CN206872743U - A kind of hydrocarbon ils pretreatment unit and a kind of hydrocarbon oil hydrogenation processing system - Google Patents
A kind of hydrocarbon ils pretreatment unit and a kind of hydrocarbon oil hydrogenation processing system Download PDFInfo
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- CN206872743U CN206872743U CN201720015252.0U CN201720015252U CN206872743U CN 206872743 U CN206872743 U CN 206872743U CN 201720015252 U CN201720015252 U CN 201720015252U CN 206872743 U CN206872743 U CN 206872743U
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Abstract
Hydrocarbon oil hydrogenation processing technology field is the utility model is related to, discloses a kind of hydrocarbon ils pretreatment unit, the device includes tunica fibrosa haptoreaction unit, mixed cell and pre-hydrotreating unit.The invention also discloses a kind of hydrocarbon oil hydrogenation processing system, the system includes hydrocarbon oil crude material pretreatment unit and main hydrogenation plant, and the main hydrogenation plant is used to carry out hydrotreating to the product of pretreatment unit output.According to hydrocarbon ils pretreatment unit of the present utility model, the metal impurities and the content of mechanical admixture that can be effectively reduced in hydrocarbon ils, especially suitable for being pre-processed to inferior raw material as residual oil, so as to effectively suppress the rise of residue fixed-bed hydrogenation reactor beds pressure drop, extend the stable operation cycle of residue fixed-bed hydrogenation reactor, and the safety in operation of device is improved, reduce the operating cost of device.
Description
Technical field
Hydrocarbon oil hydrogenation processing technology field is the utility model is related to, specifically, a kind of hydrocarbon ils is the utility model is related to and locates in advance
Device is managed, the utility model further relates to a kind of hydrocarbon oil hydrogenation processing system.
Background technology
In recent years, with the aggravation of crude oil heaviness, in poor quality trend, the increase of crude oil difficulty of processing, light oil yield
Reduce so that the focus of global Oil Refining Industry is transferred to processing of heavy oil and made full use of up.
Residual hydrogenation technology directly obtains the excellent lightweight production of some properties because it can substantially improve heavy oil property
Product, total liquid yield is high, is received significant attention as the new technology of a kind of heavy oil deep processing and heavy oil lighting.Due to slag
Objectionable impurities and the undesirable components such as most of sulphur of crude oil, nitrogen, most metal, colloid, asphalitine have been remained in oil,
Its mean molecule quantity is big, viscosity is high, density is big, carbon residue is high, hydrogen-carbon ratio is low, therefore is fixed to residual oil raw material at bed hydroprocessing
During reason, the metal impurities (such as Fe, Ca, V, Ni) in residual oil raw material, particularly Fe and mechanical admixture are easy to sink
In space of the product between the surface of catalyst and catalyst granules, one side blocking catalyst aperture, catalyst is caused to lose
It is living, on the other hand cause beds pressure drop quickly to raise, make device frequent shutdowns with more catalyst changeout, so as to drop significantly
The low service efficiency of commercial plant and the life-span of catalyst, economic benefit reduce.
Industrial production confirms that residual hydrogenation fixed bed reactor catalyst bed pressure drop rises mainly due to residual oil raw material
In mechanical admixture (Fe, Ca, Na, greasy filth and iron rust etc.), the polymer such as coke powder and colloid, asphalitine enter reactor,
Fouling is deposited in beds, partly free radical or non-free contracting occur at high temperature for the complex mixture with coke forming property
Close reaction, the generation for aggravating this condensation reaction can be catalyzed again by being deposited on the metal of catalyst surface, make beds green coke,
Block.
In residue fixed-bed hydrogenation process, catalyst is in addition to coking and deactivation, the poisoning effect of metallic sodium in raw material, again
The deposition of metal (mainly Ni and V) sulfide and the principal element for causing it to inactivate, and this inactivation is irreversible.
Coking and it is irreversible poison, inactivate caused by metal deposit, make residual oil hydrocatalyst service life very short, one
As only time of 6 months to 1 year, and be unable to regeneration.Therefore, how to prevent metal deposit, coking and cause to be catalyzed
Agent activity reduces, reaction bed blocks, and extends the service cycle of residual hydrogenation equipment, is just needed badly into the development of residual hydrogenation technology
The key problem of solution.
CN1393515A discloses a kind of heavy resid hydrotreating method, this method in former residual hydrogenation reaction system
One or more and former bed identical beds are set up in the beds of one reactor, while each newly-increased
Beds on open up a new charging aperture, gone into operation in device and use the throat-fed of raw material initial stage, when first anti-
Answer device beds pressure drop to increase to the pressure drop upper limit, use next throat-fed instead successively, wherein, raw feed mouth enters with original
The operating condition of material mouth raw material is identical.It is however a drawback of the method that equipment investment and loaded catalyst are added, and
Charging aperture is set up on high-tension apparatus, reduces the safety in operation of device.
CN102311786A discloses a kind of process for hydrogenating residual oil of extension fixture service cycle, including：It is being hydrogenated with
Under conversion condition, the mixture of feed residue and hydrogen passes through at least one hydrogenation reaction containing catalyst for hydrotreatment of residual oil
Device；In the Steady-state inactivation stage of catalyst for hydrotreatment of residual oil, feed residue is switched into the distillate containing vulcanizing agent, and make
The cut oil-hydrogen mixture carries out wet method vulcanization, the note sulfur content vulcanized every time back through described hydrogenation reactor
For the 1.0%-5.0% of total catalyst weight, normal technological process and feedstock oil are switched to again after noting sulphur；Described sulphur
Change number to be 1500-3000 hours per the interval time vulcanized twice at least once.But it this method increase device
Operating Complexity, using excessive high-temperature high pressure valve, reduce the security of device.
CN1335368A discloses a kind of weight, process for hydrogenating residual oil, including：Weight, residual oil raw material first pass around pre- place
Reason, is then mixed with hydrogen, after reaction temperature needed for heating reaches, is reacted into residual hydrogenation reaction system,
Reactant is separated into piece-rate system, wherein, described preprocessing process is that heavy resid raw material reaches required by heat exchange
After temperature, filtered into the adsorption filtration system equipped with absorption filter agent, the operating condition of the adsorption filtration is：Temperature
100-320 DEG C, volume space velocity is 2.0-8.5h during liquid-1, operating pressure 0.1-0.3MPa.But there is the use of adsorbent in the method
Amount is big and the shortcomings that frequent is replaced in shut-down.
In summary, existing residue fixed-bed hydrogenation technique still has metal impurities and dirty thing deposition so that catalysis
The rise of agent bed pressure drop is fast, device service cycle short deficiency.
Utility model content
The purpose of this utility model is to provide a kind of hydrocarbon ils pretreatment unit, using the device to hydrocarbon ils (particularly residual oil)
Pre-processed, the metal impurities and other machinery impurity content that can be effectively reduced in hydrocarbon ils, pretreated hydrocarbon ils is made
For the feedstock oil of fixed bed hydrogenation handling process, it can effectively suppress beds pressure drop and raise too fast deficiency, extend dress
The stable operation cycle put.
According to one side of the present utility model, the utility model provides a kind of hydrocarbon ils pretreatment unit, the device
Including tunica fibrosa haptoreaction unit, mixed cell and pre-hydrotreating unit,
The tunica fibrosa haptoreaction unit includes at least one tunica fibrosa haptoreaction subelement and at least one oil
Moisture ion unit, the tunica fibrosa haptoreaction subelement are used to receive hydrocarbon oil crude material, and by the hydrocarbon oil crude material with taking off gold
Belong to agent contact, the water-oil separating subelement is used to the liquid mixture of tunica fibrosa haptoreaction subelement output carrying out profit
Separation, respectively obtains oil phase and aqueous phase；
The mixed cell is used to mix the oil phase that water-oil separating subelement exports with hydrogen, and the mixed cell includes
At least one blender, the blender include at least one gas passage and at least one fluid passage, the gas passage
Abutted between the fluid passage by a component, the component at least partially has a porose area, and described to have porose area to have flat
Equal aperture is the through hole of nano-scale, and the gas passage is used to accommodate the hydrogen, and the fluid passage is described for accommodating
Oil phase, the hydrogen can be injected into the oil phase by the average pore size for the through hole of nano-scale；
The pre-hydrotreating unit includes liquid phase pre-hydrogenator, for the gas-liquid mixture for exporting mixed cell
Contacted with the catalyst that catalytic hydrodemetallation acts on, carry out liquid phase pre-hydrotreating reaction.
According to second of the present utility model aspect, the utility model provides a kind of hydrocarbon oil hydrogenation processing system, and this is
System includes hydrocarbon oil crude material pretreatment unit and main hydrogenation plant, and the main hydrogenation plant is used for the production to pretreatment unit output
Thing carries out hydrotreating, wherein, the hydrocarbon oil crude material pretreatment unit is the pretreatment described in the utility model one side
Device.
According to hydrocarbon ils pretreatment unit of the present utility model, the metal impurities that can be effectively reduced in hydrocarbon ils and machinery are miscellaneous
The content of matter, especially suitable for being pre-processed to inferior raw material as residual oil, add so as to effectively suppress residue fixed-bed
The rise of hydrogen reactor beds pressure drop, extends the stable operation cycle of residue fixed-bed hydrogenation reactor, and improves dress
The safety in operation put, reduce the operating cost of device.
Brief description of the drawings
Accompanying drawing is to be further understood for providing to of the present utility model, and a part for constitution instruction, and following
Embodiment be used to explain the utility model together, but do not form to limitation of the present utility model.
Fig. 1 is used for the structural representation for illustrating the mixing arrangement that the utility model preferably uses.
Fig. 2 is used to illustrate a kind of preferred embodiment according to hydrocarbon oil hydrogenation processing system of the present utility model.
Description of reference numerals
1：For abutting gas passage and the component of fluid passage
2：Housing 3：Gas material entrance
4：Liquid material entrance 5：Liquid material exports
201：Hydrocarbon ils 203：The metal remover aqueous solution
204：Tunica fibrosa contact reactor 205：Gun barrel
206：Solid sediment 207：Aqueous phase
208：Blender 209：Hydrogen
210：Pre-hydrogenator 211：Product liquid
212：Main hydrogenation reactor 213：Recycle hydrogen
221：Pump 222：Pump
Embodiment
Specific embodiment of the present utility model is described in detail below.It is it should be appreciated that described herein
Embodiment is merely to illustrate and explained the utility model, is not limited to the utility model.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to one side of the present utility model, the utility model provides a kind of hydrocarbon ils pretreatment unit, the device
Including tunica fibrosa haptoreaction unit, mixed cell and pre-hydrotreating unit.
The tunica fibrosa haptoreaction unit includes at least one tunica fibrosa haptoreaction subelement and at least one oil
Moisture ion unit, the tunica fibrosa haptoreaction subelement are used to receive hydrocarbon oil crude material, and by the hydrocarbon oil crude material with taking off gold
Belong to agent contact, the water-oil separating subelement is used to the liquid mixture of tunica fibrosa haptoreaction subelement output carrying out profit
Separation, respectively obtains oil phase and aqueous phase.
In the tunica fibrosa haptoreaction unit, the quantity of the tunica fibrosa haptoreaction subelement can be one or two
More than individual.When the quantity of the tunica fibrosa haptoreaction subelement is two or more, water-oil separating subelement can be shared, i.e.,
The liquid mixture that each tunica fibrosa haptoreaction subelement exports is respectively fed to carry out water-oil separating in water-oil separating subelement；
The water-oil separating subelement suitable with tunica fibrosa haptoreaction number sub-cells, each tunica fibrosa haptoreaction can also be set
The corresponding water-oil separating subelement of unit.
The tunica fibrosa haptoreaction subelement includes at least one tunica fibrosa contact reactor, and the tunica fibrosa contact is anti-
Device is answered from top to bottom to include feed end successively and be provided with filametntary mass transfer space.
The feed end of the tunica fibrosa contact reactor is used to receive hydrocarbon ils and metal remover, and by hydrocarbon ils and metal remover
It is sent into mass transfer space and is contacted.The hydrocarbon ils and the metal remover can be connect by same charging aperture into tunica fibrosa
Touch in reactor.In a preferred embodiment, the feed end is provided with hydrocarbon oil feed mouth and metal remover charging aperture,
The hydrocarbon oil feed mouth is used to receive the hydrocarbon ils, and the metal remover charging aperture is used to receive the metal remover.
From the further hydrocarbon ils improved into mass transfer space and the mixing uniformity of metal remover, so as to improve demetalization effect
The angle of rate is set out, and in the tunica fibrosa contact reactor, is provided with least between the charging aperture and the mass transfer space
The filament that one fluid distributor, the hydrocarbon ils and the metal remover are flowed into mass transfer space via the fluid distributor
Surface.The pattern of the fluid distributor is not particularly limited, and its instantiation can include but is not limited to hole flow pattern
Device and overflow type distributor.The quantity of the fluid distributor can be one, or two or more.Preferably, it is described
Fluid distributor is two or more, and two or more fluid distributor is is connected in series, i.e., fluid passes sequentially through fluid distributor.
In the mass transfer space set filament boundling, into mass transfer space hydrocarbon ils and metal remover in filament surface
Sprawl and flow through filament surface, cause metal remover and the metal ion haptoreaction in hydrocarbon ils in the process, remove hydrocarbon
Metal ion in oil.The filametntary material can depending on the species of hydrocarbon ils and metal remover, be resistant to hydrocarbon ils and
Metal remover corrosion is defined.Usually, the filament can be wire and/or nonmetal wire.Specifically, the filament
The one kind that can be but be not limited in stainless steel wire, carbon steel wire, glass fiber, Fypro silk and polyester fiber silk
Or two or more combination.
The filametntary diameter is not particularly limited, and can be conventional selection.Usually, the filametntary diameter can
Think 1-10mm, preferably 3-6mm.
The water-oil separating subelement is used to receive the liquid mixture from the outflow of tunica fibrosa haptoreaction subelement, and will
The liquid mixture carries out water-oil separating, respectively obtains oil phase and aqueous phase.
The water-oil separating subelement can use common various separation methods that tunica fibrosa haptoreaction subelement is defeated
The liquid mixture gone out is separated.Specifically, the water-oil separating subelement, which can use, centrifuges, in standing separation
One or more kinds of combinations carries out water-oil separating.As a preferable example, the water-oil separating subelement includes oil
Water separation tank, come from tunica fibrosa haptoreaction subelement liquid mixture enter gun barrel in carry out standing separation,
It is divided into oil phase and aqueous phase, and oil phase and aqueous phase is exported respectively.
The water-oil separating subelement can be arranged on the inside of tunica fibrosa contact reactor, can also be arranged on tunica fibrosa
The outside of contact reactor.
In one embodiment, the water-oil separating subelement is arranged on the inside of tunica fibrosa contact reactor.At this
In embodiment, storage tank can be set in the bottom of tunica fibrosa contact reactor, outlet is set in the bottom of storage tank, alternatively existed
The top of the storage tank sets outlet.The storage tank connects with mass transfer space, straight from the liquid mixture of filament end outflow
Tap into and water-oil separating is carried out in the storage tank, turn into oil reservoir and water layer, respectively by being arranged on going out for reservoir bottom or sidepiece
Mouthful discharge, can be by water layer by being arranged on bottom or the sidepiece of the storage tank when being also provided with the top of storage tank outlet
Outlet discharge, oil reservoir are then produced by the outlet on the top for being arranged on the storage tank.In this embodiment, water-oil separating is single
Depending on quantity of the quantity of member with tunica fibrosa contact reactor, i.e., each tunica fibrosa contact reactor sets water-oil separating
Unit.
In another embodiment, the water-oil separating subelement is arranged on the outside of tunica fibrosa contact reactor.
In the embodiment, discharge end is set in the bottom of tunica fibrosa contact reactor and for connecting tunica fibrosa contact reactor
Discharge end and the feed end of water-oil separating subelement transport pipeline, the discharge end is used to be flowed out by filametntary end
Liquid mixture send out tunica fibrosa contact reactor, and be sent into transport in pipeline, the liquid mixture is transported by described
Pipeline and enter water-oil separating subelement in carry out water-oil separating.In this embodiment, the quantity of water-oil separating subelement can
Think one, can also be depending on the quantity of tunica fibrosa contact reactor, you can shared with multiple tunica fibrosa contact reactors
One water-oil separating subelement, can also tunica fibrosa contact reactor one water-oil separating subelement is set, such as：In fibre
When the quantity for tieing up film haptoreaction subelement is two or more, it can be set in the downstream of each tunica fibrosa haptoreaction subelement
Water-oil separating subelement.
The mixed cell is used to mix the oil phase that water-oil separating subelement exports with hydrogen, and obtained gas-liquid is mixed
Charging of the compound as pre-hydrotreating unit.
The mixed cell includes at least one blender, and the blender includes at least one gas passage and at least one
Individual fluid passage, abutted between the gas passage and the fluid passage by a component, the component is at least partially
There is porose area, the through hole for having porose area that there is average pore size to be nano-scale (hereinafter also referred to as nano-pore), the gas leads to
Road is used to accommodate the hydrogen, and the fluid passage is used to accommodate the oil phase, and the hydrogen can pass through the average pore size
It is injected into for the through hole of nano-scale in the oil phase.Now, even if the Partial Liquid Phase by pre-hydrogenator output is not produced
Thing is circulated, and enough hydrogen can be also provided for hydrogenation reaction, so as to effectively improve the effective treating capacity of pre-hydrogenator, and
And more preferable pre-hydrotreating reaction effect can be obtained.
In the utility model, term " fluid passage " is the space for referring to accommodate hydrocarbon ils；Term " gas passage " refers to
The space of hydrogen can be accommodated.
The average pore size of the nano-pore is not more than 1000nm, if average pore size is 1nm to 1000nm.It is highly preferred that institute
The average pore size for stating nano-pore is 30nm to 1000nm.It is further preferred that the average pore size of the nano-pore be 30nm extremely
800nm, such as 50nm to 500nm.The average pore size is determined using ESEM method.
The component can be the common element that can abut fluid passage and gas passage.Specifically, the component can
Think combinations more than one or both of perforated membrane, porous plate and void channels.
The void channels refer to that the wall of passage is porous.The inner surface of the void channels and/or outer surface can
To adhere to perforated membrane, the aperture of the through hole on pipeline can be so adjusted, such as：Through hole on the wall of the pipeline can
Think micron openings, the through hole being attached on the perforated membrane on the inner surface and/or outer surface of the pipeline can be with nano-pore, this
In utility model, the pipeline that the perforated membrane that through hole therein is nano-pore is attached with inner surface and/or outer surface is also considered as
It is nano-pore to have the through hole in porose area.In the utility model, term " micron openings " refers to that average pore size is more than 1000nm hole, institute
The average pore size for stating micron openings is preferably not greater than 20 μm, more preferably not more than 15 μm, more preferably no more than 10 μm.
As an example of the pipeline with perforated membrane, the void channels can be membrane tube.Passage in the void channels
Quantity is not particularly limited, and usually, the quantity of the passage in the void channels can be 4-20 bars.
The component at least partially has porose area, the length direction extension for having porose area along the component.Preferably,
It is described to there is porose area to cover whole component (that is, by with the average pore size between described fluid passage and the gas passage
For the component adjoining of the through hole of nano-scale, the hydrogen is injected into by the through hole in the oil phase).It is described to have hole
Area has the through hole that the average pore size is nano-scale, so that hydrogen passes through the leading to for nano-scale with average pore size
Hole is injected into the oil phase.The porosity for having porose area is preferably 5-75%, so can be by enough hydrogen preferably
It is dispersed and dissolved in oil phase.The porosity for having porose area is more preferably 10-45% (such as 10-25%).The porosity is
Refer to the percentage for the cumulative volume for thering is the pore volume in porose area to occupy porose area, determined using nitrogen adsorption methods method.
The material for forming the component can be inorganic material (such as inorganic ceramic), or organic material, as long as shape
Chemical interaction occurs for the oil phase do not isolated into the material of the component with hydrogen and water-oil separating unit.
In actual mechanical process, the component and a housing can be used cooperatively, so as to form the blender.Institute
That states housing is internally provided with least one component, and the inner space of the housing is separated into fluid passage by the component
And gas passage.The housing has gas material entrance, liquid material entrance and liquid material outlet, the fluid passage
Both ends enter with the liquid material entrance and the liquid material outlet, the gas passage with the gas material respectively
Mouth connection.
Filling rate of the component in the housing typically can be 10-90%, such as 50-70%.The filling rate is
The space and the percent value of the total measurement (volume) of housing that finger component occupies.
Fig. 1 shows a kind of preferred embodiment of the blender.As shown in figure 1, (component in Fig. 1 is more to component 1
Hole pipeline) it can be used cooperatively with housing 2.That is, at least one component 1 is placed in housing 2, and makes the outer wall and shell of component 1
Existential Space between the inwall of body 2.By the passage that component 1 surrounds as the oil phase isolated for accommodating water-oil separating subelement
Fluid passage, the space that the inwall of the outer wall of component 1 and housing 2 is formed is as the gas passage for being used to accommodate hydrogen；Or
The passage that component 1 surrounds is as the gas passage for accommodating hydrogen, the space that the outer wall of component 1 is formed with the inwall of housing 2
Fluid passage as the oil phase isolated for accommodating water-oil separating subelement.Preferably, the passage conduct surrounded of component 1
The fluid passage for the oil phase isolated for accommodating water-oil separating subelement, the sky that the outer wall of component 1 is formed with the inwall of housing 2
Between as accommodating the gas passage of hydrogen.
In the passage that the component surrounds as accommodating the fluid passage of the oil phase that water-oil separating subelement is isolated,
When the space that the inwall of the outer wall of the component and the housing is formed is as being used to accommodate the gas passage of hydrogen, such as Fig. 1 institutes
Show, gas material entrance 3, liquid material entrance 4 and liquid material outlet 5 can be set on housing 2, the fluid passage
Both ends connect with liquid material entrance 4 and liquid material outlet 5 respectively, and the gas passage connects with gas material entrance 3.Will
Hydrogen is sent into housing 2 by gas material entrance 3, and the oil phase that water-oil separating subelement is isolated is sent into the passage of component 1
In, in the presence of pressure differential, hydrogen is entered by the hole on tube wall in the oil phase that the water-oil separating subelement is isolated,
So as to obtain the charging of pre-hydrogenator.
In the example that this is more highly preferred to, the blender can be arranged on to the arrival end of the pre-hydrogenator,
So as to which the gas-liquid mixture of blender output is sent directly into pre-hydrogenator as charging.
The small volume of the blender, and installation method is easy.Such as：The blender can be arranged on by ring flange
On the entrance pipe of pre-hydrogenator, realize and mixed while hydrocarbon ils is transported with hydrogen.
The pre-hydrotreating unit includes liquid phase pre-hydrogenator, for the gas-liquid mixture for exporting mixed cell
Contacted with the catalyst that catalytic hydrodemetallation acts on, carry out liquid phase pre-hydrotreating reaction.
The pre-hydrogenator can be common hydrogenation reactor.Preferably, the pre-hydrogenator is tubular type
Reactor.The length of the tubular reactor and the ratio of internal diameter can be 5-200：1, preferably 8-100：1, more preferably 10-
20：1.
The pre-hydrogenator can use batch reactor, can also use flow reactor.Preferably, institute
State pre-hydrogenator and use flow reactor.It is highly preferred that the pre-hydrogenator uses fixed bed reactors.Enter one
Preferably, the pre-hydrogenator uses tubular fixed-bed reactor to step.
Can be that various types of hydrocarbon ils are pre-processed according to pretreatment system of the present utility model.Preferably, institute
State hydrocarbon ils and contain residual oil, such as decompression residuum and/or reduced crude.When the hydrocarbon ils contains residual oil, the hydrocarbon ils preferably also contains
There is one kind or two in coking wax slop, catalytic slurry, FCC recycle oil, deasphalted oil, visbreaking light oil and visbreaker tar
The combination of the kind above, so as to reduce the viscosity of residual oil.
According to hydrocarbon ils pretreatment unit of the present utility model, in operation, by hydrocarbon ils and metal remover can be contained
The aqueous solution is sent into the tunica fibrosa contact reactor of tunica fibrosa haptoreaction subelement, and hydrocarbon ils and metal remover are in filametntary table
Sprawl contact in face so that metal remover and the metal ion haptoreaction in hydrocarbon ils, the metal ion in hydrocarbon ils is transferred to water
Xiang Zhong；Water-oil separating is carried out in water-oil separating subelement from the liquid mixture of filametntary end outflow, respectively obtains water
The oil phase that phase and metal ion content reduce；The oil phase that metal ion content is reduced is sent into mixed cell, is mixed with hydrogen
Close, obtain the gas-liquid mixture containing hydrogen；Obtained gas-liquid mixture is sent into pre-hydrogenator, with adding with catalysis
The catalyst contact of hydrogen demetalization, carries out pre-hydrotreating reaction, and so as to further reduce the tenor in hydrocarbon ils, colloid contains
Amount, asphalt content etc..
The metal remover is preferably to have chelation and the de- gold suitably used in filament surface to metal ion
Belong to agent.Preferably, the metal remover is the group more than one or both of carboxylic acid, phosphoric acid, carboxylate and phosphate
Close.The instantiation of the metal remover can include but is not limited to sodium tripolyphosphate, calgon, ethylenediamine tetra-acetic acid,
Combination more than one or both of diethyl pentetic acid and citric acid.Business metal remover can also be used, is such as purchased
From the YX-F-101 type metal removers of Yueyang Yuxiang Technology Co., Ltd..
The dosage of the metal remover can be selected according to the property of hydrocarbon ils.Usually, the metal remover is institute
State the 0.01-0.05 weight % of the total amount of hydrocarbon ils.
The dosage of water can be selected according to the dosage of hydrocarbon ils.Usually, the dosage of water can be the total amount of hydrocarbon ils
5-30 weight %, the preferably total amount of hydrocarbon ils 7-20 weight %, more preferably hydrocarbon ils total amount 9-15 weight %.The de- gold
Category agent is dissolved in the water, and is sent into as a solution in the tunica fibrosa contact reactor.
The operating condition of the tunica fibrosa contact reactor can be selected according to the species of the metal remover of use.One
As, the temperature in the mass transfer space of tunica fibrosa contact reactor may be controlled to 60-200 DEG C, be preferably controlled to 100-180
DEG C, more preferably control is 130-150 DEG C.Pressure in the mass transfer space of the tunica fibrosa contact reactor may be controlled to 0.3-
3MPa, is preferably controlled to 0.8-1.8MPa, and the pressure is absolute pressure.
The hydrocarbon ils is preferably preheated, to improve catalytic efficiency before tunica fibrosa contact reactor is entered.
The operating condition of the water-oil separating subelement can be selected according to specific oil-water separation method, without spy
Do not limit.
Can be by oil phase and hydrogen that water-oil separating subelement is isolated under normal conditions in the blender of mixed cell
In mixed.
Oil phase is mixed with hydrogen using blender of the present utility model, even in relatively low hydrogen injection amount, and will not
Under conditions of pre- hydrogenation product circulation, it can also be reacted for liquid-phase hydrogenatin and enough hydrogen is provided.Usually, the feeding amount of hydrogen with
The volume ratio of hydrocarbon ils is generally not higher than 200, preferably not higher than 150.Specifically, it is existing when the hydrocarbon ils is residual oil
In Residue Hydrotreating Technology, the dosage of hydrogen is big, and the volume ratio of hydrogen and residual oil raw material is generally more than 500；But use this reality
Oil phase is mixed with hydrogen with new blender, the feeding amount of hydrogen and the volume ratio of residual oil can be 30-120, be preferably
60-100。
From the angle of the further effect for improving pre-hydrotreating reaction, preferably hydrogen is sent into and handled in liquid-phase hydrogenatin
In hydrocarbon ils under temperature and pressure, for example, when the hydrocarbon ils is residual oil, it is 330-450 DEG C (excellent that hydrogen preferably is sent into temperature
Elect 350-400 DEG C as) and pressure be in 4-20MPa (be preferably 6-15MPa) hydrocarbon ils.
The catalyst with catalytic hydrodemetallation effect can be selected according to the species of hydrocarbon ils, without special
Limit.Usually, the catalyst with catalytic hydrodemetallation effect can contain carrier and be supported on the carrier
On vib metals element and group VIII metallic element.The vib metals element is preferably molybdenum and/or tungsten, described
Group VIII metallic element is preferably cobalt and/or nickel.The vib metals element and group VIII metallic element are in the load
Load capacity on body can be selected according to the species of the catalyst acted on catalytic hydrodemetallation.Usually, with institute
State with catalytic hydrodemetallation effect catalyst total amount on the basis of and in terms of oxide, the vib metals element
Content can be 1-15 weight %, the content of the group VIII metallic element can be 0.5-8 weight %.The carrier can
Think the heat-resistant inorganic oxide of the carrier of the various catalyst for being adapted as that there is catalytic hydrodemetallation to act on, such as aoxidize
Silicon and/or aluminum oxide.The carrier of the catalyst with catalytic hydrodemetallation effect can also be loaded with conventional various
Auxiliary agent, no longer it is described in detail herein.
The operating condition of the pre-hydrogenator, it can be selected according to the hydrogenation mode that pre-hydrogenator uses
Select.For example, it is fixed bed reactors in the pre-hydrogenator, and when hydrocarbon ils is residual oil, the catalyst bed of pre-hydrogenator
Temperature in layer can be 330-450 DEG C, preferably 350-400 DEG C, and the pressure (absolute pressure) in pre-hydrogenator can be with
For 4-20MPa, preferably 6-15MPa, the volume space velocity of hydrocarbon oil-hydrogen mixture can be 0.5-5h-1。
According to second of the present utility model aspect, the utility model provides a kind of hydrocarbon oil hydrogenation processing system, and this is
System includes hydrocarbon oil crude material pretreatment unit and main hydrogenation plant, wherein, the hydrocarbon oil crude material pretreatment unit is according to this reality
With the pretreatment unit described in new one side.
The pretreatment unit has been carried out being described in detail above, is no longer described in detail herein.
The main hydrogenation plant is used to carry out hydrotreating to the product of pretreatment unit output, can be common hydrogenation
Processing unit, such as fixed bed hydrogenation processing unit.
Fig. 2 shows a kind of preferred embodiment according to hydrocarbon oil hydrogenation processing system of the present utility model, below in conjunction with
The preferred embodiment is described in detail Fig. 2.
As shown in Fig. 2 the hydrocarbon oil hydrogenation processing system includes tunica fibrosa contact reactor 204, gun barrel 205, mixed
Clutch 208, pre-hydrogenator 210 and main hydrogenation reactor 212.Gun barrel 205 is arranged on tunica fibrosa haptoreaction
The lower section of device 204 and with the bottom connection of tunica fibrosa contact reactor 204, to receive what is flowed out from tunica fibrosa contact reactor 204
Liquid mixture, and it is carried out water-oil separating, respectively obtain oil phase and aqueous phase.Blender 208 is arranged on pre-hydrogenator
210 bottom inlet end, for receiving the oil phase isolated from gun barrel 205, and by hydrogen injection oil phase, form gas
Liquid mixture.Pre-hydrogenator 210 is used for the gas-liquid mixture for receiving blender 208 to export, and by it with adding with catalysis
The catalyst of hydrogen demetalization is contacted under liquid-phase hydrogenatin treatment conditions.Main hydrogenation reactor 212 is used to be hydrogenated with advance
The liquid product 211 that reactor 210 exports carries out hydrogenation reaction.
Hydrocarbon oil hydrogenation processing system shown in Fig. 2 can be operated with the following method：Hydrocarbon ils 201 is passed through into pump 221
It is sent into tunica fibrosa contact reactor 204, while the metal remover aqueous solution 203, hydrocarbon is sent into tunica fibrosa contact reactor 204
Oil and metal remover sprawl contact in filament surface, and the metal ion in hydrocarbon ils is transferred in aqueous phase.Tunica fibrosa contact is anti-
The liquid mixture for answering device 204 to export enters in gun barrel 205, water-oil separating is carried out, from positioned at gun barrel 205
The outlet discharge solid sediment 206 of bottom, aqueous phase 207, water are discharged by the outlet being arranged in the side wall of gun barrel 205
Phase 207 can be circulated for preparing the metal remover aqueous solution 203, and oil phase is then by being arranged on going out for the top of gun barrel 205
Mouth discharge.The oil phase that gun barrel 205 is discharged is entered by pump 222 in the fluid passage of blender 208, while to blender
Hydrogen 209 is sent into 208 gas passage so that hydrogen enters liquid by the component of adjacent fluid passage and gas passage
Mixed in passage with oil phase, obtain gas-liquid mixture.It is anti-that the gas-liquid mixture that blender 208 exports flows up into pre- hydrogenation
Answer in device 210, contact with the catalyst with catalytic hydrodemetallation effect under liquid-phase hydrogenatin treatment conditions, be hydrogenated with advance
Reaction.The product liquid 211 and recycle hydrogen 213 that pre-hydrogenator 210 exports enter in main hydrogenation reactor 212 together,
Hydrotreating is carried out under trickle bed hydroprocessing condition.
Illustrate the utility model with reference to embodiments, but and be not so limited the scope of the utility model.
In following examples and comparative example, average pore size is determined using ESEM method.
In following examples and comparative example, pressure is in terms of gauge pressure.
Embodiment 1-2 is used to illustrate the utility model.
Embodiment 1
The present embodiment is pre-processed to residual oil raw material using the method shown in Fig. 2 and is entered pretreated residual oil raw material
Row hydrogenation, wherein, the quantity of tunica fibrosa contact reactor and gun barrel is 1.
The residual oil raw material used in the present embodiment is the miscella of coking wax slop and decompression residuum, wherein, coking weight wax
The content of oil is 50 weight %, and the property of residual oil raw material is listed in table 1.
The metal remover used in the present embodiment is YX-F-101 types metal remover (purchased from the limited public affairs of Yueyang space Xiang science and technology
Department), metal remover is 0.01 weight % relative to the dosage of residual oil raw material.
Filament in the mass transfer space cylinder of the tunica fibrosa contact reactor used in the present embodiment for 316 series not
Become rusty steel wire (being purchased from Xinghua Xin Fan stainless steel products factory), and the draw ratio of mass transfer space cylinder is 6：1, tunica fibrosa contact reactor
The volume of mass transfer space cylinder is 0.3L, filametntary filling than for 6% (in the mass transfer space of fiber-film contact, filament
Volume account for cylinder volume percentage)；The operating condition of tunica fibrosa contact reactor is：130 DEG C of temperature, pressure 1.0MPa
(absolute pressure), liquid hourly space velocity (LHSV) 20h-1, relative to residual oil raw material, water injection rate is 10 weight %.
In the present embodiment, the product discharged from fiber-film contact is stood into 2h in gun barrel, is separated into oil phase
And aqueous phase.
The component for being used to abut fluid passage and gas passage in the present embodiment, in the blender used is by porous material
The pipeline of formation (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, is evenly distributed with 19 passages, each on pipeline
The internal diameter of passage is 3.3mm, and the average pore size in the hole on tube wall is 50nm, 20%) porosity of tube wall is；Passage on pipeline
As fluid passage, space that the outer wall of pipeline and the inwall of housing are formed is as gas passage, pipeline filling rate in the housing
For 60%.Temperature in fluid passage is 360 DEG C, pressure 8.0MPa.
In the present embodiment.The catalyst loaded in tubular reactor is RDM-2B (purchased from sinopec catalyst Chang Ling point public affairs
Department), the ratio of height to diameter of beds is 14 in tubular reactor, and the operating condition of tubular reactor is：Temperature is 360 DEG C, pressure
Power is 8.0MPa (absolute pressure), hydrogen to oil volume ratio 90：1, the volume space velocity of charging is 1.3h-1。
In the present embodiment, main hydrogenation reactor uses trickle bed hydrogenation reaction technique, for the company of Beijing Tuo Chuan companies production
Continuous high pressure fixed bed hydrogenation pilot-plant, the device is connected using 3 reactors, on the basis of the flow direction of material, positioned at most upper
The catalyst of filling is RDM-3B (being purchased from sinopec catalyst Chang Ling branch company) in first reactor (that is, one is anti-) of trip,
The catalyst of filling is RMS-1 (purchased from sinopec catalyst Chang Ling point public affairs in second reactor (that is, two is anti-) in middle reaches
Department), the catalyst of filling (is grown for RCS-1 purchased from sinopec catalyst in the 3rd reactor (that is, three is anti-) of most downstream
Ridge branch company), the filling ratio of three kinds of catalyst is 2：3：5, the operating condition of device is：Pressure is 16.4MPa (absolute pressures
Power), temperature is 380 DEG C, and hydrogen to oil volume ratio 800, volume space velocity is 0.2h during liquid-1。
The present embodiment is pre-processed using following technological process to residual oil raw material, and pretreated residual oil raw material is entered
Row hydrotreating.
Residual oil raw material and metal remover are sent into tunica fibrosa contact reactor and carry out demetalization reaction, tunica fibrosa contact is anti-
The liquid mixture for answering device to flow out, which enters in gun barrel, carries out water-oil separating, and (its nature parameters is in table 1 for the oil phase isolated
In list) enter blender in mix with hydrogen after, by obtained gas-liquid mixture be sent into pre-hydrogenator in, progress pre-add
Hydrogen reacts, and the product (its nature parameters is listed in table 1) that pre-hydrotreating reaction obtains enters as the charging of main hydrogenation reactor
Hydrogenation reaction is carried out in main hydrogenation reactor, the experimental result after main hydrogenation reactor is continuously run 9000 hours arranges in table 2
Go out (reactor pressure decrease refers to 9000 hours post-reactor entrances of operating and the pressure differential of outlet in table 2).
Table 1
Table 2
Embodiment 2
The present embodiment is pre-processed residual oil raw material using method same as Example 1, unlike：
(1) quantity of tunica fibrosa contact reactor and gun barrel is 2, and under each tunica fibrosa contact reactor
Trip sets a gun barrel, i.e. the oil phase that the gun barrel of embodiment 1 is isolated subsequently enters second tunica fibrosa and connect
Touch in reactor and demetalization is carried out using metal remover, obtain liquid mixture into carrying out profit in second gun barrel
Separation, obtained oil phase enters in blender to be mixed with hydrogen, wherein, the tunica fibrosa contact reactor positioned at upstream is referred to as one
Level tunica fibrosa contact reactor, the profit that the liquid mixture for being obtained to one-level tunica fibrosa contact reactor is separated point
It is referred to as one-level gun barrel from tank, the tunica fibrosa contact reactor positioned at downstream is referred to as secondary fiber film contact reactor,
The gun barrel separated for the liquid mixture obtained to secondary fiber film contact reactor is referred to as two level profit point
From tank.
(2) water injection rate of tunica fibrosa contact reactor is 10 weight %, metal remover dosage relative to residual oil raw material use
Measure and listed for 0.007 weight %, the property of residual oil raw material in table 3.
Experimental result is listed in table 3.
Table 3
Comparative example 1
Residual oil raw material is pre-processed using method same as Example 1, and pretreated residual oil raw material is entered
Row hydrogenation, unlike, tunica fibrosa contact reactor is not used, but residual oil raw material is sent directly into blender to enter with hydrogen
After row mixing, it is sent into pre-hydrogenator and is hydrogenated with advance.Wherein, the experimental result of pre-hydrogenator is listed in table 4.
Table 4
Embodiment 1-2's as a result, it was confirmed that being pre-processed using method of the present utility model to residual oil raw material, can also have
Metal in effect ground removing residual oil raw material, reduces its viscosity, density and carbon residue, extends the main operation period of hydrogenation device of residual oil.
Preferred embodiment of the present utility model described in detail above, still, the utility model is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the present utility model, the technical solution of the utility model can be entered
The a variety of simple variants of row, these simple variants belong to the scope of protection of the utility model.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means, in order to avoid unnecessary repetition, the utility model is to each
The possible combination of kind no longer separately illustrates.
In addition, it can also be combined between a variety of embodiments of the present utility model, as long as it is not disobeyed
Thought of the present utility model is carried on the back, it should equally be considered as content disclosed in the utility model.
Claims (12)
1. a kind of hydrocarbon ils pretreatment unit, the device includes tunica fibrosa haptoreaction unit, mixed cell and pre-hydrotreating
Unit,
The tunica fibrosa haptoreaction unit includes at least one tunica fibrosa haptoreaction subelement and at least one profit point
Ion unit, the tunica fibrosa haptoreaction subelement are used to receive hydrocarbon oil crude material, and by the hydrocarbon oil crude material and metal remover
Contact, the water-oil separating subelement are used to the liquid mixture of tunica fibrosa haptoreaction subelement output carrying out profit point
From respectively obtaining oil phase and aqueous phase；
The mixed cell is used to mix the oil phase that water-oil separating subelement exports with hydrogen, and the mixed cell is included at least
One blender, the blender include at least one gas passage and at least one fluid passage, the gas passage and institute
State and abutted by a component between fluid passage, the component at least partially has a porose area, described to have porose area to have average hole
Footpath is the through hole of nano-scale, and the gas passage is used to accommodate the hydrogen, and the fluid passage is used to accommodate the oil phase,
The hydrogen can be injected into the oil phase by the average pore size for the through hole of nano-scale；
The pre-hydrotreating unit includes liquid phase pre-hydrogenator, for the gas-liquid mixture and tool for exporting mixed cell
There is the catalyst contact that catalytic hydrodemetallation acts on, carry out liquid phase pre-hydrotreating reaction.
2. device according to claim 1, it is characterised in that the tunica fibrosa haptoreaction subelement includes at least one
Tunica fibrosa contact reactor, the tunica fibrosa contact reactor from top to bottom include feed end and are provided with filament successively
Mass transfer space, the feed end is used to receive hydrocarbon ils and metal remover, and hydrocarbon ils and metal remover are sent into mass transfer space
Contacted.
3. device according to claim 2, it is characterised in that the feed end is provided with hydrocarbon oil feed mouth and metal remover
Charging aperture, the hydrocarbon oil feed mouth are used to receive the hydrocarbon ils, and the metal remover charging aperture is used to receive the metal remover.
4. device according to claim 3, it is characterised in that in the tunica fibrosa contact reactor, in the charging aperture
At least one fluid distributor is provided between the mass transfer space, the hydrocarbon ils and the metal remover are via the fluid
The filametntary surface that distributor is flowed into mass transfer space.
5. device according to claim 1, it is characterised in that the component is in perforated membrane, porous plate and void channels
One or more kinds of combinations.
6. device according to claim 1 or 5, it is characterised in that the mixing arrangement also includes housing, the housing
At least one component is internally provided with, the inner space of the housing is separated into the component into fluid passage and gas leads to
Road.The housing has gas material entrance, liquid material entrance and liquid material outlet, the both ends difference of the fluid passage
With the liquid material entrance and the liquid material outlet, the gas passage connects with the gas material entrance.
7. device according to claim 1 or 5, it is characterised in that the average pore size of the through hole is 10-1000nm.
8. device according to claim 1, it is characterised in that the pre-hydrogenator is tubular reactor.
9. device according to claim 8, it is characterised in that the length of the tubular reactor and the ratio of internal diameter are 5-
200：1.
10. according to the device described in any one in claim 1,8 and 9, it is characterised in that the pre-hydrogenator is solid
Fixed bed reactor.
11. a kind of hydrocarbon oil hydrogenation processing system, the system includes hydrocarbon oil crude material pretreatment unit and main hydrogenation plant, the master
Hydrogenation plant is used to carry out hydrotreating to the product of pretreatment unit output, it is characterised in that the hydrocarbon oil crude material pretreatment
Device is the pretreatment unit described in any one in claim 1-10.
12. system according to claim 11, it is characterised in that the main hydrogenation plant is fixed bed hydrogenation processing dress
Put.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110093187A (en) * | 2018-01-29 | 2019-08-06 | 中国石油化工股份有限公司 | The method of catalytic cracked oil pulp Combined machining |
| CN111298722A (en) * | 2018-12-12 | 2020-06-19 | 中国石油化工股份有限公司 | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material |
| WO2022089521A1 (en) * | 2020-10-28 | 2022-05-05 | 中国石油化工股份有限公司 | Heavy oil hydrogenation reaction system and heavy oil hydrogenation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110093181A (en) * | 2018-01-29 | 2019-08-06 | 湖南长岭石化科技开发有限公司 | Catalytic cracked oil pulp takes off solid method |
| CN110093187A (en) * | 2018-01-29 | 2019-08-06 | 中国石油化工股份有限公司 | The method of catalytic cracked oil pulp Combined machining |
| CN110093187B (en) * | 2018-01-29 | 2021-04-09 | 中国石油化工股份有限公司 | Method for combined processing of catalytic cracking slurry oil |
| CN110093181B (en) * | 2018-01-29 | 2021-06-04 | 湖南长岭石化科技开发有限公司 | Method for removing solid from catalytic cracking oil slurry |
| CN111298722A (en) * | 2018-12-12 | 2020-06-19 | 中国石油化工股份有限公司 | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material |
| WO2022089521A1 (en) * | 2020-10-28 | 2022-05-05 | 中国石油化工股份有限公司 | Heavy oil hydrogenation reaction system and heavy oil hydrogenation method |
| EP4238636A4 (en) * | 2020-10-28 | 2024-10-30 | China Petroleum & Chem Corp | Heavy oil hydrogenation reaction system and heavy oil hydrogenation method |
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