CN104927902B - A kind of wax oil hydrogenation processing method - Google Patents
A kind of wax oil hydrogenation processing method Download PDFInfo
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Abstract
The invention provides a kind of wax oil hydrogenation processing method, including：Hydrogen is sent into wax oil raw material by average pore size for the hole of nano-scale, obtains hydrogeneous wax oil；The hydrogeneous wax oil is sent into tubular reactor, contacted under liquid-phase hydrogenatin treatment conditions with the hydrogenation catalyst being seated in the tubular reactor.Even if the present invention is with relatively low hydrogen-oil ratio and at a high space velocity, it also can effectively remove the sulphur in wax oil and nitrogen and make part aromatic hydrocarbons saturation, improve the hydrogen-to-carbon ratio of wax oil, so as to obtain high-quality catalytic cracking unit raw material.
Description
Technical field
The present invention relates to a kind of wax oil hydrogenation processing method.
Background technology
In recent years, it is on the rise with increasingly scarcity, crude oil heaviness, the in poor quality trend of petroleum resources, and with warp
The development of Ji, the demand of light-end products is increased increasingly, therefore, the lighting of mink cell focus maximum, maximizing the benefits turn into oil refining
The target that enterprise is pursued.
The Main Means of mink cell focus working process are hydrocracked, catalytic cracking and delayed coking.It is hydrocracked due to throwing
Provide larger, running cost is high, it is difficult to processing coked waxy oil and residual oil limit its application, delayed coking because liquid yield is low,
The application of the factors such as poor product quality is also restricted.Hydrocarbon Content by Catalytic Cracking Operation expense is low, and light oil yield is high, gasoline products matter
Measure, the weight inferior raw material such as wax oil and residual oil can be processed, so as to obtain extensive technique application.
As China is more and more tighter to petrol and diesel oil target level of product quality, how to solve sulfur content of catalytic cracking gasoline height, urge
Change focus of the problem of cracked diesel oil sulphur and arene content are high, Cetane number is low as Recent study.Develop very at present
The pre- hydrogen addition technology of more catalytic cracking catalysts, auxiliary agent and technology, wherein catalytically cracked material, which turns into, solves catalytic gasoline sulphur
The high effective means of content.Hydrogenation not only reduces sulphur, nitrogen and arene content to catalytically cracked material in advance, also advantageously improves catalysis and splits
Change conversion ratio, increase catalytic cracking is gently received, and reduces content of sulfur in gasoline, gasoline olefin and diesel cetane-number also make moderate progress.
In the various methods of straight-run gas oil lighting, wax oil hydrogenation is one fine as the technique of catalytically cracked material
Process route.Wax oil is stripped of most of sulphur, nitrogen impurity, and saturation part aromatic hydrocarbons after hydrotreating, improves hydrogen and contains
Amount, and then the feed stock conversion of catalytic cracking can be improved, coke yield is reduced, catalytic cracking yield of light oil is improved, obtains
The product that quality improves, the sulfur content of obtained gasoline is low, and gasoline olefin and diesel cetane-number also make moderate progress；Meanwhile wax
Oily hydrotreating can also the low-sulfur diesel-oil of by-product 15%, improve the diesel and gasoline ratio of refinery.Therefore wax oil hydrogenation processing generation oil is as catalysis
The technique of cracked stock also obtains universal technique application.
Wax tailings sulphur, nitrogen content are high, and particularly basic n content is high, and carbon residue is high, and arene content is high, is directly entered catalysis
Cracking unit handling ease makes catalyst lose catalytic activity, causes catalyst serious inactivation, so as to cause catalytic cracking unit
Yield of gasoline is low, and coke yield rises, therefore wax tailings carry out weighted BMO spaces and are more necessary relative to other wax oil components.
CN1313379A discloses a kind of method of poor-quality raw material for catalytic cracking weighted BMO spaces, this method by raw material successively
Contacted with hydrogenation protecting agent, Hydrodemetalation catalyst and Hydrobon catalyst, be 5.0-10.0 MPas, temperature in hydrogen dividing potential drop
For 330-420 DEG C, hydrogen to oil volume ratio 300-1000：1st, liquid hourly space velocity (LHSV) is 0.2-1.2 hours-1Under conditions of with hydrogen react,
Reacted effluent recycles through refrigerated separation, hydrogen-containing gas, and product liquid enters fractionating system.After raw material is hydrogenated
Sulphur, nitrogen and tenor reduce, and can be used directly as catalytically cracked material.
CN101007964A discloses a kind of method of hydrotreating for producing fine quality catalytic cracking raw material, feedstock oil and hydrogen it is mixed
Compound carries out hydro-upgrading reaction in the presence of hydrogenation catalyst, and its reaction product obtains naphtha after refrigerated separation and evaporated
Point, diesel oil distillate and gas oil fraction, wherein, hydrogenation catalyst by hydrogenation protecting agent, optional Hydrodemetalation catalyst and
Hydrotreating catalyst form, on the basis of integer catalyzer volume, wherein hydrogenation protecting agent, Hydrodemetalation catalyst and add
The admission space percentage of hydrogen processing catalyst is respectively 2-15 volume %, 0-30 volume % and 55-95 volumes.
CN102344826A discloses a kind of combined hydrogenation method for producing fcc raw material and fine-quality diesel oil.This method is set
The hydroconversion reaction zone of two parallel feeds, a shared hydrogen gas system and a shared rear piece-rate system, wherein first adds
The charging of hydroformylation reaction zone is wax oil raw material, and the charging of the second hydroconversion reaction zone is diesel raw material.Two entrance hydrogen for reacting area
Partial pressure is 5.0-11.0MPa.
CN1896192A discloses a kind of wax oil hydrogenation processing and catalytic cracking two-way combined process, wherein, wax oil
Enter hydrotreater together with heavy catalytic cycle oil, catalytic cracking diesel oil, in the presence of hydrogen and hydrogenation catalyst
Hydrogenation reaction is carried out, separation reaction product obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenation tail oil, and hydrogenation tail oil enters
Catalytic cracking unit, carries out cracking reaction in the presence of catalytic cracking catalyst, and dry gas, liquefied gas, catalysis are obtained after separation
Cracking gasoline, catalytic cracking diesel oil, heavy catalytic cycle oil and slurry oil, catalytic cracking diesel oil and heavy catalytic cycle oil follow
Ring is to hydrotreater.
Urge wax oil to carry out hydrotreating although with the above method, qualified raw material can be provided for catalytic cracking；But
The above method is using conventional trickle bed hydrogenation technique, it is necessary to recycle hydrogen and its EGR, and during the operation of device
Air speed is low, causes equipment investment and operating cost higher.
The content of the invention
It is an object of the invention to overcome needed existing for existing wax oil hydrogenation handling process recycle hydrogen and need low
The technical problem run under air speed, there is provided a kind of wax oil hydrogenation processing method, hydrotreating is carried out to wax oil using this method, i.e.,
Make to carry out at a high space velocity with relatively low hydrogen-oil ratio, can also obtain preferable hydrotreating effect, be met as urging
Wax oil after the hydrogenation of the requirement of change cracked stock.
The invention provides a kind of wax oil hydrogenation processing method, this method includes：By average pore size it is nanometer by hydrogen
The hole of size is sent into wax oil, obtains hydrogeneous wax oil；The hydrogeneous wax oil is sent into tubular reactor, handled in liquid-phase hydrogenatin
Under the conditions of contacted with the hydrogenation catalyst being seated in the tubular reactor.
Wax oil is handled using the method for the present invention, even if with relatively low hydrogen-oil ratio and at a high space velocity,
Sulphur, the nitrogen in wax oil can be effectively removed, and makes part aromatic hydrocarbons saturation, improves the hydrogen-to-carbon ratio of wax oil after hydrogenation, so as to
Obtain high-quality catalytically cracked material.
The method of the present invention is used to be sent into hydrogen in wax oil for the hole of nano-scale by average pore size, can be by more
Hydrogen be dissolved in wax oil, undissolved hydrogen can be then highly dispersed in wax oil, be so able to ensure that hydrogenation reaction in liquid
Carried out in phase, improve hydrogenation reaction speed, reduce the trend of catalyst green coke, catalyst is kept higher catalytic activity, prolong
The service life of long catalyst, so as to extend the stable operation cycle of hydrogenation plant.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is used for the structure of adjacent fluid passage and gas passage in the air and liquid mixer that schematically the explanation present invention uses
A kind of preferred embodiment of part.
Fig. 2 is a kind of cross-sectional view of the component shown in Fig. 1.
Fig. 3 is another cross-sectional view of the component shown in Fig. 1.
Fig. 4 is the structural representation for the air and liquid mixer that the present invention uses.
Fig. 5 is a kind of embodiment of the wax oil hydrogenation processing method of the present invention.
Fig. 6 is the another embodiment of the wax oil hydrogenation processing method of the present invention.
Fig. 7 is another embodiment of the wax oil hydrogenation processing method of the present invention.
Fig. 8 is used to illustrate the annexation between air and liquid mixer and tubular reactor.
Description of reference numerals
1：Air and liquid mixer 10：Component
101：Tube wall 102：Passage
103：Perforated membrane 11：Gas access
12：Liquid inlet 13：Liquid outlet
14：Housing 2：Hydrogen
3：Wax oil 4：Tubular reactor
5：Ring flange 6：Ring flange
7：Ring flange 8：Ring flange
9：Wax oil after hydrogenation
Embodiment
The invention provides a kind of wax oil hydrogenation processing method, this method includes：By average pore size it is nanometer by hydrogen
The hole of size is sent into wax oil, obtains hydrogeneous wax oil；The hydrogeneous wax oil is sent into tubular reactor, handled in liquid-phase hydrogenatin
Under the conditions of contacted with the hydrogenation catalyst being seated in the tubular reactor.
In the present invention, the average pore size is that the average pore size in the hole of nano-scale typically can be 1nm to 1000nm, excellent
Elect 30nm to 1000nm, more preferably 30nm to 800nm, more preferably 50nm to 500nm as.The average pore size uses
ESEM method determines.
From the further dispersion mixing for improving hydrogen in the wax oil, and then enable hydrogen faster more uniformly
The angle being dispersed in the wax oil is set out, and the ratio that the quantity in the hole that aperture is in the range of 50-500nm accounts for total hole number is
More than 95%, such as 95-98%.
It can be in static wax oil by hydrogen injection, hydrogen injection can also be in the wax oil of flow regime.It is excellent
Hydrogen injection is in the wax oil of flow regime by choosing, so can while wax oil is transported, by hydrogen injection wax oil, from
And obtain the production efficiency further improved.When hydrogen injection is in the wax oil of flow regime, the injection of the hydrogen
Speed is v1And with gh-1·m-2（Represent within the unit interval, pass through the total amount of the hydrogen in hole in unit area）Meter, the wax
The flow velocity of oil is v2And with kgh-1·m-2（Represent the quality of wax oil passed through in the unit interval on unit section）Meter, v1/v2
Preferably 0.000625-0.09, it can so obtain the hydrogen dispersing and dissolving effect further improved.It is highly preferred that v1/v2=
0.005-0.06（Such as 0.005-0.01）, the hydrogen dispersing and dissolving effect that can not only so obtain, and can obtain compared with
High production efficiency.
Various methods can be used to inject hydrogen in the wax oil for the hole of nano-scale by average pore size.
In the preferred embodiment of the present invention, hydrogen is injected into the wax oil by a kind of air and liquid mixer,
The air and liquid mixer include it is at least one be used for accommodate the wax oil fluid passage and it is at least one be used for accommodate the hydrogen
The gas passage of gas, abutted between the fluid passage and the gas passage by a component, at least part of the component
To have porose area, the hole for having porose area that there is the average pore size to be nano-scale, the hydrogen is by the average pore size
The hole of nano-scale is injected into the wax oil.In the present invention, term " fluid passage " is the space for referring to accommodate wax oil；Art
Language " gas passage " is the space for referring to housing hydrogen gas.
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 in the hole of nano-scale, the hydrogen is injected into by the hole in the wax oil）.It is described to have porose area tool
There is the hole that the average pore size is nano-scale, so that hydrogen is injected into by described with average pore size for the hole of nano-scale
In the wax oil.The porosity for having porose area is preferably 5-75%, so enough hydrogen can preferably be disperseed and be dissolved
In wax oil.The porosity for having porose area is more preferably 10-45%（Such as 20-25%）.The porosity refers to have in porose area
Pore volume occupies the percentage of the cumulative volume of porose area, is determined using nitrogen adsorption methods.
The component can be that the various hydrogen that can make to be contained in the gas passage are by the average pore size
The hole of nano-scale and enter the component being contained in the wax oil in the fluid passage.In an example, the component by
Porous material is formed, and the average pore size in hole therein is nano-scale.In another example, the component includes matrix（That is,
Tube wall）And the perforated membrane of attachment on the matrix, described matrix have through hole, the perforated membrane can be located at described matrix
The surface contacted with the wax oil being contained in the fluid passage on and/or positioned at described matrix with being contained in the gas
On the surface of hydrogen contact in passage.Preferably, the perforated membrane be located at described matrix with being contained in the fluid passage
On the surface of interior wax oil contact.Hole in the perforated membrane is the hole that previously described average pore size is nano-scale.It is described
The average pore size of through hole on matrix is not particularly limited, as long as can pass through gas.Preferably, it is logical in described matrix
The average pore size in hole is 1nm to 1000 μm（Such as 50-200 μm）.
The shape of the component can be selected according to the position relationship of fluid passage and gas passage, to enable to
The fluid passage and the gas passage are defined by component adjoining.
In one embodiment of the invention, the component is the pipeline with least one passage.The pipeline
There is hole, and the average pore size in the hole is previously described nano-scale on tube wall.
In another embodiment of the invention, the component is the pipeline with least one passage, the pipeline
The inwall of passage and/or the outer wall of pipeline on be attached with perforated membrane, the tube wall of the pipeline has a through hole, on the perforated membrane
Hole be hole that average pore size is nano-scale, the component with this structure is referred to as membrane tube below.Specifically, such as Fig. 1-3
Shown, the component is the membrane tube with least one passage.Membrane tube pipeline with through hole using on tube wall 101 is used as base
Body, pipeline have at least one passage 102, perforated membrane are attached with the inwall of passage 102 and/or the outer wall of pipeline of pipeline
103.The average pore size of through hole on tube wall is not particularly limited, if can make hydrogen by, usually can be 1nm extremely
1000μm（Such as 50-200 μm）；Hole on the perforated membrane is the hole that previously described average pore size is nano-scale.
In above two embodiment, the quantity of the pipeline or the passage in the membrane tube is preferably at least two,
Such as 4-20 bars.
In actual mechanical process, when the component is pipeline or membrane tube, the air and liquid mixer can also include shell
Body, the housing are internally provided with least one pipeline, deposited between the outer wall of the pipeline and the inwall of the housing
In space.Specifically, as shown in figure 4, component 10 can be used cooperatively with housing 14.That is, at least one component 10 is placed in shell
In body 14, and make Existential Space between the outer wall of component 10 and the inwall of housing 14.Passage on the component, which is used as, to be used to hold
Receive the fluid passage of wax oil, the space that the inwall of the outer wall of the component and the housing is formed, which is used as, to be used to accommodate hydrogen
The gas passage；Or the passage on the component is as accommodating the gas passage of hydrogen, the component
The space that the inwall of outer wall and the housing is formed is as the fluid passage for accommodating wax oil.Preferably, the component
On passage as accommodating the fluid passage of wax oil, sky that the inwall of the outer wall of the component and the housing is formed
Between as accommodating the gas passage of hydrogen.
Filling rate of the component in the housing typically can be 10-90%, such as 50-70%.The filling rate refers to
The space and the percent value of the total measurement (volume) of housing that component occupies.
Passage on the members as accommodating the fluid passage of wax oil, the outer wall of the component with it is described
When the space that the inwall of housing is formed is as being used to accommodate the gas passage of hydrogen, as shown in figure 4, can be on housing 14
Gas access 11, liquid inlet 12 and liquid outlet 13 be set, the both ends of the fluid passage respectively with liquid inlet 12 and liquid
The connection of body outlet 13, the gas passage connect with gas access 11.Hydrogen is sent into housing 14 by gas access 11, will
Wax oil is sent into the passage of component 10, in the presence of pressure differential, hydrogen is entered by the hole on tube wall in the wax oil, from
And obtain hydrogeneous wax oil.
The material for forming the component can be inorganic material（Such as inorganic ceramic）, or organic material, as long as shape
With hydrogen and wax oil chemical interaction will not occur for the material into the component.
The amount for the hydrogen being sent into the wax oil can be selected according to the impurity content in the wax oil.Existing wax
In oily hydrogenation technique, the dosage of hydrogen is big, and the volume ratio of hydrogen and wax oil is generally more than 500.The method of the present invention is by hydrogen
It is sent into by the hole of the nano-scale of average pore size in the wax oil, hydrogen high degree of dispersion can be made and be dissolved in the wax oil
In, so as to provide enough hydrogen sources for hydrogenation reaction；Also, in the method for the present invention, hydrogenation reaction is carried out in the liquid phase, can
Reaction heat is taken out of in time.Therefore, even if method of the invention reduces the amounts of hydrogen being sent into the wax oil, can also obtain good
Hydrotreating effect, and reduce the trend of catalyst green coke.According to the inventive method, feeding amount and the wax of the hydrogen
The volume ratio of oil（That is, hydrogen to oil volume ratio）Can be 30-180, preferably 90-150.
With the method for the invention it is preferred to hydrogen is sent into the wax oil of heating, can so hydrogen be set preferably to dissolve
And be dispersed in wax oil, and it is also beneficial to transporting for wax oil.Preferably, hydrogen feeding temperature and pressure is in hydrogenation temperature
In the wax oil under hydrogenation pressure, the trend that hydrogen escapes from hydrogeneous wax oil so can be further reduced.Specifically, can be with
By hydrogen feeding temperature be 330-420 DEG C and pressure is 4-20MPa（Such as 10-20MPa）Wax oil in.
The tubular reactor refers to the reactor with compared with larger ratio of height to diameter.Specifically, the height of the tubular reactor
Ratio with internal diameter can be 5-200：1（Such as 10-20：1）.The internal diameter of the tubular reactor can be conventional selection, such as
Can be 20-2000mm（Such as 50-500mm）.Compared with tank reactor, on the one hand reaction can be reduced using tubular reactor
The volume of device, on the other hand passing through previously described air and liquid mixer（It is pipeline or membrane tube particularly in the component）When,
Directly the air and liquid mixer is arranged on the material inlet pipeline of the tubular reactor, operation is flexibly and conveniently.
The method according to the invention, hydrogeneous wax oil can be sent into tubular reactor in a manner of flowing up, can also
It is sent into a manner of flowing downward in tubular reactor.Preferably, the hydrogeneous wax oil is sent into pipe in a manner of flowing up
In formula reactor, so during the course of the reaction, dissolving and being dispersed in the hydrogen in wax oil will not assemble to form big bubble substantially
And escape, enough hydrogen sources are provided for hydrogenation reaction, obtain preferable hydrotreating effect, and further reduce catalyst green coke
Trend, catalyst is kept higher catalytic activity, further extend the service life of catalyst, so as to further extending plus
The stable operation cycle of hydrogen production device.
Contact of the hydrogeneous wax oil with hydrogenation catalyst can be carried out under liquid-phase hydrogenatin treatment conditions.The liquid phase adds
Hydrogen processing refers to that continuous phase under hydroprocessing conditions is liquid phase, and whole or substantially all gas phase is dispersed in liquid as dispersed phase
Xiang Zhong.Usually, temperature can be 330-420 DEG C；In terms of gauge pressure, pressure can be 4-20MPa（Such as 10-20MPa）.It is described to contain
The air speed of hydrogen wax oil can also be conventional selection.The method of the present invention, even if the hydrogeneous wax oil passes through institute with higher air speed
Hydrogenation catalyst is stated, can also obtain preferably hydrogenation effect.Therefore, the volume space velocity of hydrogeneous wax oil is preferred in method of the invention
For 0.5-5h-1（Such as 2-4h-1）.
The method according to the invention, the quantity of the tubular reactor can be 1, or more than 2.In the pipe
When the quantity of formula reactor is more than 2, the tubular reactor can be to be connected in series, or be connected in parallel, may be used also
Think series connection and combination in parallel.It is described be connected in series the hydrogenation for referring to the output of previous tubular reactor after logistics be next
The charging of tubular reactor；Described be connected in parallel refers to do not have material exchange between tubular reactor.
Using previously described air and liquid mixer by hydrogen injection wax oil, to obtain hydrogeneous wax oil, and by hydrogeneous wax oil
The internal diameter for the outlet for being used to export hydrogeneous wax oil when being sent into tubular reactor, on the air and liquid mixer is r1, the reactor
The internal diameter of the upper entrance for being used to input hydrogeneous wax oil is r2, r1/r2=0.6-1（Such as 0.85-1）.Connect it is described outlet and it is described enter
The internal diameter of the pipe of mouth is r3, r1/r3=0.85-1.5（Such as 0.85-1）.So hydrogeneous wax oil is more stable in transport process, energy
It is enough to obtain preferably hydrogenation effect.
The method of the present invention can carry out hydrotreating to the wax oil in various sources.Usually, the wax oil steams for normal pressure
During evaporating, vacuum distillate of the recovered (distilled) temperature in 350-520 DEG C, can be straight-run gas oil, wax tailings, visbreaking wax oil and
It is more than one or both of depitching wax oil.
The hydrogenation catalyst can be the various catalyst with hydrogenation catalyst effect that wax oil hydrogenation field is commonly used.One
As, the hydrogenation catalyst contains carrier and loads vib metals on the carrier and group VIII metal, institute
It is preferably molybdenum and/or tungsten to state vib metals, and the group VIII metal is preferably cobalt and/or nickel.The vib metals
It can be selected with the load capacity of group VIII metal on the carrier according to the species of hydrogenation catalyst.Usually, with
On the basis of the total amount of the hydrogenation catalyst and in terms of oxide, the content of the vib metals can be 1-15 weight %,
The content of the group VIII metal can be 0.5-8 weight %.The carrier can be the various hydrogenation catalysts that are adapted as
The heat-resistant inorganic oxide of carrier, such as silica and/or aluminum oxide.It can also be loaded with the carrier of the hydrogenation catalyst
Conventional various auxiliary agents, are no longer described in detail herein.
It is a kind of preferred embodiment of the method according to the invention shown in Fig. 5.In this embodiment, mixed in gas-liquid
Hydrogen 2 is injected in wax oil 3 in clutch 1, obtains hydrogeneous wax oil.Hydrogeneous wax oil enter tubular reactor 4 in hydrogenation catalyst
Contact, so as to carry out hydrogenation reaction, wax oil 9 after being hydrogenated with.According to the embodiment, multiple tubular reactors can be set,
Can be to be connected in series between multiple tubular reactors, or be connected in parallel, can also be series connection and combination in parallel.
When multiple tubular reactors are connected in series, along the flow direction of material, it is anti-that air and liquid mixer can be arranged on to first tubular type
Answer the arrival end of device；Can also be as shown in fig. 6, the arrival end in each tubular reactor 4 sets air and liquid mixer 1 respectively.
When multiple tubular reactors are connected in parallel, an air and liquid mixer can be only set, wax oil is mixed with hydrogen, then will be obtained
Hydrogeneous wax oil be respectively fed in multiple tubular reactors for being connected in parallel；Can also be as shown in Figure 7 in each tubular reactor 4
Arrival end air and liquid mixer 1 is set respectively.
It can adopt and air and liquid mixer 1 is connected on entrance pipe in various manners, such as：Can be in air and liquid mixer 1
Both ends respectively set a ring flange（Fig. 8 is shown in which a ring flange 5）, each with the flange on corresponding entrance pipe
Disk is tightly connected（As shown in figure 8, the ring flange 5 of air and liquid mixer one end is tightly connected with the ring flange 6 on entrance pipe）；Enter
The other end of mouth pipeline is connected by ring flange 7 with the ring flange 8 of the arrival end of tubular reactor 4.
Wax oil is adapted as the raw material of catalytic cracking, therefore the method for the present invention after the hydrogenation obtained by the method for the present invention
Suitable for being combined with wax catalysis process.
The present invention is described in detail with comparative example with reference to embodiments, but and be not so limited the present invention model
Enclose.
In following examples and comparative example, average pore size is determined using ESEM method, pressure is in terms of gauge pressure.
Embodiment 1-3 is used for the method for illustrating the present invention.
Embodiment 1
The wax oil raw material used in the present embodiment is second line of distillation straight-run gas oil, and its property is listed in table 1.
The present embodiment carries out hydrotreating using the method shown in Fig. 5 to wax oil.Wherein, the structure of air and liquid mixer is as schemed
The structure for being used to abut the component of fluid passage and gas passage shown in 4, in air and liquid mixer is the pipe formed by porous material
Road（Commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, be evenly distributed with 19 passages on pipeline, each passage it is interior
Footpath is 3.3mm, and the average pore size in the hole on tube wall is 50nm, and the hole number that aperture is in the range of 50-55nm accounts for total hole count
The ratio of amount is 98%, and the porosity of tube wall is 20%）；Passage on pipeline as fluid passage, the outer wall of pipeline and housing
The space that inwall is formed is as gas passage, and filling rate is 60% to pipeline in the housing.
Temperature and pressure in the fluid passage of air and liquid mixer is identical with hydrogenation reaction temperature and pressure.Air and liquid mixer
Material outlet internal diameter and tubular reactor material inlet internal diameter ratio be 1, the material outlet of air and liquid mixer
The ratio of the internal diameter of pipeline of the internal diameter with being connected the material outlet of air and liquid mixer and the material inlet of tubular reactor is 1.
Concrete operations are as follows：Hydrogen is injected into wax oil raw material by air and liquid mixer（Wherein, the flow velocity and wax oil of hydrogen
The ratio of the flow velocity of raw material is 0.006, and the flow velocity of hydrogen is with gh-1·m-2Meter, the flow velocity of wax oil raw material is with kgh-1·m-2
Meter）, obtain hydrogeneous wax oil.Hydrogeneous wax oil is sent into tubular fixed-bed reactor（Internal diameter is 65mm, and tubular reactor is interior according to thing
The flow direction of stream, according to 1：2：4：3 volume ratio loads the wax oil hydrogenation protective agent that the trade mark is RG-20, trade mark RDM-32 successively
Wax oil hydrogenation metal remover, the trade mark be RVS-420 wax oil hydrogenation desulfurizing agent and the trade mark be RDA-30 the de- virtue of wax oil hydrogenation
Catalyst.Wherein, the de- virtue catalysis of wax oil hydrogenation protective agent, wax oil hydrogenation metal remover, wax oil hydrogenation desulfurizing agent and wax oil hydrogenation
Agent is purchased from Sinopec catalyst Chang Ling branch company, and the filling ratio of height to diameter of catalyst is 14 in tubular reactor）In, in table 1
Contacted under conditions of shown with hydrogenation catalyst, wax oil after being hydrogenated with, its property is listed in table 2.
Comparative example 1
Hydrotreating is carried out to wax oil raw material using method same as Example 1, unlike, in air and liquid mixer
Component is the pipeline that is formed by porous material, and the average pore size in the hole on the tube wall of the pipeline is 5 μm, porosity 35%, aperture
The ratio for accounting for total hole in the hole in 5-5.5 μ ms is 95%（It is public commercially available from Tianyuan environment engineering finite responsibility in Beijing
Department）.
The property of wax oil is listed in table 2 after obtained hydrogenation.
Comparative example 2
This comparative example carries out hydrotreating using trickle bed hydrogenation technique to feedstock oil, uses fixed bed reactors, reaction
According to the flow direction of logistics in device, according to 1：2：4：3 volume ratio loads wax oil hydrogenation protective agent, the board that the trade mark is RG-20 successively
The wax oil hydrogenation desulfurizing agent that number the wax oil hydrogenation metal remover for being RDM-32 and the trade mark are RVS-420, the trade mark are RDA-30 wax
Oily hydrogenation dearomatization catalyst.Wherein, the filling ratio of height to diameter of catalyst is 4.
Concrete operations flow is：By feedstock oil and hydrogen in SV type static mixers（Have purchased from Shanghai Shanghai dragon petrochemical industry project
Limit company）In be well mixed.Obtained mixture is sent into from the tops of fixed bed reactors, under conditions of table 1 is listed with
Hydrogenation catalyst contacts, and carries out hydrogenation reaction, wax oil after being hydrogenated with from the bottom of fixed bed reactors, its property is in table 2
List.
Comparative example 3
Hydrotreating is carried out to wax oil using with the identical method of comparative example 2, unlike, reaction condition is as shown in table 1.
The property of wax oil is listed in table 2 after obtained hydrogenation.
Table 1
| Reaction condition | Embodiment 1 | Comparative example 2 | Comparative example 3 |
| Reaction pressure, MPa | 14.0 | 14.0 | 14.0 |
| Reaction velocity, h-1 | 1.6 | 1.6 | 0.8 |
| Reaction temperature, DEG C | 370 | 370 | 370 |
| Hydrogen to oil volume ratio, V/V | 90 | 90 | 500 |
Table 2
Embodiment 2
Hydrotreating is carried out to wax oil raw material using method same as Example 1, difference is as follows.
（1）The wax oil raw material used in the present embodiment is coking wax slop, and its property is listed in table 4.
（2）Component in air and liquid mixer is membrane tube as shown in Figure 3（It is public commercially available from Tianyuan environment engineering finite in Beijing
Department；The average pore size in the hole on matrix is 100 μm；The average pore size in the hole on perforated membrane is 500nm, and aperture is on perforated membrane
The ratio for accounting for total hole in the hole in the range of 500-550nm is 95%；The porosity of perforated membrane is 25%）；Perforated membrane is located at membrane tube
On outer wall；7 passages are evenly distributed with, the internal diameter of each fluid passage is 6mm；Using the passage in membrane tube as fluid passage,
Using the space that the inwall of the outer wall of membrane tube and housing is formed as gas passage, the filling rate of membrane tube in the housing is 50%.
（3）The injection rate of hydrogen is 0.008 with the ratio of flowing velocity of the wax oil in fluid passage.
（4）The service condition of tubular reactor is listed in table 3.
The property of obtained hydrogenation wax oil is listed in table 4.
Table 3
| Reaction pressure, MPa | 16.0 |
| Reaction velocity, h-1 | 2.0 |
| Reaction temperature, DEG C | 370 |
| Hydrogen to oil volume ratio, V/V | 150 |
Table 4
| Project | Coking wax slop raw material | Embodiment 2 |
| Density/kg/m3 | 955.3 | 919.8 |
| Initial boiling point/DEG C | 327 | 315 |
| 10%/℃ | 464 | 438 |
| 30%/℃ | 487 | 479 |
| Less than 520 DEG C ends contents/weight % | 38.5 | 45.5 |
| Carbon/weight % | 87.17 | 87.03 |
| Hydrogen/weight % | 10.98 | 12.38 |
| Total sulfur/weight % | 1.12 | 0.33 |
| Total nitrogen/weight % | 0.73 | 0.26 |
| Alkali nitrogen/wppm | 1824 | 756 |
| Saturated hydrocarbons/weight % | 52.9 | 63.4 |
| Aromatic hydrocarbon/weight % | 35.6 | 33.8 |
| Colloid/weight % | 11.2 | 2.6 |
| Asphalitine/weight % | 0.3 | 0.2 |
| Carbon residue/weight % | 3.2 | 1.0 |
| Metal/wppm | 17.2 | 1.5 |
Embodiment 3
Hydrotreating is carried out to wax oil raw material using method same as Example 1, difference is as follows.
（1）The wax oil raw material used in the present embodiment is visbreaking wax oil, and its property is listed in table 6.
（2）Component in air and liquid mixer is membrane tube as shown in Figure 2（It is public commercially available from Tianyuan environment engineering finite in Beijing
Department；The average pore size in the hole on matrix is 100 μm；The average pore size in the hole on perforated membrane is 250nm, and aperture is on perforated membrane
The ratio for accounting for total hole in the hole in the range of 250-260nm is 95%；The porosity of perforated membrane is 25%）；Perforated membrane is located at membrane tube
On inwall；7 passages are evenly distributed with, the internal diameter of each fluid passage is 6mm；Using the passage in membrane tube as fluid passage,
Using the space that the inwall of the outer wall of membrane tube and housing is formed as gas passage, filling rate is 65% to membrane tube in the housing.
（3）The ratio of the internal diameter of the internal diameter of the material outlet of air and liquid mixer and the material inlet of tubular reactor is
0.85, the internal diameter of the material outlet of air and liquid mixer enters with the material of the material outlet and tubular reactor that are connected air and liquid mixer
The ratio of the internal diameter of the pipeline of mouth is 1.
（4）The injection rate of hydrogen is 0.008 with the ratio of flowing velocity of the wax oil in fluid passage.
（5）The service condition of tubular reactor is listed in table 5.
The property of obtained hydrogenation wax oil is listed in table 6.
Table 5
| Reaction pressure, MPa | 13.0 |
| Reaction velocity, h-1 | 3.0 |
| Reaction temperature, DEG C | 385 |
| Hydrogen to oil volume ratio, V/V | 120 |
Table 6
| Project | Visbreaking wax oil raw material | Embodiment 3 |
| Density/kg/m3 | 912.5 | 894.5 |
| Initial boiling point/DEG C | 229 | 204 |
| 10%/℃ | 367 | 337 |
| 50%/℃ | 409 | 385 |
| 95%/℃ | 446 | 439 |
| Carbon/weight % | 86.57 | 86.75 |
| Hydrogen/weight % | 11.73 | 12.81 |
| Total sulfur/weight % | 0.95 | 0.23 |
| Total nitrogen/weight % | 0.75 | 0.21 |
| Basic nitrogen/wppm | 3328 | 685 |
| Saturated hydrocarbons/weight % | 64.8 | 70.3 |
| Aromatic hydrocarbon/weight % | 30.9 | 28.1 |
| Colloid/weight % | 4.2 | 1.5 |
| Asphalitine/weight % | 0.1 | 0.1 |
| Carbon residue/weight % | 0.8 | 0.2 |
| Metal/wppm | 7.5 | 1.1 |
Embodiment 1-3's as a result, it was confirmed that using the present invention method to wax oil carry out hydrotreating, even if with low hydrogen/gasoline ratio
And carried out under high-speed, it also can effectively remove sulphur, the nitrogen in wax oil（Including basic nitrogen）, metal and carbon residue, satisfy simultaneously
With part aromatic hydrocarbons, increase the hydrogen content of wax oil.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of wax oil hydrogenation processing method, this method comprise the steps of：By average pore size it is nano-scale by hydrogen
Hole be sent into temperature be 330-420 DEG C and wax oil raw material that pressure is 4-20MPa in, obtain hydrogeneous wax oil, the feeding amount of hydrogen
Volume ratio with the wax oil is 30-180；The hydrogeneous wax oil is sent into tubular reactor in a manner of flowing up,
Contacted under liquid-phase hydrogenatin treatment conditions with the hydrogenation catalyst being seated in the tubular reactor.
2. according to the method for claim 1, wherein, the average pore size is that the average pore size in the hole of nano-scale is 1-
1000nm。
3. according to the method for claim 1, wherein, by hydrogen feeding temperature be 330-420 DEG C and pressure is 10-20MPa
Wax oil in.
4. the method according to claim 1 or 3, wherein, the feeding amount of hydrogen and the volume ratio of the wax oil are 90-150.
5. according to the method described in any one in claim 1-3, wherein, hydrogen is injected into institute by a kind of air and liquid mixer
State in wax oil, so as to obtain the hydrogeneous wax oil, the air and liquid mixer includes at least one liquid for being used to accommodate the wax oil
Body passage and at least one gas passage for being used to accommodate the hydrogen, pass through between the fluid passage and the gas passage
One component abuts, and the component at least partially has a porose area, described to have porose area to have the average pore size for nano-scale
Hole, the hydrogen are injected into the wax oil by the average pore size for the hole of nano-scale.
6. according to the method for claim 5, wherein, the component is the pipeline with least one passage, the pipeline
Tube wall on there is through hole, the through hole is the hole that average pore size is nano-scale；Or the inwall of the passage of the pipeline and/
Or perforated membrane is attached with the outer wall of pipeline, the tube wall of the pipeline has a through hole, and the hole on the perforated membrane is average pore size
For the hole of nano-scale.
7. according to the method for claim 6, wherein, the air and liquid mixer also includes housing, and the housing has gas
Entrance, liquid inlet and liquid outlet, the housing are internally provided with least one pipeline, the outer wall of the pipeline with
Existential Space between the inwall of the housing, passage on the pipeline as the fluid passage, the outer wall of the pipeline with
The space that the inwall of the housing is formed as the gas passage, the both ends of the fluid passage respectively with the liquid inlet
Connected with the liquid outlet, the gas passage connects with the gas access.
8. according to the method for claim 5, wherein, the air and liquid mixer is arranged on the entrance of the tubular reactor
End.
9. according to the method for claim 1, wherein, the wax oil is straight-run gas oil, wax tailings, visbreaking wax oil and de- drip
One or more in blue or green wax oil.
10. according to the method for claim 1, wherein, the ratio of height to diameter of the tubular reactor is 5-200：1.
11. according to the method for claim 1, wherein, the liquid-phase hydrogenatin treatment conditions include：Temperature is 330-420 DEG C,
Pressure is 4-20MPa, and the volume space velocity of the hydrogeneous wax oil is 0.5-5h-1。
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Citations (4)
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|---|---|---|---|---|
| US4857168A (en) * | 1987-03-30 | 1989-08-15 | Nippon Oil Co., Ltd. | Method for hydrocracking heavy fraction oil |
| CN101132854A (en) * | 2004-11-16 | 2008-02-27 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| CN101992048A (en) * | 2009-08-11 | 2011-03-30 | 中国石化集团洛阳石油化工工程公司 | Reactor and application thereof to hydrocarbon oil liquid-solid two-phase hydrogenation |
| CN102120934A (en) * | 2010-01-12 | 2011-07-13 | 中国石油化工集团公司 | Circulating liquid phase hydrogenation method |
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2014
- 2014-03-21 CN CN201410108494.5A patent/CN104927902B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857168A (en) * | 1987-03-30 | 1989-08-15 | Nippon Oil Co., Ltd. | Method for hydrocracking heavy fraction oil |
| CN101132854A (en) * | 2004-11-16 | 2008-02-27 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| CN101992048A (en) * | 2009-08-11 | 2011-03-30 | 中国石化集团洛阳石油化工工程公司 | Reactor and application thereof to hydrocarbon oil liquid-solid two-phase hydrogenation |
| CN102120934A (en) * | 2010-01-12 | 2011-07-13 | 中国石油化工集团公司 | Circulating liquid phase hydrogenation method |
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