CN108003924A

CN108003924A - Improve the Heavy oil hydrogenation method of catalyst utilization

Info

Publication number: CN108003924A
Application number: CN201610965437.8A
Authority: CN
Inventors: 吴锐; 韩照明; 刘涛; 张彦杰; 葛培忠; 王军; 唐军; 孙庭阁; 王志勇
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-11-01
Filing date: 2016-11-01
Publication date: 2018-05-08
Anticipated expiration: 2036-11-01
Also published as: CN108003924B

Abstract

The invention discloses a kind of Heavy oil hydrogenation method for improving catalyst utilization.After the molten hydrogen of heavy oil feedstock oil saturation, first by weighted BMO spaces area, hydrodemetallization and partial desulfurization reaction are carried out；Reaction effluent enters hydrotreating reaction area with hydrogen, carries out hydrodesulfurization and hydrodenitrogeneration reaction；Wherein the reaction temperature of weighted BMO spaces reaction zone is higher than the reaction temperature in hydrotreating reaction area.In the method for the present invention, weighted BMO spaces reaction zone is reacted at higher temperatures, the most of metal impurities that can be stripped of in material, so that the deactivation cause of desulphurization catalyst and/or denitrification catalyst is changed into only coking deactivation from conventional metal deposit and coking deactivation in hydrotreating reaction area, so that desulphurization catalyst and denitrification catalyst can carry out regeneration treatment after using a cycle, extend the service cycle of hydrogenation plant, so as to add the operational efficiency of device, economy is improved.

Description

Improve the Heavy oil hydrogenation method of catalyst utilization

Technical field

The present invention relates to petroleum refining field, more particularly to a kind of Heavy oil hydrogenation method for improving catalyst utilization.

Background technology

At present, domestic and international refined products market will be in continuous upward trend to the demand of light, middle matter oil product, to fuel oil etc. The demand of heavy oil product is then on a declining curve.Further, since the pressure of environmental protection increasingly increases, various countries generally improve oil The quality criteria requirements of the especially automobile-used petrol and diesel oil product of product., can be with more economical rational generation under above-mentioned market trend Valency realize heavy oil lighting and can make obtained product meet the oil Refining Technologies of constantly harsh petrol and diesel oil product specification into One of technology of domestic and international oil Refining Technologies developer's focus development.

In the various processes of heavy oil product lighting, heavy oil product is subjected to hydrotreating first, is then hydrogenated with It is a kind of preferable technical process that tail oil, which carries out catalyzed cracking processing,.By hydrogenation, significantly reduce metal in these raw materials, Sulphur, nitrogen, asphalt content, improve hydrogen-carbon ratio, and then excellent raw material is provided for devices such as catalytic cracking and delayed cokings.At present Main hydrogenation technique mainly has ebullated bed, suspension bed, moving bed and fixed-bed process, wherein suspension bed and moving bed process also It is very immature, and cost is higher.Ebullated bed investment is higher, and operation difficulty is larger.Fixed bed is low, easy to operate because of cost And security is small, technology maturation, thus develop very fast.

In the prior art, realized by being provided with multiple hydrogenation reactors of multiple hydrogenation catalyst beds to heavy oil product Hydrotreating.But the usual viscosity of heavy oil product is larger, metal impurities or asphalitine are higher, in hydrogenation process, metal and Coke can be gradually deposited on catalyst, easily make rapid catalyst deactivation, and bed blocks, pressure rise, this phenomenon is the One hydrogenation reactor is especially serious, moreover, when the pressure drop in first reactor reaches or approaches the theoretical pressure drop upper limit, instead Answer and easily occur hot spot in device, device can only be forced to stop work at this time, shorten the service cycle of heavy oil product hydrotreater.

It is former that CN1349554A discloses a kind of up-flow reactor system hydrotreating heavy with stratiform catalyst bed The method of material.With the upflow fixed bed reactor hydrotreating metal of the catalyst of at least two different hydrogenation activities, sulphur and The heavy charge of carbon containing residual matter pollution.But this method cycle of operation is short, it is usually no more than 1 year.

Itd is proposed in CN1484684A replaceable reactor and can short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction method, should It is traditional down-type fixed-bed reactor that reactor is protected in patent, if Ca, Fe content are higher in raw material, due to reaction Logistics from top to bottom, if the gap between these solid impurity blocking catalysts, though in protective agent duct deposited metal energy When power does not arrive saturation capacity, this reactor pressure decrease can also raise, so that another reactor must be switched to.

CN102453530A discloses a kind of method of hydrotreating of processing heavy oil product, heavy oil product feedstock oil and hydrogen mixing Enter hydrogenation protecting reaction zone afterwards, then immediately proceed to hydrotreating reaction area, at least two parallel connections be set in hydrogenation protecting area Can switch the up flow type hydrogenation protecting reactor used in turn.The invention is had using the method for four kinds of hydrogenation protecting agent gradings Beneficial to removing metal, with the service life for preventing from blocking and improving major catalyst, extend the operation cycle of device.But this method is to device The increase rate of the cycle of operation is still little.

The content of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of Heavy oil hydrogenation method for improving catalyst utilization, especially It is that one kind can give full play to differential responses area catalyst performance, increases the heavy oil hydrogenation treatment method of device service cycle.

The Heavy oil hydrogenation method provided by the present invention for improving catalyst utilization, including herein below：

（1）At least one weighted BMO spaces reaction zone and a hydrotreating reaction area are provided；Bag in weighted BMO spaces reaction zone Hydrogenation protecting catalyst and Hydrodemetalation catalyst are included, Hydrobon catalyst is included in hydrotreating reaction area and hydrogenation is de- Nitrogen（Carbon residue converts）Catalyst；

（2）Heavy oil feedstock oil, the recycle oil in weighted BMO spaces area and hydrogen enter mixer and form the molten hydrogen logistics of saturation simultaneously together Discharge gaseous hydrogen；

（3）From step（2）The molten hydrogen logistics of saturation enter weighted BMO spaces reaction zone, liquid is carried out under the conditions of weighted BMO spaces Metal impurities are removed 40wt%~90wt% by phase hydrogenation reaction, and sulphur is removed 20wt%~70wt%, obtain tenor reduction Reaction effluent；

（4）Step（3）Obtained reaction effluent enters isolated first hydrogen-rich gas of the first high-pressure separator and the first liquid Body, separating obtained first hydrogen-rich gas use after can isolating hydrogen after further treatment through compressor compresses Posterior circle；

（5）Step（4）A first obtained liquid part is recycled back to weighted BMO spaces reaction zone, and another part enters hydrotreating Reaction zone, under hydroprocessing conditions, is contacted with Hydrobon catalyst and hydrodenitrogenation catalyst, obtain sulfur content and The reaction effluent that nitrogen content reduces；

（6）Step（5）Obtained reaction effluent enters isolated second hydrogen-rich gas of the second separator and second liquid；Point Go back to hydrotreating reaction area through desulfurization and compressor compresses Posterior circles from the second hydrogen-rich gas of gained, separating obtained second liquid into Enter fractionating system.

Hydrotreating method according to the present invention, wherein step（3）The average reaction temperature of weighted BMO spaces reaction zone compared with Step（5）The average reaction temperature in hydrotreating reaction area wants 5~40 DEG C high, preferably 10~30 DEG C high.

Hydrotreating method according to the present invention, wherein, step（1）It is middle that more than two weighted BMO spaces reactions are provided Area, which is usually arranged in parallel, the reaction zone of changeable operation.Therefore, it is of the invention Method can also include step（7）, can be by it after one of weighted BMO spaces reaction zone cannot meet service requirement Reaction process is cut out, and second weighted BMO spaces reaction zone is cut in technological process, the weighted BMO spaces reaction zone cut out The displacement of catalyst can be carried out, that is, draws off the old catalyst of inactivation, reloads fresh and/or regenerated catalyst.

The weighted BMO spaces reaction zone cannot meet that service requirement refers to：The effluent of weighted BMO spaces reaction zone can not Meet that the pressure drop of at least one catalyst bed in the feed needs or weighted BMO spaces reaction zone of downstream hydrogenation treatment region reaches There is hot spot in the pressure drop upper limit or catalyst bed.

It is described can not meet downstream hydrogenation processing reaction zone the standards of feed needs can be：Weighted BMO spaces reaction zone Tenor in outlet product liquid exceedes setting.Specifically, judging weighted BMO spaces reaction zone outlet product liquid is The standard of the no feed needs for meeting downstream hydrogenation treatment region is the tenor in effluent liquid（Refer to W metal, V, Fe, The summation of Na and Ca equal sizes）The μ g/g of 8 μ g/g~50 are exceeded, have been preferably the μ g/g of 10 μ g/g~30.

The pressure drop upper limit designs 0.4~0.8 times, preferably 0.5~0.8 times of maximum pressure drop for reactor.It is described Hot spot is that the radial temperature difference at least one catalyst bed is 15~50 DEG C, preferably 15~30 DEG C.

In the heavy oil hydrogenation treatment method of the present invention, the heavy oil feedstock oil refers to by topped crude, petroleum residual oil, oil The hydro carbons for the high asphalt content that sand, pitch, shale oil, liquefaction coal or reclaimed oil obtain.Heavy oil feedstock oil usually contains various Pollutant, its carbon residue is high, and the impurity content such as sulphur and nitrogen is high, its tenor is typically larger than 30mg/g.The method of the present invention is especially It is adapted to the heavy oil feedstock of processing high metal content, is especially suitable for processing metal (nickel+vanadium) content and is more than 60mg/g and/or iron content More than 10mg/g and/or calcium content is more than the heavy oil feedstock of 10mg/g.

In the method for the present invention, the hydrogenation protecting catalyst that weighted BMO spaces reaction zone uses can be that residual hydrogenation is protected Agent, or prepared according to feedstock property by this area conventional method.Residual hydrogenation protective agent is this area conventional catalyst, can be with Using commercial goods.The hydrogenation protecting agent using porous refractory inorganic oxide such as aluminium oxide as carrier, group VIB and/or The oxide of VIII race's metal such as W, Mo, Co, Ni etc. is the catalyst of active component, such as by the limited public affairs of Sinopec's share Take charge of the FZC series residual hydrogenation protective agents of catalyst branch company production.

The Hydrodemetalation catalyst can be residuum hydrogenating and metal-eliminating catalyst, or according to feedstock property by this It is prepared by field conventional method.These catalyst are typically all the group VIB using porous refractory inorganic oxide such as aluminium oxide as carrier And/or VIII one or more of oxides of race's metal such as W, Mo, Co, Ni etc. be active component, be selectively added other each The catalyst of the elements such as kind auxiliary agent such as P, Si, F, B.The Hydrodemetalation catalyst, on the basis of the gross weight of catalyst, And in terms of oxide, the content of molybdenum and/or tungsten is 0.5~15 weight %, the content of cobalt and/or nickel is 0.3~8 weight %, remaining Measure as alumina support.The alumina support is a kind of alumina support in bimodal hole, its pore volume for 0.5~2.0 milliliter/ Gram, specific surface area is 120~350 meters²/ gram, aperture accounts for total pore volume 30~90% in 10~30 nanometers of pore volume, and aperture is 100 ~2000 nanometers of pore volume accounts for total pore volume 10~50%, and bore dia is less than 10 nanometers, between 30-100 nanometers and is more than The sum of 2000 nanometers pore volume accounts for total pore volume below 20%.Arrive in order to balance reactant molecule diffusion process and reaction needed for Active surface, the catalyst with the bimodal pore distribution of macropore and mesoporous are shown in weighted BMO spaces reaction zone reaction process Preferable performance.In weighted BMO spaces reaction zone, the admission space ratio of hydrogenation protecting catalyst and Hydrodemetalation catalyst Generally 5:95~95:5, it is preferably 10:90~60:40.

Heavy oil hydrogenation treatment method according to the present invention, wherein in weighted BMO spaces reaction zone, preferably in the de- gold of hydrogenation The downstream of metal catalyst can also include Hydrobon catalyst.The loadings of Hydrobon catalyst are hydrodemetallisation catalyst The 5%~30% of agent loadings.

The Hydrobon catalyst can be the common residuum hydrodesulfurization catalyst in this area, or according to raw material Property is prepared by this area conventional method.Catalyst is typically all using porous refractory inorganic oxide such as aluminium oxide as carrier the The oxide of VI B races and/or VIII race's metal such as W, Mo, Co, Ni etc. are active component, are selectively added other various auxiliary agents such as P, the catalyst of the element such as Si, F, B.Due to restricted to tenor in weighted BMO spaces reaction zone product in this technology, it is The more preferable overall performance optimization for playing catalyst system uses improved Hydrobon catalyst, the overall performance of the catalyst Between conventional Hydrodemetalation catalyst and Hydrobon catalyst, i.e. the more conventional hydrodesulfurization in aperture of the catalyst Catalyst is bigger, holds metal ability with preferable, its more conventional Hydrodemetalation catalyst of activity is slightly higher, has stronger add Hydrogen desulphurizing ability.

The Hydrobon catalyst, on the basis of the gross weight of catalyst, and in terms of oxide, molybdenum and/or tungsten Content is 10~25 weight %, and the content of cobalt and/or nickel is 1~6 weight %, and surplus is alumina support.The aluminium oxide Pore volume is not less than 0.35 ml/g, and specific surface area is 150~350 meters²/ gram, aperture accounts for total pore volume in 6~15 nanometers of pore volume More than 70%.

In the method for the present invention, reaction condition can be according to the reaction effect that the property and requirement of raw material reach by this area General knowledge determines.In general the reaction condition of weighted BMO spaces reaction zone is that reaction pressure is 5MPa~35MPa, preferably It is that 10MPa~20MPa, average reaction temperature are 340 DEG C~430 DEG C, preferably operates at 340 DEG C~420 DEG C, volume is empty during liquid Speed is generally in 0.1h^-1~5.0h^-1, preferably 0.3h^-1~3.0h^-1In the range of, hydrogen to oil volume ratio is 200~2000, is preferably 300~1500, liquid phase circulation ratio（The mass ratio of recycle oil/fresh feed oil）For 0.1:1~10:1, preferably 0.2:1~3:1.

In the method for the present invention, the weighted BMO spaces reaction zone can set one or more hydrogenation protecting to react Device, each hydrogenation protecting reactor is at least provided with a hydrogenation protecting catalyst bed, if being provided with multiple catalyst beds, The recycle oil of the molten hydrogen of saturation can be squeezed between reaction bed, to reach reduction catalyst bed temperature rise and reaction is replenished in time The purpose of required hydrogen.

In the method for the present invention, the mixer used can be eddy mixer or static mixer, jet mixing Device etc. mixer.

In the method for the present invention, the catalyst used in hydrotreating reaction area can be that the common heavy oil product in this area adds Hydrogen handles catalyst, and optimum catalyst property can be optimized according to feedstock property.Catalyst generally comprises a variety of, such as hydrogenation Desulphurization catalyst and hydrodenitrogenation catalyst etc..These catalyst be typically all using porous refractory inorganic oxide such as aluminium oxide as The oxide of carrier, group VIB and/or VIII race's metal such as W, Mo, Co, Ni etc. are active component, are selectively added other each The catalyst of the elements such as kind auxiliary agent such as P, Si, F, B.

In the hydrotreating reaction area, the admission space of Hydrobon catalyst and hydrodenitrogenation catalyst is than general For 20:80~80:20, it is preferably 40:60~70:30.

The hydrodenitrogenation catalyst, on the basis of the gross weight of catalyst, and in terms of oxide, molybdenum and/or tungsten Content is 12~30 weight %, and the content of cobalt and/or nickel is 3~12 weight %, and surplus is alumina support.The aluminium oxide Pore volume is not less than 0.35 ml/g, and specific surface area is 150~350 meters²/ gram, aperture accounts for total pore volume in 6~15 nanometers of pore volume 40~75%.

The method according to the invention, can also include Hydrodemetalation catalyst wherein in hydrotreating reaction area, hydrogenation Catalyst for demetalation is seated in the upstream of Hydrobon catalyst, and the loadings of Hydrodemetalation catalyst are hydrotreating reaction The 2%~30% of area's catalyst total filling amount.

In hydrotreating reaction area catalyst filling order be usually make reaction stream successively with hydrodemetallisation catalyst Agent, Hydrobon catalyst and hydrodenitrogenation catalyst contact, also have the technology of these types of catalyst mixed packing certainly.On State the technology contents that Catalyst packing technology is well known to those skilled in the art.Catalyst can use commercial goods, as in The FZC series residuum hydrogenating and metal-eliminating catalysts of petrochemical industry Fushun Petrochemical Research Institute of state development and production, desulphurization catalyst and de- Nitrogen catalyst, can also prepare according to this area existing method.

In the method for the present invention, the reaction condition in hydrotreating reaction area is that reaction pressure is 5MPa~35MPa, preferably It is that 10MPa~20MPa, average reaction temperature are 320 DEG C~420 DEG C, preferably operates at 330 DEG C~410 DEG C, volume is empty during liquid Speed is 0.1h^-1~5.0h^-1, preferably 0.3h^-1~3.0h^-1, hydrogen to oil volume ratio is 200~1500, is preferably 300~1200.

In the method for the present invention, weighted BMO spaces belong to serial operation, therefore two reactions with hydrotreating two reaction zones The pressure in area is same pressure rating, because the presence of pressure drop might have difference slightly.

In the method for the present invention, hydrodemetallization and partial hydro-desulfurization reaction are substantially carried out in weighted BMO spaces reaction zone, It is operated at a higher temperature, is conducive to the progress of demetalization reaction, so that the activity of Hydrodemetalation catalyst can It is fully used.The material for being stripped of a large amount of metal impurities is further reacted into hydrotreating reaction area.Due to A large amount of metal impurities are stripped of, murder by poisoning of the material to hydrotreating zone catalyst into hydrotreating reaction area is greatly lowered, The utilization rate of Hydrobon catalyst and hydrodenitrogenation catalyst can be significantly improved, extends the use of hydrotreating zone catalyst Service life, and then effectively extend the service cycle of a whole set of hydrotreater.For the operation of Proper Match two reaction zones, hydrogenation The average reaction temperature in pretreatment reaction area is 5~40 DEG C high compared with the average reaction temperature in hydrotreating reaction area, preferably high by 10~ 30℃。

In the method for the present invention, hydrotreating reaction area can set a reactor, can also set more reactors, 2~5 are usually set, is preferably provided with 2~3 reactors.The number of each catalyst in reactor bed is generally 1~5, It is preferred that 1~3, if setting more than two catalyst beds, quenching hydrogen can be squeezed between bed, with control reaction temperature Degree, Hydrodemetalation catalyst, Hydrobon catalyst are loaded in hydrotreating reaction area successively along the flow direction of reaction stream With hydrodesulfurization nitrogen catalyst.In the method for the present invention, in each catalyst bed the loadings of catalyst can according to feedstock property, The requirement of selected catalyst and product property comes specifically chosen.

To reach more preferable effect, the changeable weighted BMO spaces reaction zone of two or more can be used.It is described changeable Implication refers to be provided with multiple weighted BMO spaces reaction zones, and each weighted BMO spaces reaction zone can individually be connected into follow-up add Hydrogen handles reaction zone, also can individually be cut out from hydrotreating reaction area.

Hydrotreating method according to the present invention, the purpose that multiple changeable weighted BMO spaces reaction zones are set be in order to The catalyst in each reactor in hydrotreating reaction area is set to obtain lasting hydrogenation protecting, therefore, Mei Gejia by switching Hydrogen pretreatment reaction zone sets the number of reactor and as long as connection relation meets the purpose that switching uses.Preferably, institute The quantity for stating weighted BMO spaces reaction zone is 2, and the weighted BMO spaces reaction zone sets 1 reactor, preferably with Mode in parallel connects, and two weighted BMO spaces reaction zones one and only one be in on-line machining state.Weighted BMO spaces The agent of order filling hydrogenation protecting, Hydrodemetalation catalyst and Hydrobon catalyst, all kinds of protective agents and catalysis in reaction zone The grading mode of agent can be determined according to the property of raw material by this area Conventional wisdom.

The present invention method in, described two weighted BMO spaces reaction zones one and only one be online it is specific It is meant that, when the first weighted BMO spaces reaction zone can not meet the feed needs or the first weighted BMO spaces of downstream hydrogenation treatment region The pressure drop of at least one catalyst bed reaches in reaction zone when there is hot spot in the pressure drop upper limit or catalyst bed, by first plus All reactors in hydrogen pretreatment reaction zone are cut out, while the reactor of the second weighted BMO spaces reaction zone is cut.When Two weighted BMO spaces reaction zones can not meet the feed needs or the second weighted BMO spaces reaction zone of downstream hydrogenation processing reaction zone In the pressure drop of at least one catalyst bed reach and occur hot spot in the pressure drop upper limit or catalyst bed and can not continue to operate When, protective agent and catalyst whole in all reactors are replaced after can stopping work with device.Can also be according to hydrotreating reaction The situation of catalyst activity cuts out the reactor of the second weighted BMO spaces reaction zone in area, while will replace protective agent and urged Reactor incision in first weighted BMO spaces reaction zone of agent, so circulation, until the catalyst in hydrotreating reaction area It can not meet running requirements.

There is no particular limitation for flow direction of the invention to raw material in hydrogenation protecting area and hydrotreating zone, weighted BMO spaces Each reactor in reaction zone and hydrotreating reaction area can be up-flow reactor or be downflow reactor.

In the prior art, in heavy oil hydroprocessing units according to Flow of Goods and Materials direction, despite the presence of the influence of cold hydrogen, still Low early and high after trend is generally presented in reaction temperature, i.e., in from start of run to the whole cycle in operating latter stage, hydrogenation is protected Protect a few class catalyst beds such as catalyst, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst Average reaction temperature is elevated successively.Meanwhile setting of the existing catalyst grade with system is with all anti-when operating latter stage Device is answered to reach synchronous inactivation, synchronously change for the purpose of agent.Therefore, in operation process, when first reactor pressure drop rise or When there is hot spot, or hydrogenation products cannot meet that needs horse back whole device out of service is to replace during downstream unit requirement Some catalyst.Catalyst in the hydrodesulfurization swum in such a case the lower and/or denitrification reactor also " has lost substantially It is living ".Therefore the operation cycle of package unit is limited be subject to first catalyst reactor service life.And even for adding Hydrogen protection uses the hydroprocessing technique of reactor handover operation（Such as CN1484684A and CN102453530A）For, it is a whole set of The service cycle of device is similarly subjected to the limitation of first catalyst reactor service life.

After substantial amounts of research has been carried out to existing hydrotreating method, present inventor is surprised to find that：It is existing In technology, after hydrotreater is stopped work because of hot spot and/or the pressure drop of hydrogenation protecting catalyst bed, device rear portion（Under Trip）Although the desulphurization catalyst and denitrification catalyst that use also have inactivated, but its deactivation cause is more because catalyst Caused by the metal that the aperture in duct is deposited blocks, and the metal of deposition is really and few inside catalyst duct.Make a concrete analysis of it Reason, applicant think：In the middle and later periods of device operating, the metal in feedstock oil " has penetrated " hydrogenation protecting catalyst and Tuo Jin Metal catalyst bed, and it has been directly entered the desulphurization catalyst and denitrification catalyst bed at rear portion.Due to desulphurization catalyst and/or The aperture of denitrification catalyst is smaller, the metal of removing cannot be introduced into inside duct so be deposited near catalyst aperture, So as to cause the inactivation of desulphurization catalyst and denitrification catalyst.In this condition, Hydrobon catalyst and/or hydrodenitrogeneration The inactivation of catalyst be not because catalyst carbon distribution in itself and caused by, but because feedstock oil penetrates hydrogenation protecting catalysis After agent bed and Hydrodemetalation catalyst bed so that more hydrodesulfurizations and/or the desulfurization of denitrification functions should be undertaken And/or denitrification catalyst is undertaken caused by the function of hydrodemetallization.Meanwhile designed for desulfurization, denitrogenation and/or take off originally , also cannot be real well due to the limitation of its catalyst pore structure after the catalyst of carbon residue undertakes partial hydrogenation demetalization function Existing demetalization function, while desulfurization, denitrogenation and/or the reduction of de- carbon residue ability are also created, and cause catalyst function Waste, so that the activity of hydrodesulfurization and/or hydrodenitrogenation catalyst cannot be fully utilized.

The present inventor has found that package unit can be divided into weighted BMO spaces reaction zone and hydrogenation by numerous studies Reaction zone is handled, wherein weighted BMO spaces reaction zone operates under of a relatively high reaction temperature, and hydrotreating reaction area is in phase To being operated under relatively low reaction temperature.The tenor of weighted BMO spaces reaction zone outlet material is controlled in technical solution first, Most of metal impurities i.e. in weighted BMO spaces reaction zone removes feedstock oil, only the metal of remaining a small amount of more difficult removing is miscellaneous Matter, while realize partial hydro-desulfurization.And weighted BMO spaces reaction zone reaction stream enter hydrotreating reaction area be Operated at relatively low temperature, i.e., carry out hydrodesulfurization and hydrogenation saturated reaction, such metal at relatively low temperature Impurity can be in the case where being not involved in reaction directly by desulphurization catalyst and/or denitrification catalyst, so as to avoid catalyst The permanent deactivation caused by metal deposit.Meet the feed needs of downstream unit by scheme optimization product.With it is existing Technology is compared, and method of the invention changes existing catalyst system and operator scheme, i.e., by the prior art according to logistics direction Low early and high after trend is presented in reaction temperature, changes into trend low after height before being presented according to logistics orienting response temperature, this hair Bright method can make full use of the activity of all catalyst, so as to increase the operational efficiency of device, improve its economy.The present invention Inventor complete the present invention on this basis.

Compared with prior art, the method have the advantages that：

1st, by the way that heavy oil hydroprocessing units are divided into weighted BMO spaces reaction zone and hydrotreating reaction area, in weighted BMO spaces Most of metal impurities in reaction zone removing material, make poison of the material to hydrotreating zone catalyst for entering hydrotreating zone Evil is greatly lowered, and can make full use of the activity of all catalyst in hydrotreating zone, compared with prior art, the operating of device Cycle can extend 30-100%, so as to add the operational efficiency of device, improve economy.

2nd, reactor is protected using switchable type in weighted BMO spaces reaction zone, substantially increases the demetalization energy of device Power, so as to process the raw material of tenor higher.

3rd, the most of metal impurities being stripped of due to weighted BMO spaces reaction zone in material so that hydrotreating reaction area The deactivation cause of middle desulphurization catalyst and/or denitrification catalyst is changed into only carbon deposit mistake from conventional metal deposit and coking deactivation It is living, so that desulphurization catalyst and denitrification catalyst can carry out regeneration treatment after using a cycle, greatly save and urge Agent buying expenses.

4th, weighted BMO spaces area uses liquid-phase hydrogenatin, on the one hand solves the purpose for reducing catalyst bed temperature rise, can have Effect avoids the generation of hot spot, at the same also significantly reduce between bed and/or between reactor quenching hydrogen injection rate, on the other hand pass through The recycle oil of hydrogenation is crossed so that part aromatic hydrocarbons obtains saturation, there is hydrogen supply, can inhibit coke formation, avoid catalyst from accumulating Charcoal inactivates, and then extends the service life of catalyst.

5th, weighted BMO spaces area is not provided with hydrogen gas circulating system, and reaction system is entrained into when largely being circulated by liquid-phase product Dissolved hydrogen come provide fresh feed carry out the required hydrogen of hydrogenation reaction, can eliminate catalyst wetting Effects of Factors and H in recycle hydrogen₂S and NH₃Influence, while also reduce single unit system circulation hydrogen system equipment investment.

It is 6th, of the invention by setting the first high-pressure separator between weighted BMO spaces reaction zone and hydrotreating reaction area, On the one hand significantly reducing the impurity such as hydrogen sulfide and ammonia in recycle oil, to the adverse effect of hydrogenation reaction, is greatly facilitated catalysis The progress of reaction, simultaneously because the diluting effect of recycle oil, is adapted to the raw material of processing high impurity content, improves technique mistake The adaptability of journey；On the other hand so that the impurity concentration such as hydrogen sulfide and ammonia is dropped into the material in hydrotreating reaction area It is low, and then the reaction temperature in hydrotreating reaction area is minimized, it is catalyzed so as to further extend in hydrotreating reaction area The service cycle of agent.

7th, the activity of the catalyst in hydrotreating reaction area is made full use of, improves the treating capacity of device, or is reduced Equipment investment.

Brief description of the drawings

Fig. 1 is the process flow diagram for the Heavy oil hydrogenation method that the present invention improves catalyst utilization.

Fig. 2 is the process flow diagram of comparative example 2-4.

Embodiment

The embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.

Attached drawing is the principle process schematic diagram of method provided by the present invention, some ancillary equipments in figure（Heat exchanger, pump Deng）Do not mark, but this is known for those of ordinary skill in the art.

A kind of flow of Heavy oil hydrogenation method for improving catalyst utilization provided by the present invention is as follows：

First come from the fresh feed residual oil of pipeline 8 and the new hydrogen from pipeline 22 and the first liquid being recycled back to through pipeline 15 production Thing enters mixer 24 and forms the molten hydrogen logistics of saturation together, and it is pre- that the molten hydrogen stream passes via line 23 of saturation and pipeline 10 enter the first hydrogenation In the reactor 1 for handling reaction zone, hydrodesulfurization and hydrodemetallization reaction are carried out in the presence of a catalyst, hydrogenation products are from the The top of reactor 1 of one weighted BMO spaces reaction zone enters the first high-pressure separator 5 through pipeline 9 and pipeline 13 and carries out gas-liquid point From separating obtained first hydrogen-rich gas 14 uses after isolating hydrogen after further treatment through compressor compresses Posterior circle, separation Gained the first product liquid part is recycled back to weighted BMO spaces area through pipeline 15, and another part is through pipeline 16 and comes from pipeline 25 New hydrogen and from pipeline 21 mixing hydrogen mixing after, in the reactor 3 and reactor 4 that sequentially enter hydrotreating reaction area, Hydrodemetallization, hydrodesulfurization and hydrodenitrogeneration reaction, reaction effluent are carried out in the presence of a catalyst enters the through pipeline 18 Two separators 6 carry out gas-liquid separation, and the separator generally includes high-pressure separator and low pressure separator, and separating obtained second is rich Hydrogen is extracted out through pipeline 20, and being pressurized Posterior circle through compressor 7 uses, and isolated second liquid is extracted out through pipeline 19 to be entered Downstream unit.

When the reactor 1 of the first weighted BMO spaces reaction zone can not meet feed needs or the reaction of downstream hydrogenation treatment region The pressure drop of at least one catalyst bed reaches in device 1 when there is hot spot in the pressure drop upper limit or catalyst bed, is cut out, and Cut the reactor 2 of the second weighted BMO spaces reaction zone（Material enters reactor 2 through pipeline 12, through 11 outflow reactor of pipeline 2）To continue to complete hydroprocessing processes, while the catalyst in the first weighted BMO spaces reaction zone reactor 1 is replaced, filled again It is stand-by to enter fresh catalyst.When the reactor 2 of the second weighted BMO spaces reaction zone can not meet downstream hydrogenation processing reaction zone The pressure drop of at least one catalyst bed reaches the pressure drop upper limit in feed needs or reactor 2 or the interior appearance of catalyst bed can not When continuing the hot spot of operation, cut out, while the reactor 1 for cutting the first weighted BMO spaces reaction zone is hydrogenated with to continue to complete Processing procedure, while the catalyst in the reactor 2 of the second weighted BMO spaces reaction zone is replaced, reload fresh catalyst and treat With.So circulation, the service life of the catalyst until reaching hydrotreating zone.

Limited below in conjunction with specific embodiment is further to the method for the present invention.Original used in embodiment and comparative example The property of material oil is listed in table 1, and the property of used catalyst is listed in table 2.In table 2, A is hydrogenation protecting catalyst, and B is the de- gold of hydrogenation Metal catalyst, C are Hydrobon catalyst, and D is hydrodenitrogeneration（Carbon residue converts）Catalyst.

1 raw material oil nature of table

2 catalyst property of table

Embodiment 1

According to the technological process described in Fig. 1, the first weighted BMO spaces that weighted BMO spaces reaction zone includes changeable operation react Area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone set a reactor 1, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series.According to Flow of Goods and Materials Direction, weighted BMO spaces reaction zone（It is online to only have a weighted BMO spaces reaction zone in operation process）It is filled with and urges in reactor Agent A, catalyst B and catalyst C, the admission space ratio of each catalyst is 2: 7: 1.Filled in hydrotreating reaction area reactor 3 There are catalyst B and catalyst C, the admission space ratio of two kinds of catalyst is 1: 9, and a loading catalyst D in reactor 4.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is high compared with hydrotreating zone, and specific reaction condition is shown in Table 3.Feedstock oil A is followed by mixer 24, reactor 1, the first high-pressure separator 5, reactor 3,4 and second separator of reactor 6, and control the metal of weighted BMO spaces reaction zone outlet effluent（Ni+V）Content is not higher than 12mg/g.At hydrogenated back end hydrogenation Manage reaction zone effluent in sulfur content be 0.20 weight %, nitrogen content 1688mg/g, carbon residue be 4.40 weight %, metal（Ni+ V）Content is 6.9mg/g.After operating 6 months, the reactor 1 of the first weighted BMO spaces reaction zone exports the metal of effluent（Ni+ V）Pressure drop of the content more than at least one catalyst bed in 12mg/g or reactor 1 reaches in the pressure drop upper limit or catalyst bed There is hot spot, cut out, and the reactor 2 for cutting the second weighted BMO spaces reaction zone continues to complete hydroprocessing processes （Feedstock oil A is followed by mixer 24, reactor 2, the first high-pressure separator 5, reactor 3, reactor 4 and second point at this time From device 6）, device still even running, generates oil quality and disclosure satisfy that downstream RFCC feed needs.When the second weighted BMO spaces are anti- The reactor 2 in area is answered to export the metal of effluent（Ni+V）Content is more than at least one catalyst bed in 12mg/g or reactor 2 The pressure drop of layer reaches in the pressure drop upper limit or catalyst bed when there is the hot spot that can not continue operation, is cut out, cut at the same time The reactor 1 of first weighted BMO spaces reaction zone continues to complete hydroprocessing processes, while to replace the second weighted BMO spaces anti- The catalyst in the reactor 2 in area is answered, it is stand-by to reload fresh catalyst.So circulation, the final device have operated 24 Month, stopped work since product quality is deteriorated, operating present invention device 1 and reactor 2 load and unload agent 2 times respectively.

Comparative example 1

According to the technological process described in Fig. 1, the first weighted BMO spaces that weighted BMO spaces reaction zone includes changeable operation react Area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone set a reactor 1, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series.According to Flow of Goods and Materials Direction, weighted BMO spaces reaction zone reactor（It is online to only have a reactor in operation process）In be filled with catalyst A, catalysis Agent B and catalyst C, the admission space ratio of each catalyst is 2: 7: 1.In hydrotreating reaction area reactor 3 equipped with catalyst B and Catalyst C, the admission space ratio of two kinds of catalyst is 1: 9, and a loading catalyst D in reactor 4.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is less than hydrotreating zone, and specific reaction condition is shown in Table 3.Feedstock oil A is followed by mixer 24, reactor 1, the first high-pressure separator 5, reactor 3,4 and second separator of reactor 6, and the metal of weighted BMO spaces reaction zone outlet effluent is not controlled（Ni+V）Content.Hydrogenated back end hydrogenation handles reaction zone stream Go out sulfur content in thing be 0.21 weight %, nitrogen content 1808mg/g, carbon residue be 4.56 weight %, metal（Ni+V）Content is 8.0mg/g.After operating 10 months, the pressure drop of at least one catalyst bed in the reactor 1 of the first weighted BMO spaces reaction zone Reach in the pressure drop upper limit or catalyst bed and hot spot occur, cut out, and cut the reaction of the second weighted BMO spaces reaction zone Device 2 continues to complete hydroprocessing processes（Feedstock oil A is followed by mixer 24, reactor 2, the first high-pressure separator at this time 5th, reactor 3,4 and second separator 6 of reactor）, device still even running, generation oil quality disclosure satisfy that downstream RFCC into Material requires.After switching reactor 2, device has operated 8 months again, is stopped work since product quality is deteriorated, the final device Operate 18 months.

Embodiment 2

According to the technological process described in Fig. 1, a weighted BMO spaces reaction zone is only set, is set in this weighted BMO spaces reaction zone A reactor 1 is put, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series, and weighted BMO spaces reaction zone Loaded catalyst accounts for the 36% of device catalyst total filling amount.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone reactor Catalyst A, catalyst B and catalyst C are filled with 1, the admission space ratio of three kinds of catalyst is 2: 6: 2.Hydrotreating reaction Catalyst B and catalyst C is housed, the admission space ratio of two kinds of catalyst is 3: 7, filling catalysis in reactor 4 in area's reactor 3 Agent C and catalyst D, the admission space ratio of two kinds of catalyst is 3: 7.The condition and result of the test of reactor hydrotreating are listed in table 2。

In operation process, the reaction temperature of weighted BMO spaces reaction zone is high compared with hydrotreating zone, and specific reaction condition is shown in Table 3.Feedstock oil A controls weighted BMO spaces reaction zone outlet effluent followed by reactor 1, reactor 3 and reactor 4 Metal（Ni+V）Content is not higher than 29mg/g.Sulfur content is 0.23 weight %, nitrogen in hydrogenated back end hydrogenation processing reaction zone effluent Content is 2186mg/g, carbon residue is 4.8 weight %, metal（Ni+V）Content is 8.7mg/g.After operating 12 months, due to product Degradation is stopped work, and the pressure drop of reactor 1 at this time has reached the 85% of the pressure drop upper limit.

Comparative example 2

According to the technological process described in Fig. 2, a weighted BMO spaces reaction zone is only set, is set in this weighted BMO spaces reaction zone A reactor 1 is put, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series, and weighted BMO spaces reaction zone Loaded catalyst accounts for the 24% of device catalyst total filling amount.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone reactor Catalyst A and catalyst B are filled with 1, the admission space ratio of two kinds of catalyst is 3: 7.In hydrotreating reaction area reactor 3 Equipped with catalyst B and catalyst C, the admission space ratio of two kinds of catalyst is 3: 7, loading catalyst C and catalyst in reactor 4 D, the admission space ratio of two kinds of catalyst is 2: 8.The condition and result of the test of hydrotreating are listed in table 2.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is less than hydrotreating zone, and specific reaction condition is shown in Table 3.Feedstock oil A does not control weighted BMO spaces reaction zone to export effluent followed by reactor 1, reactor 3 and reactor 4 Metal（Ni+V）Content.In hydrogenated back end hydrogenation processing reaction zone effluent sulfur content be 0.24 weight %, nitrogen content be 2276mg/g, carbon residue are 4. 85 weight %, metal（Ni+V）Content is 8.8mg/g.After operating 12 months, due to product quality Variation is stopped work, and the pressure drop of reactor 1 at this time has reached the 85% of the pressure drop upper limit.

Embodiment 3

According to the technological process described in Fig. 1, the first weighted BMO spaces that weighted BMO spaces reaction zone includes changeable operation react Area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone set a reactor 1, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series.According to Flow of Goods and Materials Direction, weighted BMO spaces reaction zone（It is online to only have a weighted BMO spaces reaction zone in operation process）It is filled with and urges in reactor Agent A, catalyst B and catalyst C, the admission space ratio of each catalyst is 3: 6: 1.Filled in hydrotreating reaction area reactor 3 There are catalyst B and catalyst C, the admission space ratio of two kinds of catalyst is 3: 7, loading catalyst C and catalyst D in reactor 4, The admission space ratio of two kinds of catalyst is 2: 8.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is high compared with hydrotreating zone, and specific reaction condition is shown in continuous Table 3.Feedstock oil B separates followed by mixer 24, reactor 1, the first high-pressure separator 5, reactor 3, reactor 4 and second Device 6, and control the metal of weighted BMO spaces reaction zone outlet effluent（Ni+V）Content is not higher than 20mg/g.Hydrogenated back end hydrogenation Handle reaction zone effluent in sulfur content be 0.21 weight %, nitrogen content 1406mg/g, carbon residue be 3.78 weight %, metal （Ni+V）Content is 9.2mg/g.After operating 3 months, the reactor 1 of the first weighted BMO spaces reaction zone exports the metal of effluent （Ni+V）Pressure drop of the content more than at least one catalyst bed in 20mg/g or reactor 1 reaches the pressure drop upper limit or catalyst bed There is hot spot in layer, cut out, and the reactor 2 for cutting the second weighted BMO spaces reaction zone continues to complete hydrotreating Journey（Feedstock oil B is followed by mixer 24, reactor 2, the first high-pressure separator 5, reactor 3, reactor 4 and second at this time Separator 6）, device still even running, generates oil quality and disclosure satisfy that downstream RFCC feed needs.When the second weighted BMO spaces The reactor 2 of reaction zone exports the metal of effluent（Ni+V）Content is more than at least one catalyst in 20mg/g or reactor 2 The pressure drop of bed reaches in the pressure drop upper limit or catalyst bed when there is the hot spot that can not continue operation, is cut out, cut at the same time Enter the reactor 1 of the first weighted BMO spaces reaction zone to continue to complete hydroprocessing processes, while replace the second weighted BMO spaces Catalyst in the reactor 2 of reaction zone, it is stand-by to reload fresh catalyst.So circulation, the final device have operated 12 A month, stopped work since product quality is deteriorated, operating present invention device 1 and reactor 2 load and unload agent 2 times respectively.

Comparative example 3

According to the technological process described in Fig. 2, a weighted BMO spaces reaction zone is only set, is set in this weighted BMO spaces reaction zone A reactor 1 is put, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series.According to Flow of Goods and Materials direction, Catalyst A and catalyst B are filled with weighted BMO spaces reaction zone reactor 1, the admission space ratio of two kinds of catalyst is 3: 7. Catalyst B and catalyst C is housed, the admission space ratio of two kinds of catalyst is 5: 5, reaction in hydrotreating reaction area reactor 3 Loading catalyst C and catalyst D in device 4, the admission space ratio of two kinds of catalyst is 4: 6.The condition and experiment knot of hydrotreating Fruit is listed in table 2.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is less than hydrotreating zone, and specific reaction condition is shown in continuous Table 3.Feedstock oil B does not control weighted BMO spaces reaction zone outlet outflow followed by reactor 1, reactor 3 and reactor 4 The metal of thing（Ni+V）Content.In hydrogenated back end hydrogenation processing reaction zone effluent sulfur content be 0.26 weight %, nitrogen content be 1687mg/g, carbon residue are 4. 23 weight %, metal（Ni+V）Content is 15.5mg/g.After operating 6 months, due to product quality Variation is stopped work, and the pressure drop of reactor 1 at this time has reached the 85% of the pressure drop upper limit.

Embodiment 4

According to the technological process described in Fig. 1, the first weighted BMO spaces that weighted BMO spaces reaction zone includes changeable operation react Area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone set a reactor 1, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series.According to Flow of Goods and Materials Direction, weighted BMO spaces reaction zone reactor（It is online to only have a reactor in operation process）In be filled with catalyst A, catalysis Agent B and catalyst C, the admission space ratio of each catalyst is 4: 5: 1.In hydrotreating reaction area reactor 3 equipped with catalyst B and Catalyst C, the admission space ratio of two kinds of catalyst is 1: 9, a loading catalyst D in reactor 4.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is high compared with hydrotreating zone, and specific reaction condition is shown in continuous Table 3.Feedstock oil C separates followed by mixer 24, reactor 1, the first high-pressure separator 5, reactor 3, reactor 4 and second Device 6, and control the metal of weighted BMO spaces reaction zone outlet effluent（Ni+V+Fe+Ca）Content is not higher than 10mg/g.It is hydrogenated Back end hydrogenation processing reaction zone effluent in sulfur content be 0.16 weight %, nitrogen content 2272mg/g, carbon residue be 3.48 weight %, Metal（Ni+V）Content is 4.6mg/g, and metal Ca contents are 0.5mg/g, and metal Fe contents are 0.2mg/g.After operating 4 months, The reactor 1 of first weighted BMO spaces reaction zone exports the metal of effluent（Ni+V+Fe+Ca）Content is more than 10mg/g or reaction The pressure drop of at least one catalyst bed, which reaches in the pressure drop upper limit or catalyst bed, in device 1 there is hot spot, is cut out, and cut Enter the reactor 2 of the second weighted BMO spaces reaction zone to continue to complete hydroprocessing processes（Feedstock oil C is followed by mixing at this time Device 24, reactor 2, the first high-pressure separator 5, reactor 3,4 and second separator 6 of reactor）, device still even running, Generation oil quality disclosure satisfy that downstream RFCC feed needs.When the reactor 2 of the second weighted BMO spaces reaction zone exports effluent Metal（Ni+V+Fe+Ca）Pressure drop of the content more than at least one catalyst bed in 10mg/g or reactor 2 reaches in pressure drop When occurring the hot spot that can not continue operation in limit or catalyst bed, cut out, while cut the reaction of the first weighted BMO spaces The reactor 1 in area continues to complete hydroprocessing processes, while replaces urging in the reactor 2 of the second weighted BMO spaces reaction zone Agent, it is stand-by to reload fresh catalyst.So circulation, the final device have operated 16 months, since product quality is deteriorated Stopped work, operating present invention device 1 and reactor 2 load and unload agent 2 times respectively.

Comparative example 4

According to the technological process described in Fig. 2, a weighted BMO spaces reaction zone is only set, is set in this weighted BMO spaces reaction zone A reactor 1 is put, hydrotreating reaction area includes the reactor 3 and reactor 4 being arranged in series.According to Flow of Goods and Materials direction, Catalyst A and catalyst B are filled with weighted BMO spaces reaction zone reactor 1, the admission space ratio of two kinds of catalyst is 4: 6. Catalyst B and catalyst C is housed, the admission space ratio of two kinds of catalyst is 1: 9, reaction in hydrotreating reaction area reactor 3 Loading catalyst C and catalyst D in device 4, the admission space ratio of two kinds of catalyst is 1: 9.The condition and experiment knot of hydrotreating Fruit is listed in table 2.

In operation process, the reaction temperature of weighted BMO spaces reaction zone is less than hydrotreating zone, and specific reaction condition is shown in continuous Table 3.Feedstock oil C does not control weighted BMO spaces reaction zone outlet outflow followed by reactor 1, reactor 3 and reactor 4 The metal of thing（Ni+V+Fe+Ca）Content.Sulfur content is 0.21 weight % in hydrogenated back end hydrogenation processing reaction zone effluent, nitrogen contains It is 3.98 weight %, metal to measure as 2936mg/g, carbon residue（Ni+V）Content is 6.3mg/g, and metal Ca contents are 1.8mg/g, gold It is 0.5mg/g to belong to Fe contents.After operating 8 months, since the pressure drop of reactor 1 reaches the pressure drop upper limit, device is forced to stop work.

The condition and result of the test of 3 hydrotreating of table

	Embodiment 1	Comparative example 1	Embodiment 2	Comparative example 2
					Feedstock oil	Feedstock oil A	Feedstock oil A	Feedstock oil A	Feedstock oil A
Pretreating zone operator scheme	Switching	Switching	Do not switch	Do not switch
					Process conditions
Hydrogen dividing potential drop, MPa	14.5	14.5	14.5	14.5
					Reaction temperature, DEG C
Reactor 1	390	370	385	373
					Reactor 2	390	370	-	-
Reactor 3	375	380	375	379
					Reactor 4	377	388	378	385
CAT	380	380	380	380
					Weighted BMO spaces area volume space velocity, h^-1	0.93	0.93	0.56	0.83
Hydrotreating zone volume space velocity, h^-1	0.28	0.28	0.31	0.26
					Weighted BMO spaces area hydrogen to oil volume ratio, Nm³/m³	700	700	700	700
Hydrotreating zone liquid phase circulation ratio, %	0.3:1	0.3:1	-	-
					Reaction generation oil nature
Sulphur, weight %	0.2	0.21	0.23	0.24
					Nitrogen, mg/g	1688	1808	2186	2276
Carbon residue, weight %	4.40	4.56	4.8	4.85
					Nickel+vanadium, mg/g	6.9	8	8.7	8.8
Calcium, mg/g
					Iron, mg/g
Service cycle, the moon	24	18	12	12
					Reactor 1 fills agent number, secondary	2	1	1	1
Reactor 2 fills agent number, secondary	2	1	-	-
					Reactor 3 and 4 fills agent number, secondary	1	1	1	1

The condition and result of the test of 3 hydrotreating of continued

	Embodiment 3	Comparative example 3	Embodiment 4	Comparative example 4
					Feedstock oil	Feedstock oil B	Feedstock oil B	Feedstock oil C	Feedstock oil C
Pretreating zone operator scheme	Switching	Do not switch	Switching	Do not switch
					Process conditions
Hydrogen dividing potential drop, MPa	14.5	14.5	14.5	14.5
					Reaction temperature, DEG C
Reactor 1	390	380	390	370
					Reactor 2	390	-	390	-
Reactor 3	375	384	375	380
					Reactor 4	377	390	377	386
CAT	380	385	380	380
					Weighted BMO spaces area volume space velocity, h^-1	1.14	0.83	1.29	0.83
Hydrotreating zone volume space velocity, h^-1	0.28	0.26	0.28	0.26
					Weighted BMO spaces area hydrogen to oil volume ratio, Nm³/m³	700	700	700	700
Hydrotreating zone liquid phase circulation ratio, %	0.6:1	-	0.8:1	-
					Reaction generation oil nature
Sulphur, weight %	0.21	0.26	0.16	0.21
					Nitrogen, mg/g	1406	1687	2272	2936
Carbon residue, weight %	3.78	4.23	3.48	3.98
					Nickel+vanadium, mg/g	9.2	15.5	4.6	6.3
Calcium, mg/g			0.5	1.8
					Iron, mg/g			0.2	0.5
Service cycle, the moon	12	6	16	8
					Reactor 1 fills agent number, secondary	2	1	2	1
Reactor 2 fills agent number, secondary	2	-	2	-
					Reactor 3 and 4 fills agent number, secondary	1	1	1	1

In order to further investigate influence of the technology to hydrotreating reaction area catalyst of the present invention, respectively to embodiment 1, Catalyst C and catalyst D after comparative example 1, embodiment 2 and the operating of comparative example 2 are dissected, and the results are shown in Table 4 and table 5.

4 catalyst C of table operatings are front and rear to dissect result

	Specific surface area, m²·g^-1	Pore volume, cm³·g^-1	Average pore size, nm	Carbon deposition quantity, g/100mL	Metal deposition capability, g/100mL
						Fresh dose	180.0	0.55	12.2	-	-
Deactivator
						Embodiment 1	110.2	0.2	7.3	19.88	-
Comparative example 1	115.2	0.22	7.6	18.28	-
						Embodiment 2	124.1	0.29	9.3	10.26	-
Comparative example 2	125.2	0.28	8.9	12.31	-
						Regenerative agent
Embodiment 1	168.7	0.49	11.6	0.08	1.29
						Comparative example 1	148.9	0.41	11.0	0.2	4.39
Embodiment 2	170.1	0.50	11.8	0.12	2.23
						Comparative example 2	145.3	0.38	10.5	0.26	6.11

5 catalyst D of table dissects result

	Specific surface area, m²·g^-1	Pore volume, cm³·g^-1	Average pore size, nm	Carbon deposition quantity, g/100mL	Metal deposition capability, g/100mL
						Fresh dose	225.0	0.48	8.5	-	-
Deactivator
						Embodiment 1	117.7	0.16	5.4	25.96	-
Comparative example 1	122.6	0.17	5.5	24.38	-
						Embodiment 2	129.2	0.21	6.5	15.36	-
Comparative example 2	130.1	0.20	6.1	18.24	-
						Regenerative agent
Embodiment 1	215.8	0.44	8.2	0.17	1.07
						Comparative example 1	204.8	0.41	8.0	0.34	2.73
Embodiment 2	217.2	0.45	8.3	0.22	1.45
						Comparative example 2	188.4	0.36	7.6	0.44	4.10

As seen from the above analysis, by varying catalyst system and operator scheme, i.e., by the prior art according to logistics direction Low early and high after trend is presented in reaction temperature（Comparative example 2）, change into low after height before being presented according to logistics orienting response temperature Trend（Embodiment 2）, while product quality is ensured, the activity of all catalyst can be made full use of, due to being hydrogenated with pre- place Reason reaction zone is stripped of most of metal impurities in material so that desulphurization catalyst and/or denitrogenation in hydrotreating reaction area The deactivation cause of catalyst is effectively carried from being changed into only coking deactivation using the metal deposit and coking deactivation of existing process technology The high utilization rate of desulphurization catalyst and/or denitrification catalyst, while also so that desulphurization catalyst and denitrification catalyst can make With regeneration treatment is carried out after a cycle, reuse, saved catalyst buying expenses, improved economy, when hydrogenation is pre- Handle reaction zone and carry out changeable operation（Embodiment 1）Afterwards, the advantage of the method for the present invention is more obvious, can greatly increase device The cycle of operation.

Further, since the sulfur content, carbon residue and tenor in this technology product are low compared with existing process technology, this The not only product quality of positive influences downstream RFCC devices, but also because reducing the tenor in RFCC chargings, can be significantly The catalyst agent consumption of RFCC devices is reduced, additional economic income is brought to enterprise.

Claims

1. a kind of Heavy oil hydrogenation method for improving catalyst utilization, including herein below：

（1）At least one weighted BMO spaces reaction zone and a hydrotreating reaction area are provided；Bag in weighted BMO spaces reaction zone Hydrogenation protecting catalyst and Hydrodemetalation catalyst are included, Hydrobon catalyst is included in hydrotreating reaction area and hydrogenation is de- Nitrogen catalyst；

2. in accordance with the method for claim 1, it is characterised in that step（2）The average response temperature of weighted BMO spaces reaction zone Degree is compared with step（3）The average reaction temperature in hydrotreating reaction area is 5~40 DEG C high.

3. in accordance with the method for claim 2, it is characterised in that inconsiderate（2）The average response temperature of weighted BMO spaces reaction zone Degree is compared with step（3）The average reaction temperature in hydrotreating reaction area is 10~30 DEG C high.

4. according to the method described in claim 1 or 2, it is characterised in that step（1）It is middle that more than two weighted BMO spaces are provided Reaction zone, which is usually arranged in parallel, the reaction zone of changeable operation.

5. in accordance with the method for claim 3, it is characterised in that further include step（6）, when one of weighted BMO spaces are anti- After answering area to meet service requirement, it is cut out into reaction process, and second weighted BMO spaces reaction zone is cut into technique stream Cheng Zhong, the weighted BMO spaces reaction zone cut out can carry out the displacement of catalyst, that is, draw off the old catalyst of inactivation, reload Fresh and/or regenerated catalyst.

6. in accordance with the method for claim 4, it is characterised in that the weighted BMO spaces reaction zone cannot meet service requirement Refer to：The effluent of weighted BMO spaces reaction zone can not meet feed needs or the weighted BMO spaces reaction of downstream hydrogenation treatment region The pressure drop of at least one catalyst bed, which reaches in the pressure drop upper limit or catalyst bed, in area there is hot spot.

7. in accordance with the method for claim 5, it is characterised in that the charging that can not meet downstream hydrogenation processing reaction zone Required standard is, the tenor in weighted BMO spaces reaction zone effluent liquid has exceeded between the μ g/g of 8 μ g/g~50 Any number；The pressure drop upper limit designs 0.4~0.8 times of maximum pressure drop for reactor；The hot spot refers at least one Radial temperature difference in a catalyst bed reaches 15~50 DEG C.

8. in accordance with the method for claim 5, it is characterised in that the free topped crude of heavy oil feedstock grease separation, oil One group of material that the hydro carbons for the high asphalt content that residual oil, oil-sand, pitch, shale oil, liquefaction coal or reclaimed oil obtain is formed；Weight The tenor of oily feedstock oil is more than 30mg/g.

9. method in accordance with claim, it is characterised in that the content of nickel+vanadium is more than in the heavy oil feedstock oil 60mg/g, and/or iron content are more than 10mg/g, and/or calcium content is more than 10mg/g.

10. in accordance with the method for claim 1, it is characterised in that the property of the Hydrodemetalation catalyst is, to urge On the basis of the gross weight of agent, molybdenum and/or tungsten and using the content that oxide is counted as 0.5~15 weight %, the content of cobalt and/or nickel For 0.3~8 weight %, surplus is alumina support；The alumina support is a kind of alumina support in bimodal hole, its Pore volume is 0.5~2.0 ml/g, and specific surface area is 120~350 meters²/ gram, aperture accounts for total pore volume in 10~30 nanometers of pore volume 30~90%, aperture accounts for total pore volume 10~50% in 100~2000 nanometers of pore volume, and bore dia is less than 10 nanometers, in 30-100 The sum of pore volume between nanometer and more than 2000 nanometers accounts for total pore volume below 20%.

11. in accordance with the method for claim 1, it is characterised in that in weighted BMO spaces reaction zone, hydrogenation protecting catalyst Admission space ratio with Hydrodemetalation catalyst is 5:95~95:5.

12. in accordance with the method for claim 1, it is characterised in that in weighted BMO spaces reaction zone, Hydrobon catalyst Loadings are 5v%~30v% of Hydrodemetalation catalyst loadings.

13. in accordance with the method for claim 1, it is characterised in that the property of the Hydrobon catalyst is, with catalysis On the basis of the gross weight of agent, molybdenum and/or tungsten and using the content that oxide is counted as 10~25 weight %, the content of cobalt and/or nickel is 1 ~6 weight %, surplus are alumina support.

14. in accordance with the method for claim 1, it is characterised in that the property of the hydrodenitrogenation catalyst is, with catalysis On the basis of the gross weight of agent, molybdenum and/or tungsten are using the content that oxide is counted as 12~30 weight %, and cobalt and/or nickel are in terms of oxide Content be 3~12 weight %, surplus is alumina support；The pore volume of the aluminium oxide is not less than 0.35 ml/g, compares surface Product is 150~350 meters²/ gram, aperture accounts for total pore volume 40~75% in 6~15 nanometers of pore volume.

15. according to any methods of claim 1-3, it is characterised in that the reaction condition of weighted BMO spaces reaction zone is, Reaction pressure is 5MPa~35MPa, and average reaction temperature is 340 DEG C~430 DEG C, and volume space velocity is 0.1h during liquid^-1~5.0h^-1, Liquid phase circulation mass ratio is 0.1:1~10:1.

16. in accordance with the method for claim 1, it is characterised in that in the hydrotreating reaction area, hydrodesulfurization catalytic The admission space of agent and hydrodenitrogenation catalyst ratio is 20:80~80:20.

17. according to any methods of claim 1-3, it is characterised in that the reaction condition in hydrotreating reaction area is, instead It is 5MPa~35MPa to answer pressure, and average reaction temperature is 320 DEG C~420 DEG C, and volume space velocity is 0.1h during liquid^-1~5.0h^-1, hydrogen Oil volume ratio is 200~1500.

18. in accordance with the method for claim 1, it is characterised in that the weighted BMO spaces reaction zone set one or Multiple hydrogenation protecting reactors, each hydrogenation protecting reactor is at least provided with a hydrogenation protecting catalyst bed.

19. in accordance with the method for claim 1, it is characterised in that contain the de- gold of hydrogenation in the hydrotreating reaction area Metal catalyst, the loadings of Hydrodemetalation catalyst usually account for the 5v% of loaded catalyst in hydrotreating reaction area~ 30v%。

20. in accordance with the method for claim 1, it is characterised in that de- containing hydrogenation in the weighted BMO spaces reaction zone Sulfur catalyst, the loadings of Hydrobon catalyst account for 0v%~30v% of loaded catalyst in pretreatment reaction area.