 350 be dispensed into sulfuration feed pipe 329 and with the vulcanizing agent and the hydrocarbon fusion of being heated, thereby reduce the bulk temperature of the vulcanizing agent/hydrocarbon mixture that is heated, perhaps after catalyzer was by prevulcanized, flushing or washing were by the catalyst bed (not shown) in low pressure catalyst charge container 302 and/or the high pressure catalyst charge container 304.

Another feature of the present invention of drawing among Fig. 2 is, fresh (needing sulfurized) hydrotreating catalyst can be dispensed into low pressure catalyst charge container 302 and high pressure catalyzer transfer vessel 304 the two, sulfuration simultaneously in two containers 302 and 304 subsequently.The setting of fresh (needing sulfurized) hydrotreating catalyst like this can be undertaken by the mode of any appropriate, for example, begin a collection of fresh (needing sulfurized) hydrotreating catalyst to be added the low pressure catalyst charge container 302 from catalyst addition hopper 312, by pipeline 306 this initial fresh hydrotreating catalyst of this batch that adds is transferred to high pressure catalyzer transfer vessel 304 subsequently, reinstall low pressure catalyst charge container 302 with another batch fresh (needing sulfurized) hydrotreating catalyst from catalyst addition hopper 312 then.Also can be equipped with second catalyst addition hopper (not shown), be exclusively used in high pressure catalyzer transfer vessel 304, be used for fresh (needing sulfurized) hydrotreating catalyst directly is dispensed into high pressure catalyzer transfer vessel 304 and by low pressure catalyst charge container 302.If require in container 302 and 304, to vulcanize simultaneously two batches of hydrotreating catalysts, just all open the flowrate control valve 330,348,358 and the adjusting on demand that lay respectively on the pipeline 328,340,362, those skilled in the art should know, can make them upwards flow through fresh (the needing sulfurized) hydrotreating catalyst that has been in advance in container 302 and 304 simultaneously the mixture while import pipe 320 and 324 of vulcanizing agent and be heated hydrocarbon and/or cold hydrocarbon like this.

Low pressure catalyst charge container 302 is made of net 370 (being communicated with pipeline 372).Any mixture that be heated hydrocarbon and/or cold hydrocarbon and remnants (unreacted) " spike " agent or the vulcanizing agent of low pressure catalyst charge container 302 are flow through in overflow is passed net 370 and is entered pipeline 372 for being transferred to and being dispensed into washing oil separator 376.Pipeline 372 has been equipped with a flow/pressure control valve 380, is used for the mixture of controlling flow piping 372 and working pressure or the operating pressure in the control low pressure catalyst charge container 302.High pressure catalyzer transfer vessel 304 is made of net 382, and any mixture of be heated hydrocarbon and/or cold hydrocarbon and remnants (unreacted) " spike " agent or vulcanizing agent can be passed net 382 and is imported into pipeline 384 for being transferred to washing oil separator 376 by pipeline 374.Pipeline 384 has been equipped with a flow/pressure control valve 386, is used for controlling from high pressure catalyzer transfer vessel 304 flowing through the mixture of pipeline 384 and working pressure and the operating pressure in the control container 304.

Preferably, the vulcanisation operation conditions in the low pressure catalyst charge container 302 comprise: 0.7KPa～1480KPa (service temperature of 0.1～200psig) working pressure and 90 ℃～370 ℃; Be more preferably 200KPa～1140KPa (service temperature of 15～150psig) working pressure and 125 ℃～325 ℃.Vulcanisation operation conditions in the high pressure catalyzer transfer vessel 304 comprise: 0.7KPa～24.2MPa (service temperature of 0.1～3500psig) working pressure and 90 ℃～370 ℃; Be more preferably 7.0MPa～24.2MPa (service temperature of 1000～3500psig) working pressure and 125 ℃～325 ℃.

In the method, can will be added in the hydroconversion reactions district from the catalyzer of the prevulcanized of high pressure transfer vessel 304 by pipeline 305.Though do not require, may wish to remove a certain amount of catalyzer from reaction zone 10, the amount that removes approximates the amount of the catalyzer that need add the prevulcanized in the reaction zone 10 to.Working order; no matter be that the catalyzer that adds prevulcanized earlier is taken out to the catalyzer that small part consumes from reaction zone again; still elder generation adds the catalyzer of prevulcanized to reaction zone again from the catalyzer granulation thing that reaction zone is taken out to the small part consumption; still be taken out to the catalyzer granulation thing of small part consumption and the catalyzer granulation thing that past reaction zone adds prevulcanized from reaction zone simultaneously; all not really important to the present invention, as long as the catalytic amount in the reaction zone is no more than the capacity of design.The transfer catalyst that is applicable to present method for example is disclosed U.S. Patent No. 5,498,327 (it is for referencial use to incorporate its full text into this paper) to reaction zone with from the method that reaction zone takes out catalyzer.

From reactor 11 take out off and on, semi-continuously or continuously be in the hydrocarbon liquid (definition) as described above, need be from the hydroconversion reactions district 10 catalyzer that consume to small part that take out, enter pipeline 198 and transfer to high pressure catalyst recovery container 304 via valve 94.The catalyzer that takes out will be about 50%～about 95% consumption usually, be more preferably that about 70%～about 80% consumes, and the catalyzer that 100% prevulcanized consumes will be polluted fully, so, there is not effective hydrocracking activity under the reaction conditions in hydroconversion zone basically.

The catalyzer that consumes at least in part in the hydrocarbon liquid has the concentration of high catalyzer to hydrocarbon liquid, preferably every pound of catalyst pulp (promptly, the catalyst weight carburation liquid weight that takes out) about 0.2～about 1.0 pounds of pelleted catalysts, being more preferably every pound of about 0.25～about 0.8 pound of pelleted catalyst of catalyst pulp, most preferably is every pound of about 0.5 pound of pelleted catalyst of catalyst pulp.Described hydrocarbon liquid can comprise the liquid hydrocarbon component, and it is transformed (becoming lighter product) or mixture that partly transformed or partly transformed and mixture unconverted liquid hydrocarbon component or hydrogen-containing gas component and any liquid ingredient as yet.

In the catalyst bed embodiment preferred of roughly filling, the catalyzer that consumes to small part of taking-up comes the volumetric layer volumetric layer of below (that is) of catalyzer of the catalyst bed 10 of autoreactor 11.Because when beginning to take out, the downward plug flow of the pelleted catalyst in the catalyst bed 10.As previously mentioned, the catalyzer that consumes to small part that takes out is transferred to high pressure catalyzer transfer vessel 304 as the spissated thick liquids slurry of the height of laminar flow regime in hydrocarbon liquid (definition as mentioned), in order to avoid the granules of catalyst (just being transferred to catalyzer transfer vessel 304) that consumes to small part that takes out by pipeline 198 by overwear vt..

The catalyzer that is applicable to present method is described in detail in U.S. Patent No. 5,472, in 928 (it is for referencial use to incorporate its full text into this paper).Preferred catalyzer comprises inorganic carrier, it may comprise zeolite, inorganic oxide (for example, silicon-dioxide, aluminum oxide, magnesium oxide, titanium dioxide and composition thereof), the amorphous refractory inorganic oxide of perhaps any II, III or IV family element, the perhaps composition of inorganic oxide.Described inorganic carrier more preferably comprises porous carrier material (for example, aluminum oxide, silicon-dioxide, silica-alumina or crystalline silicon aluminate).Be deposited on inorganic carrier or the porous carrier material and/or interior be one or more metals or metallic compound (for example, oxide compound), wherein, described metal is selected from IB, VB, VIB, VIIB and the VIII family of periodictable.The representative instance of these metals is iron, cobalt, nickel, tungsten, molybdenum, chromium, vanadium, copper, palladium and platinum and combination thereof.Preferably molybdenum, tungsten, nickel, cobalt, platinum and palladium and combination thereof.The appropriate catalyst example of preferred classes comprises: nickel-tungsten, nickel-molybdenum, cobalt-molybdenum or nickel-cobalt-molybdenum, they be deposited on be selected from down the group material porous inorganic oxide on and/or in: the combination of silicon-dioxide, aluminum oxide, magnesium oxide, zirconium white, Thorotrast, boron oxide (boria) or hafnia or inorganic oxide, for example, silica-alumina, silica-magnesia, aluminum oxide-magnesium oxide etc.

Catalyzer of the present invention can further comprise additive, for example, and phosphorus, boron, clay (comprising pillared clays), borophosphoric acid or yellow phosphorus (phosphor), and/or halogen (for example, fluorine and chlorine).The amount that the borophosphoric acid compound can exist based on total catalyst (promptly, inorganic oxide carrier adds metal oxide) weight calculate in about 10wt%～about 40wt% scope, more preferably in about 15wt%～about 30wt% scope, and the amount that halogen and yellow phosphorus are used is less than about 10wt% of total catalyst weight.

Though metal component (promptly, cobalt, nickel, molybdenum etc.) amount that can be any appropriate exists, but catalyzer of the present invention based on total catalyst (promptly, inorganic oxide carrier adds metal oxide) weight calculate the metal component preferably comprise about 0.1wt%～about 60wt%, more preferably about 5wt% of total catalyst weight～about 50wt%.The metal of VIII family is used with the less amount of about 0.1wt%～about 30wt% usually, and the group vib metal is then used with the bigger amount of about 1.25wt%～about 50wt% usually.The atomic ratio of VIII family and group vib metal can change in wide region, preferably about 0.01～about 15, more preferably and most preferably in about 0.1～about 5 scopes about 0.05～about 10.

Family in the periodictable that above relates to is from the periodic table of elements that is published in the following document: Lange ' s Handbook of Chemistry (the 12nd edition), John A.Dean edits, copyright 1979 belongs to McGraw-Hill, Inc., perhaps The Condensed ChemicalDictionary (the 10th edition), Gessner G.Hawley revision, copyright 1981 belongs to LittonEducational Publishing Inc.

In a preferred embodiment of catalyzer, be molybdenum oxide (MoO by the oxidation hydrotreating catalyst or the metal oxide component of inorganic carrier or the load of porous carrier material ₃) or MoO ₃And the combination or the MoO of cobalt oxide (CoO) ₃And the combination of nickel oxide (NiO), wherein, MoO ₃Exist with bigger amount.The porous inorganic carrier is more preferably aluminum oxide.Go up the MoO that exists at catalyzer inorganic carrier (aluminum oxide) ₃Amount based on the combined wt of inorganic carrier and metal oxide in about 1wt%～about 60wt% scope, preferably in about 1wt%～about 35wt% scope, more preferably in about 2wt%～about 8wt% scope.When having CoO (or NiO), its amount based on the combined wt of catalyzer inorganic carrier and metal oxide in about 30wt% scope at the most, preferably in about 0.5wt%～about 20wt% scope, more preferably in about 1wt%～about 6wt% scope.Oxidation hydrotreating catalyst or metal oxide component can prepare like this: the aqueous solution of metal oxide is deposited on the porous inorganic carrier substance, and thorough drying again, perhaps such catalyzer can be purchased from each catalyzer supply and buy.Catalyst preparation technology is routine techniques and be that people know normally, may comprise dipping, grinding, co-precipitation etc., then roasting.

In embodiment preferred of the present invention, catalyzer will have the size of homogeneous, it is spheric preferably, and the normal state Gaussian distribution curve of mean diameter is in about 1/64 inch～about 1/4 inch scope, more preferably in about 1/16 inch～about 1/8 inch scope.In order to keep the particle of single-size, preferably, at least about 70%, preferably at least about 80% more preferably at least about 90% catalyst particle size the average catalyst particle size about 20% with interior, preferred about 10% with interior and more preferably from about 5% with interior (wherein, average particle size particle size is based on the particulate longest dimension).

Be clear that for a person skilled in the art that from discussion above though the granules of catalyst of present method has size, shape and the density of homogeneous, the chemical property of catalyzer and metallographic character can become according to selected process object and processing condition.For example, use (requiring minimum hydrocracking) if selected catalyzer may be different from nature fully so that at utmost hydrogenating desulfurization and hydrocracking are the selected catalyzer of processing intent for demetalization.The Xuan Ding catalyst type with above-mentioned performance is disposed in any hydroconversion reactions district in view of the above.Hydrocarbon feed stream preferably passes through in the mode that for example upwards flows through catalyzer, so that to the hydrocarbon feed stream hydrotreatment by catalyzer.More preferably, in each embodiment of the present invention, use described catalyzer.

Further set forth method of the present invention by following specific embodiments of the invention.In the embodiment method, greater than about 343 ℃ and contain greater than the 1ppm metal with greater than the hydrocarbon feed stream of 500ppm sulphur and feed hydroconversion reactions district (it fills the granular hydrotreating catalyst that remains on reaction pressure), begin to make described hydrocarbon feed stream upwards to flow through described catalyzer and boiling point from wherein reclaiming reaction effluent.The character of selected feedstream, the character of catalyzer and reaction conditions (comprising flow velocity, temperature of reaction and reaction pressure) and reactor system is remained roughly packed bed type reactor assembly, wherein, the combination restriction bed of catalyzer and fluid velocity expand into length exceed be the packed bed state described bed roughly holoaxial to below 10% of length.More preferably, described bed is expanded remain on be the packed bed state described bed roughly holoaxial to below 5% of length, more preferably below 1%.Preferred reaction pressure is greater than 343 ℃, more preferably in 343 ℃～482 ℃ scopes in the hydroconversion reactions district.Preferred reaction pressure is greater than 7.0MPa (1000psig) in the hydroconversion reactions district, more preferably at 7.0MPa～24.2MPa (in 1000～3500psig) scopes.

In the hydrotreatment process, a certain amount of hydrotreating catalyst sulfuration in the treatment zone is produced the sulfurized catalyzer, at least a portion sulfurized catalyzer is added the hydroconversion reactions district, simultaneously reaction zone is remained on reaction pressure.

Need the sulfurized hydrotreating catalyst or be fresh hydrotreating catalyst, or the combination of fresh hydrotreating catalyst and regenerated hydrotreating catalyst.Though can comprise the other component except that needing the sulfurized catalyzer in described a certain amount of hydrotreating catalyst, it is not preferred usually.A certain amount of hydrotreating catalyst (for example is added to treatment zone, be added to treatment zone by slurry) with hydrocarbonaceous liquid and a certain amount of hydrotreating catalyst, take out at least a portion hydrocarbon liquid from treatment zone again, described amount is heated until catalyst temperature in 90 ℃～370 ℃ scopes.When reaching the temperature that needs, vulcanizing agent is added in the treatment zone and preparation sulfurized catalyzer.Suitable vulcanizing agent comprises H ₂S and H ₂, usually with 10: 1～1: 10 mol ratio.

The method example that vulcanizing agent is added in the treatment zone comprises, will contain H ₂The gaseous matter of S feeds treatment zone, to filling hydrotreating catalyst and containing H ₂Gas is in 200KPa～20, the treatment zone pressurization in the pressure in the 000KPa scope and 90 ℃～370 ℃ scopes under the temperature of (preferably in 125 ℃～325 ℃ scopes, more preferably in 150 ℃～285 ℃ scopes).Catalyzer in the treatment zone remained under the given pressure contact time enough (be less than 24 hours usually, preferably be less than 10 hours, more preferably less than 5 hours) with vulcanizing agent and vulcanize described catalyzer at least in part.Reduce the pressure in the treatment zone then, take out at least a portion of vulcanizing agent from treatment zone.

An alternative method example that vulcanizing agent is added in the treatment zone comprises that a certain amount of hydrotreating catalyst is added to treatment zone, and this amount comprises fresh hydrotreating catalyst; Then, make the hydrocarbon liquid flow of being heated cross the hydrotreating catalyst of measuring described in the treatment zone, until the temperature of catalyzer in 90 ℃～150 ℃ scopes; Subsequently, (under 15～3500psig) the pressure treatment zone is pressurizeed at 0.2MPa～24.2MPa; Continue to make the hydrocarbon liquid flow of being heated to cross catalyzer in the treatment zone, until the temperature of catalyzer in 125 ℃～325 ℃ scopes; Make cured blend flow through the catalyzer in the treatment zone and prepare the sulfurized catalyzer.

The sulfurized hydrogenation conversion catalyst is added in the hydroconversion reactions district, and the temperature of reaction zone is preferably greater than 150 ℃ greater than 125 ℃, and pressure then is not less than the reaction pressure in hydroconversion reactions district.The method that the sulfurized hydrogenation conversion catalyst is added to the hydroconversion reactions district comprises, adds hydrocarbon liquid in the interior sulfurized catalyzer of treatment zone; Formation comprises the slurry of hydrocarbon liquid and at least a portion sulfurized catalyzer; Slurry with this hydrocarbon liquid and sulfurized catalyzer is added in the hydroconversion reactions district again, keeps reaction zone in reaction pressure simultaneously.

Be contained in the reaction zone 10 mobile reaction system upwards preferably in the reactor 11, reacting fluid enters reaction zone 10 by opening for feed 14, upwards flows through reaction zone 10 moving-burden bed reactors in mobile mode upwards, and reaction effluent flows out from pipeline 16.Catalyst presulfurizing method is effective for such reaction zone: as the reaction zone of ebullating bed reactor system operation or as having replacement catalyst system in operation (that is, having the ability of under reaction pressure roughly catalyzer being transferred to reaction zone and being taken out from reaction zone), the reaction zone of packed bed type reactor assembly operation roughly.For reactor assembly being remained roughly packed bed type reactor assembly, described replacement catalyst system in operation is the counter-current operation system, wherein, catalyzer and fluid velocity combination restriction bed expand into length exceed be the packed bed state described bed roughly holoaxial to below 10% of length.More preferably, described bed is expanded remain on be the packed bed state described bed roughly holoaxial to below 5% of length, more preferably below 1%.One preferably roughly packed bed type reactor assembly enlighten in U.S. Patent No. 5,076, in 908 (it is for referencial use to incorporate its disclosure into this paper).

In implementing Fig. 1,2 extensively during the method for the preferred embodiment of the invention of explaination, be the minimum average B configuration fcc raw material upgrading activity level of the specific selected whole adverse current moving catalyst bed (for example, catalyst bed 10) of catalytic reforming reaction.For example, for the moving-bed in the demetalization reaction system (for example, catalyst bed 10), minimum average B configuration upgrading activity about catalyst bed is such, that is, when it during by the moving-bed under the demetalization condition, it has removed the metal of necessary amount from hydrocarbon feed stream.Equally, for the desulphurization reaction system, when it during by the moving-bed under the desulfurization condition, moving catalyst bed (for example, catalyst bed 10) has been removed the sulphur of necessary amount from hydrocarbon feed stream.So those technician will understand, will depend on pollutent (for example, metal, sulphur, nitrogen, the asphaltene etc.) dustiness of expectation about the minimum average B configuration upgrading activity level of specific reaction system, it is that the oil refining personnel wish to remove from heavy oil feedstock.Demetalization or desulfurization (etc.) degree will the downstream process of experience be determined by economic conditions and heavy oil feedstock usually.

It is about the raw material demetalization that the preferred upgrading of the present invention is used.For such upgrading, the temperature and pressure in the reaction zone can be the representative condition of conventional demetalization operation.Pressure is usually above 3.45MPa (500psig).Temperature is usually above 315 ℃, and preferably is higher than 371 ℃.Usually, temperature is higher, removes metal more rapidly; But temperature is higher, and the metals capacity efficient of the catalyst for demetalation of application is lower.Though the demetalization reaction can be carried out when not having the hydrogen of interpolation, uses hydrogen usually, therefore, require fully and equably to be distributed in the moving-bed with any gas that discharges from raw material.Preferred hydroprocessing condition to the hydrocarbon feed stream hydrotreatment in the hydroconversion reactions district comprises: the temperature of reaction of 343 °～482 ℃ (650 °～900) and 7.0MPa～24.2MPa (reaction pressure of 1000～3500psig).

Embodiment by following preferred embodiment has set forth the present invention.In the presence of the hydrogen hydrocarbon feed stream is being fed hydroconversion reactions district (it fills the granular hydrotreating catalyst that remains under the reaction pressure), beginning to make described hydrocarbon feed stream upwards to flow through described catalyzer and from wherein reclaiming reaction effluent.Reaction pressure is to be required concrete operations and reaction pre-selected, and it is usually greater than 3.6MPa (500psig), preferably at 7.0MPa～24.2MPa (in 1000～3500psig) the temperature range.Temperature of reaction (it is enough to the hydrocarbon feed stream hydrotreatment) is in the temperature range of 343 °～482 ℃ (650 °～900).In operation, take out the hydrotreating catalyst of first deal, keep reaction zone simultaneously under reaction pressure from the hydroconversion reactions district.Wish that the hydroconversion reactions district fills the roughly packed bed of catalyzer, when taking out the hydrotreating catalyst of first deal from reaction zone, catalyzer begins roughly to carry out plug flow downwards in the hydroconversion reactions district.

Preferable methods further is included in the hydrotreating catalyst of sulfuration second deal in the treatment zone and produces the sulfurized catalyzer.In embodiment preferred of present method, the sulfurized catalyzer is to produce like this: add the hydrotreating catalyst of second deal toward treatment zone, this second deal comprises fresh hydrotreating catalyst; With the heating of the hydrotreating catalyst of second deal until catalyst temperature 90 ℃～370 ℃, preferably in 125 ℃～325 ℃ temperature range; Add vulcanizing agent and prepare the sulfurized catalyzer toward treatment zone again.If catalyzer is added to treatment zone as the slurry in hydrocarbon stream for example, may require before sulfuration, to remove at least a portion hydrocarbon stream.Can flow through catalyzer by the liquid flow that makes vulcanizing agent or Containing Sulfur agent and add vulcanizing agent.Also can add vulcanizing agent by the container that contains hydrotreating catalyst in the treatment zone being pressurizeed with vulcanizing agent.Relate to and with vulcanizing agent the catalyzer in treatment zone pressurization is reached the vulcanization process that is enough to time of catalyst vulcanization and comprise this step, promptly, reduce the pressure in the treatment zone, the catalyzer in the treatment zone is pressurizeed again and catalyzer is further vulcanized with the vulcanizing agent of second deal.Repeat the application that this circulation can Gong be required by suitable sulfuration until catalyzer.

In order to use flowing fluid stream to catalyzer heating and/or sulfuration, embodiment preferred of the present invention comprises, makes the hydrocarbon liquid flow of being heated cross the hydrotreating catalyst of second deal in the treatment zone, until catalyst temperature in 90 ℃～145 ℃ scopes; Subsequently, treatment zone is pressurizeed; Continue to make the hydrocarbon liquid flow of being heated to cross catalyzer in the treatment zone, until catalyst temperature in 125 ℃～325 ℃ scopes; Then, add vulcanizing agent in the hydrocarbon liquid that is heated and produce cured blend; Make cured blend flow through the catalyzer in the treatment zone and prepare the sulfurized catalyzer.Preferred vulcanizing agent comprises H ₂S (for example, comes the H of the recirculation flow that reclaims since reaction effluent ₂S), dimethyl sulfide and dimethyl disulfide.Can be by present method sulphurized catalyst at low temperatures, for example, be lower than 370 ℃, preferably in 125 ℃～325 ℃ temperature ranges, more preferably in 150 ℃～285 ℃ temperature ranges, vulcanize.In can the low pressure vessel in treatment zone at 200KPa (15psig) or sulphurized catalyst under the high pressure more; (sulfuration is perhaps vulcanized in the two under the pressure in 1000～3500psig) scopes at for example 7.0MPa～24.2MPa in the high pressure vessel in treatment zone.

Under the pressure higher, the sulfurized catalyzer is added the hydroconversion reactions district, so that make catalyzer flow into reaction zone than reaction pressure.Suitably, catalyzer is added to reaction zone as the slurry in hydrocarbon stream, that is, and by hydrocarbon liquid being added in the treatment zone in the sulfurized catalyzer; Form the slurry of a kind of hydrocarbonaceous liquid and at least a portion sulfurized catalyzer; Slurry with this hydrocarbon liquid and sulfurized catalyzer is added in the hydroconversion reactions district again.

Embodiment

Embodiment

Salic porous carrier material of described granules of catalyst or aluminum oxide inorganic carrier.Be deposited on the aluminum oxide porous property carrier substance and/or interior be to contain NiO and/or MoO ₃Oxidation hydrotreating catalyst component.On the aluminum oxide porous property carrier substance and/or the Mo content of interior existence be about 3wt% based on the combined wt of aluminum oxide porous property carrier substance and oxidation hydrotreating catalyst component.On the aluminum oxide porous property carrier substance and/or the Ni content of interior existence be about 1wt% based on the combined wt of aluminum oxide porous property carrier substance and oxidation hydrotreating catalyst component.The surface-area of granules of catalyst is about 120 square metres of every grams.

Most of catalysis granulates are spherical in shape usually, and the mean diameter value is about 6 Tyler standard sieves～about 8 Tyler standard sieves, and long-width ratio is about 1.The average crush strength of catalysis granulate is about 5 ft lbfs.The metal load ability of catalyzer or most of catalysis granulates is every cubic centimetre of about 0.3 gram metals of catalysis granulate loose measure.

Catalyst sample is packed into vulcanization reaction device (205 ℃ of heating down, with middle turning oil (MCO) overflow).After 30 minutes, turning oil in the middle of discharging continues pumping with MCO and passed through catalyzer (unlatching relief outlet) 30 minutes again.Stop to flow of MCO, allow excessive oil discharge from catalyzer.Then, use the 5.0vol%H of 13.2MPa ₂S is (in H ₂In) to the catalyzer pressure treatment in the vulcanization reaction device 2.5 hours.Reduce pressure 790KPa and be cooled to 38 ℃ of the vulcanization reaction device that will fill catalyzer again.Remove remaining MCO with heptane flushing catalyzer, drying reclaims for analyzing.Sulphur content shown in the Table I test A is to use dimethyl disulfide at the sulphur content percentage ratio that exists on by standardized liquid vulcanization process sulfurized catalyzer under 316 ℃.

Table I has also been listed the sulphur content of using on the following method sulfurized catalyzer: the method for using above-mentioned test A (for example, test B), the method for application test A, but when beginning (for example wash catalyzer without MCO, test C), the method of application test A, but 316 ℃ (for example, test D) or at 149 ℃ (for example, test E), perhaps vulcanized 1.25 hours down, then 316 ℃ of sulfurations 1.25 hours (for example, test F) down at 204 ℃.Result in the Table I shows, under test conditions, uses once contact and circulates in 204 ℃ and suitably vulcanized catalyzer.State of vulcanization under 204 ℃ is than 149 ℃ or higher at 316 ℃.Twice vulcanisation cycle is better slightly than a round-robin result.From the state of vulcanization of catalyzer, optimum be curing temperature remain on 204 ℃ following 1.25 hours, then at 316 ℃ (test F) appearred in following 1.25 hours.

Table I

Test	??A	??B	??C	??D	??E	??F
							Catalyst pretreatment	Wetting with middle turning oil	Wetting with middle turning oil	Exsiccant	Wetting with middle turning oil	Wetting with middle turning oil	Wetting with middle turning oil
Curing temperature	??204℃	??204℃	??204℃	??316℃	??149℃	??204℃/316℃
							The number of times of vulcanisation cycle	??1	??2	??1	??1	??1	??1
Curing time, each circulation	2.5 hour	2.5 hour	2.5 hour	2.5 hour	2.5 hour	2.5 hour
							The sulphur content of sulfurized catalyzer	??76％	??82％	??77％	??62.5％	??69.1％	??90.5％

Three catalyst samples have been tested: by the H of above-mentioned test A preparation ₂The catalyst sample of S prevulcanized (sample G); The catalyst sample (sample H) 316 ℃ of following prevulcanizeds is handled in the prevulcanized of application standard dimethyl disulfide liquid; And the catalyst sample (sample I) that does not have prevulcanized.

Each catalyst sample is splashed into the Arabic heavy atmospheric resids (4.3% sulphur, 24.6ppm nickel, 82.4ppm vanadium and 11.3API proportion) that is heated to 371 ℃ and simulation splashes into moving-burden bed reactor with catalyzer under temperature of reaction.After 24 hours, take out catalyzer from Residual oil, use solvent washing, drying is analyzed residual sulphur content.

Sulphur content on the catalyst sample catalyzer, wt%

G????????????????????2.83

H????????????????????2.79

I????????????????????2.68

These results have enlightened, and the total sulphur content on each of three catalyst samples is roughly the same.

After the hot oil processing, use atmospheric resids raw material and tested the desulphurizing activated of catalyst sample G, H and I with following properties.

Proportion, ° API 8.9

Sulphur, wt% 4.51

MCR，wt％???????????????16.6

V，ppm??????????????????358

Ni，ppm?????????????????70

Asphaltene, wt% 13.6

Nian Du @100 ℃, cSt 285

At 13.9MPa pressure, 0.75hr ^-1Flow velocity under, make atmospheric resids raw material and H ₂Contact on every kind of catalyzer is (once by 760 liters of H ₂The hydrogen stream of/kg oil).At preceding 250 hours, temperature of reaction is remained on 378 ℃.Between 250 hours～750 hours, temperature of reaction is remained on 402 ℃.

Fig. 3 is a width of cloth normalization method hygrogram, it illustrate keep the stripper bottom (under 0.75LHSV, supposition 1.5 ^ThThe activation energy of level kinetics and 30 kilocalories/gram mole) product sulphur content required normalization method temperature of reaction when 2.2wt%.As shown in Figure 3, use H ₂The catalyzer that S handles prevulcanized is than conventional unvulcanized catalyzer more active (that is, lower temperature of reaction) 3.9 ℃ (7 °F).The dimethyl disulfide prevulcanized that application charges is higher comes the catalyzer of prevulcanized than more active 9.4 ℃ of conventional unvulcanized catalyzer (17).These data sheet were understood before catalyzer is added to the moving bed reaction system unexpected benefit to presulfiding of catalyst (even supposition is in case be added to reaction zone with catalyzer, the sulfur component of the raw material that catalyzer is just being handled is vulcanized rapidly).

Claims (14)

1. a prolongation is used for the method for cycling time of catalyzer of the hydrotreatment of heavy hydrocarbon liquid flow, described hydrotreatment is to have at least one reaction zone and a moving-burden bed reactor system that is used for the pretreating zone of presulfiding of catalyst is carried out, wherein, described heavy hydrocarbon streams upwards flows through reaction zone, this reaction zone fills to the catalyzer of small part prevulcanized, it in treatment zone by to the small part prevulcanized.

2. the method for claim 1, described moving-burden bed reactor system is selected from down the group system: (i) fixed-bed reactor system; (ii) can replace the boiling class and the expansion class reactor system of catalyzer in operation; The roughly packed bed type reactor assembly that (iii) has the system of replacement catalyzer in operation.

3. the process of claim 1 wherein that described heavy hydrocarbon liquid flow is an atmospheric resids.

4. the process of claim 1 wherein, by following steps in treatment zone with presulfiding of catalyst:

A) add a certain amount of hydrotreating catalyst in treatment zone, described amount comprises fresh hydrotreating catalyst;

B) heating described amount hydrotreating catalyst, until catalyst temperature in 90 ℃～370 ℃ scopes; And

C) in treatment zone, add the catalyzer of prevulcanized agent with the preparation prevulcanized.

5. the method for claim 4 wherein, is vulcanized hydrotreating catalyst under 125 ℃～325 ℃ temperature.

6. the method for claim 4, wherein, the step of adding a certain amount of hydrotreating catalyst in the treatment zone comprises:

A) a kind of slurry that comprises hydrocarbon liquid and a certain amount of hydrotreating catalyst of preparation;

B) slurry that will comprise hydrocarbon liquid and hydrotreating catalyst is added in the treatment zone; And

C) take out at least a portion hydrocarbon liquid from treatment zone.

7. the method for claim 4, wherein, the step of adding the prevulcanized agent in the treatment zone comprises:

A) under the temperature of the pressure of 0.2～24.2MPa and 90 ℃～370 ℃ to the treatment zone pressurization that fills hydrotreating catalyst and prevulcanized agent and produce to the catalyzer of small part prevulcanized; And

B) take out at least a portion prevulcanized agent from treatment zone.

8. the method for claim 7, wherein, described prevulcanized agent comprises S-contained substance, it is selected from H ₂S and be lower than the S-contained substance that decomposes under about 370 ℃ temperature.

9. the method for claim 8, wherein, described prevulcanized agent comprises H ₂S.

10. the method for claim 9, wherein, described prevulcanized agent comprises and contains H ₂And H ₂The gaseous recycle stream of S.

11. the method for claim 7, wherein, described catalyzer to the small part prevulcanized is to produce under 125 ℃～325 ℃ the temperature and under the pressure of 5.0MPa～20MPa.

12. the method for claim 11, wherein, described catalyzer to the small part prevulcanized is to produce under 150 ℃～285 ℃ temperature.

13. the method for claim 4, wherein, the step of adding the prevulcanized agent in the treatment zone comprises:

A) add a certain amount of hydrotreating catalyst in treatment zone, described amount comprises fresh hydrotreating catalyst;

B) make the hydrocarbon liquid flow of being heated cross the hydrotreating catalyst of described amount in the treatment zone, until catalyst temperature in 90 ℃～145 ℃ scopes;

C) (under 15～3500psig) the pressure treatment zone is pressurizeed at 0.2MPa～24.2MPa subsequently;

D) continue to make the hydrocarbon liquid flow of being heated to cross catalyzer in the described treatment zone, until catalyst temperature in 125 ℃～325 ℃ scopes;

E) make the prevulcanized mixture flow through the catalyzer in the described treatment zone and prepare to the catalyzer of small part prevulcanized.

14. the method for claim 13, wherein, described catalyzer to the small part prevulcanized is to produce under 150 ℃～285 ℃ temperature.

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