CN104927903B - A kind of process for hydrogenating residual oil - Google Patents
A kind of process for hydrogenating residual oil Download PDFInfo
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- CN104927903B CN104927903B CN201410108855.6A CN201410108855A CN104927903B CN 104927903 B CN104927903 B CN 104927903B CN 201410108855 A CN201410108855 A CN 201410108855A CN 104927903 B CN104927903 B CN 104927903B
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Abstract
The invention provides a kind of process for hydrogenating residual oil, including：Hydrogen is sent into residual oil raw material by average pore size for the hole of nano-scale, obtains hydrogeneous residual oil；The hydrogeneous residual 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, tenor, sulfur content and the carbon residue of residual oil can be also effectively reduced, obtains preferable hydrotreating effect, while the resin and asphalt content of residual oil can also be reduced.Also, the method for the present invention can reduce the trend of catalyst green coke, catalyst is kept higher catalytic activity, extend the service life of catalyst, so as to extend the stable operation cycle of hydrogenation plant.
Description
Technical field
The present invention relates to a kind of process for hydrogenating residual oil.
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 residual oil maximum, maximizing the benefits turn into oil refining and looked forward to
The target that industry is pursued.
One of the important means of residual hydrocracking technology as current processing of heavy oil, it cannot be only used for producing high quality
Light Fuel and petrochemical materials, also it can provide quality raw materials for secondary processing process.Residual hydrocracking technology can be divided into
Fixed bed, ebullated bed, suspension bed and the type of moving bed four, wherein fixed bed hydrogenation technology are easily operated because its technique is simple
And developed rapidly.But the property of residual oil is poor, density is big, viscosity is big, carbon residue is high, hydrogen-carbon ratio is low and tenor is high, because
And during hydrotreating is carried out to residual oil using fixed bed hydrogenation technique, due to the deposition and carbon deposit of metal, easily
Catalyst inactivation is caused, bed pressure drop raises, and device is short service cycle.
For above mentioned problem existing for fixed bed hydrogenation technique, researcher proposes many improved methods.
US6554994B1 discloses a kind of method of metal reduced in heavy charge, carbon residue and sulphur impurity, this method
Including in the presence of hydrogen gas, making heavy charge flow upwardly through fixed bed reactors, there is lower catalytic in fixed bed reactors
Agent bed and upper catalyst bed layer, wherein, the hydrogenation activity of the catalyst in the lower catalyst bed layer is urged less than top
The hydrogenation activity of catalyst in agent bed, wherein, heavy charge and hydrogen is evenly distributed on the transversal of beds
On face；Make heavy charge and hydrogen simultaneously with sufficiently low speed, so that the average ratio of beds is no more than 5%.
CN101519603B discloses the hydrotreating method of a kind of high-sulfur, high-metal residual oil, and this method is included residual oil
With catalytic cracking recycle oil in presence of hydrogen with hydroprocessing condition, contacted with residual oil hydrocatalyst carry out hydrotreating
Reaction, separation reaction product obtain gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue, wherein, residual oil hydrocatalyst is
The combination of at least two catalyst, i.e. up-flow reactor catalyst and fixed bed hydrogenation catalyst, and upstream is seated in respectively
In formula reactor and fixed bed reactors, the filling ratio of the up-flow reactor catalyst and fixed bed hydrogenation catalyst is
30：70-70：30；The up-flow reactor catalyst is a kind of oval ball catalyst, the major semiaxis a of the oval ball
Ratio with semi-minor axis b is 1.05-2.5, and 3-8 bar grooves, the groove are provided with along major semiaxis a directions on the oval ball
Depth be b/8-2b/3；The up-flow reactor catalyst, on the basis of the gross weight of catalyst and in terms of oxide, molybdenum
And/or the content of tungsten is 0.5-15 weight %, the content of cobalt and/or nickel is 0.3-8 weight %, and surplus is alumina support；It is described
Alumina support is a kind of alumina support in bimodal hole, and its pore volume is 0.8-1.6 mls/g, specific surface area 150-350
Rice2/ gram, aperture accounts for the 40-90% of total pore volume in the pore volume of 10-30 nanometers, and aperture accounts for total pore volume in the pore volume of 100-2000 nanometers
10-50%.
CN1990834B discloses a kind of process for hydrogenating residual oil, and this method includes feedstock oil and hydrogen mixing is laggard
Enter hydrogenation protecting reactor, carry out being hydrogenated with removing impurities qualitative response, hydrogenation protecting reactor outlet from bottom to up by beds
Logistics is directly entered fixed bed finishing reactor without isolation, carries out hydrofining reaction, wherein, divide in hydrogenation protecting reactor
Section is filled with two or more catalyst, and catalyst has identical carrier, the active metal of the catalyst of bottom filling
Load capacity is lower than the active metal load capacity of adjacent upper catalyst agent, and the reaction condition of the hydrogenation protecting reactor is：Hydrogen
Partial pressure 10-20MPa, 340-440 DEG C of average reaction temperature, hydrogen to oil volume ratio 200-1200Nm3/m3, volume space velocity 0.1- during liquid
3h-1。
CN102465034A discloses a kind of processing method of poor residuum, and this method comprises the following steps：
（1）By residual oil and optional heavy distillate and the optional catalytic cracked oil pulp for isolating solid dust, in hydrogen
In the presence of gas, into up-flow reactor, contacted with up flow type hydrogenation catalyst and carry out hydrotreating reaction, intermediate reaction product
Without isolation；
（2）Step（1）After obtained intermediate reaction product mixes with catalytic cracking recycle oil, into trickle bed reactor,
Contacted with hydrotreating catalyst and carry out hydrotreating reaction, the reaction product for separating trickle bed reactor obtains gas, hydrogenation
Naphtha, hydrogenated diesel oil and hydrogenated residue；
（3）Step（2）The hydrogenated residue of gained enters catalytic cracking unit together with optional vacuum gas oil (VGO), in cracking
Cracking reaction is carried out in the presence of catalyst, separation reaction product obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking bavin
Oil, catalytic cracking recycle oil and catalytic cracked oil pulp, the catalytic cracking recycle oil of gained are recycled to trickle bed reactor entrance.
Although with the residual hydrocracking technique of up-flow reactor, due to the expansion of beds, in certain journey
The service life of catalyst is extended on degree, but greatly and needs that is run under low-speed to ask there are still hydrogen gas consumption
Topic.
The content of the invention
It is an object of the invention to overcome hydrogen gas consumption existing for existing residual hydrocracking technique big and need
The technical problem run under low-speed, there is provided a kind of process for hydrogenating residual oil, residual oil is handled using this method, even if
Carry out with relatively low hydrogen-oil ratio and at a high space velocity, can also obtain preferable hydrotreating effect.
The invention provides a kind of process for hydrogenating residual oil, this method includes：By average pore size it is nanometer by hydrogen
The hole of size is sent into residual oil raw material, obtains hydrogeneous residual oil；The hydrogeneous residual oil is sent into tubular reactor, in liquid-phase hydrogenatin
Contacted under treatment conditions with the hydrogenation catalyst being seated in the tubular reactor.
Residual oil is handled using the method for the present invention, even if with relatively low hydrogen-oil ratio and at a high space velocity,
Tenor, sulfur content and the carbon residue of residual oil can be effectively reduced, obtains preferable hydrotreating effect, while can also reduce
The resin and asphalt content of residual oil.
Also, use the method for the present invention to be sent into hydrogen in residual oil raw material for the hole of nano-scale by average pore size,
More hydrogen can be dissolved in residual oil raw material, undissolved hydrogen can be then highly dispersed in residual oil raw material, such energy
Enough ensure that hydrogenation reaction is carried out in the liquid phase, improve hydrogenation reaction speed, reduce the trend of catalyst green coke, keep catalyst
Higher catalytic activity, extend the service life of catalyst, so as to extend the stable operation cycle of hydrogenation plant.The side of the present invention
Method can also obtain preferably hydrogenation effect without recycle oil and/or flux oil, improve the effective treating capacity 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 process for hydrogenating residual oil of the present invention.
Fig. 6 is the another embodiment of the process for hydrogenating residual oil of the present invention.
Fig. 7 is another embodiment of the process for hydrogenating residual oil 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：Residual oil raw material 4：Tubular reactor
5：Ring flange 6：Ring flange
7：Ring flange 8：Ring flange
9：Residual oil after hydrogenation
Embodiment
The invention provides a kind of process for hydrogenating residual oil, this method includes：By average pore size it is nanometer by hydrogen
The hole of size is sent into residual oil raw material, obtains hydrogeneous residual oil；It is anti-that the hydrogeneous residual oil is sent into tubular type in a manner of flowing up
Answer in device, contacted under liquid-phase hydrogenatin treatment conditions 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 residual oil raw material, and then enable hydrogen faster more equal
The angle being dispersed in evenly in the residual oil raw material is set out, and the quantity in the hole that aperture is in the range of 50-500nm accounts for total hole number
Ratio be more than 95%, such as 95-98%.
It can be the residual oil original that hydrogen injection can also be in flow regime in static residual oil raw material by hydrogen injection
In material.It is preferred that hydrogen injection is in the residual oil raw material of flow regime, so can be while residual oil raw material be transported, by hydrogen
In gas injection residual oil raw material, so as to obtain the production efficiency further improved.Hydrogen injection is being in the residual oil of flow regime
When in raw material, the injection rate of the hydrogen is v1And with gh-1·m-2（Represent within the unit interval, by unit area
The total amount of the hydrogen in hole）Meter, the flow velocity of the residual oil raw material is v2And with kgh-1·m-2（Represent unit section in the unit interval
On the quality of residual oil raw material that passes through）Meter, v1/v2Preferably 0.000625-0.09, it can so obtain the hydrogen further improved
Qi leel dissipates solute effect.It is highly preferred that v1/v2=0.005-0.06（Such as 0.005-0.01）, the hydrogen that can not only so obtain
Qi leel dissipates solute effect, and can obtain higher production efficiency.
Various methods can be used to inject hydrogen in the residual oil raw material for the hole of nano-scale by average pore size.
In the preferred embodiment of the present invention, hydrogen is injected into the residual oil raw material by a kind of air and liquid mixer
In, the air and liquid mixer include it is at least one be used for accommodate the residual oil raw material fluid passage and it is at least one be used for accommodate
The gas passage of the hydrogen, abutted between the fluid passage and the gas passage by a component, the component is extremely
Small part is has porose area, and the hole for having porose area that there is the average pore size to be nano-scale, the hydrogen passes through described average
Aperture is injected into the residual oil raw material for the hole of nano-scale.In the present invention, term " fluid passage " is to refer to accommodate slag
The space of oily raw material；Term " 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 residual oil raw material）.It is described to have hole
Area has the hole that the average pore size is nano-scale, so that hydrogen passes through the hole quilt with average pore size for nano-scale
Inject in the residual oil raw material.The porosity for having porose area is preferably 5-75%, so can preferably divide enough hydrogen
Dissipate and be dissolved in residual oil raw material.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 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 residual oil raw material in the fluid passage.In an example, the structure
Part is formed by porous material, and the average pore size in hole therein is nano-scale.In another example, the component includes matrix
And attachment perforated membrane on the matrix, described matrix have a through hole, the perforated membrane can be located at described matrix with
It is contained on the surface of the residual oil raw material contact in the fluid passage, can also be positioned at described matrix with being contained in the gas
On the surface of hydrogen contact in body passage.Preferably, the perforated membrane is located at leading to being contained in the liquid for described matrix
On the surface of residual oil raw material contact in road.Hole in the perforated membrane is that previously described average pore size is nano-scale
Hole.The average pore size of through hole in described matrix is not particularly limited, as long as can pass through gas.Preferably, the base
The average pore size of through hole on body 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 residual oil raw material, 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
The gas passage of hydrogen；Or the passage on the component is as the gas passage for accommodating hydrogen, the structure
The space that the inwall of the outer wall of part and the housing is formed is as the fluid passage for accommodating residual oil raw material.Preferably,
Passage on the component is as the fluid passage for accommodating residual oil raw material, the outer wall of the component and the housing
The space that inwall is formed is as the gas passage for accommodating 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 residual oil raw material, the outer wall of the component with
When the space that the inwall of the housing is formed is as being used to accommodate the gas passage of hydrogen, as shown in figure 4, can be in housing
Gas access 11, liquid inlet 12 and liquid outlet 13 be set on 14, the both ends of the fluid passage respectively with liquid inlet 12
Connected with liquid outlet 13, the gas passage connects with gas access 11.Hydrogen is sent into housing 14 by gas access 11
In, residual oil raw material is sent into the passage of component 10, in the presence of pressure differential, hydrogen is passed through described in the hole entrance on tube wall
In residual oil raw material, so as to obtain hydrogeneous residual 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 residual oil chemical interaction will not occur for the material into the component.
The amount for the hydrogen being sent into the residual oil raw material can be selected according to the impurity content in the residual oil raw material.
In existing 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.The present invention
The hole of method nano-scale that hydrogen is passed through into average pore size be sent into the residual oil raw material, hydrogen high degree of dispersion can be made simultaneously
It is dissolved in the residual oil raw material, so as to provide enough hydrogen sources for hydrogenation reaction；Also, in the method for the present invention, hydrogenation is anti-
It should in the liquid phase carry out, reaction heat can be taken out of in time.Therefore, even if method of the invention, which reduces, is sent into the residual oil raw material
In amounts of hydrogen, can also obtain good hydrotreating effect, and reduce the trend of catalyst green coke.According to the inventive method,
The feeding amount of the hydrogen and the volume ratio of the residual oil raw material（That is, hydrogen to oil volume ratio）Can be 30-120, preferably 70-
100。
With the method for the invention it is preferred to hydrogen is sent into the residual oil raw material of heating, hydrogen so can be made preferably
Dissolve and be dispersed in residual oil raw material, and be also beneficial to transporting for residual oil raw material.Preferably, hydrogen is sent into temperature and pressure
In the residual oil raw material under hydrogenation temperature and hydrogenation pressure, it so can further reduce what hydrogen escaped from hydrogeneous residual oil
Trend.Specifically, hydrogen can be sent into the residual oil raw material that temperature is 330-450 DEG C and pressure is 4-20MPa.
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 residual 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 residual 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 residual 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 residual 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 330-450 DEG C, and pressure can be 4-20MPa（Such as 10-20MPa）.The hydrogeneous residual oil
Air speed can also be conventional selection.The method of the present invention, even if the hydrogeneous residual oil is urged with higher air speed by the hydrogenation
Agent, it can also obtain preferably hydrogenation effect.Therefore, the volume space velocity of hydrogeneous residual oil is preferably 0.5- in method of the invention
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 residual oil raw material, to obtain hydrogeneous residual oil, and will be hydrogeneous
The internal diameter for the outlet for being used to export hydrogeneous residual oil when residual oil is sent into tubular reactor, on the air and liquid mixer is r1, it is described anti-
The internal diameter for answering the entrance for being used for inputting hydrogeneous residual oil on device is r2, r1/r2=0.6-1.Connect the pipe of the outlet and the entrance
Internal diameter be r3, r1/r3=0.85-1.5（Such as 0.85-1）.So hydrogeneous residual oil is more stable in transport process, can obtain
Preferably hydrogenation effect.
The method of the present invention can carry out hydrotreating to the residual oil in various sources.Usually, in the residual oil raw material
Residual oil can be reduced crude and/or decompression residuum.
The residual oil raw material can be with all residual oil.Preferably, the residual oil also contains at least one flux oil, such energy
The viscosity of residual oil is enough reduced, obtains more preferable hydrotreating effect.The flux oil can be that conventional various can reduce slag
The oil of the viscosity of oil.Preferably, the flux oil is not higher than 450mm in 100 DEG C of viscosity2/ s, it can so obtain more preferable
Hydrogenation effect.The viscosity uses method specified in GB265-88 to determine.The flux oil can be specifically selected from but unlimited
In coking wax slop, catalytic cracked oil pulp, FCC recycle oil, visbreaking light oil, visbreaker tar and deasphalted oil.The flux oil
Content can be selected according to the property of flux oil and residual oil.Usually, it is described on the basis of the total amount of the residual oil raw material
The content of residual oil can be 50-98 weight %, and the content of the flux oil can be 2-50 weight %.
The hydrogenation catalyst can be the various catalyst with hydrogenation catalyst effect that residual 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 residual oil raw material 3 in clutch 1, obtains hydrogeneous residual oil.Hydrogeneous residual oil enters in tubular reactor 4 urges with hydrogenation
Agent contacts, so as to carry out hydrogenation reaction, residual oil 9 after being hydrogenated with.According to the embodiment, multiple pipe reactions can be set
Device, can be to be connected in series between multiple tubular reactors, or be connected in parallel, can also be series connection and group in parallel
Close.When multiple tubular reactors are connected in series, along the flow direction of material, air and liquid mixer can be arranged on to first pipe
The arrival end of formula reactor；Can also be as shown in fig. 6, the arrival end in each tubular reactor 4 sets air and liquid mixer respectively
1.When multiple tubular reactors are connected in parallel, an air and liquid mixer can be only set, residual oil raw material is mixed with hydrogen, so
Obtained hydrogeneous residual oil is respectively fed to afterwards in multiple tubular reactors for being connected in parallel；Can also be as shown in Figure 7 in each pipe
The arrival end of formula reactor 4 sets air and liquid mixer 1 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.
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.
In following examples and comparative example, pressure is in terms of gauge pressure.
Embodiment 1-3 is used for the method for illustrating the present invention.
Embodiment 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 present embodiment carries out hydrotreating using the method shown in Fig. 5 to residual oil raw material.Wherein, the structure of air and liquid mixer
As shown in figure 4, the structure for being used to abut the component of fluid passage and gas passage in air and liquid mixer is to be formed by porous material
Pipeline（Commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, 19 passages, each passage are evenly distributed with pipeline
Internal diameter be 3.3mm, the average pore size in the hole on tube wall is 50nm, and accounting for for the hole number that aperture is in the range of 50-55nm is total
The ratio of hole number is 98%, and the porosity of tube wall is 20%）；Passage on pipeline is as fluid passage, the outer wall and shell of pipeline
The space that the inwall of body is formed is as gas passage, and filling rate is 60% to pipeline in the housing.
Temperature in the fluid passage of air and liquid mixer is 370 DEG C, pressure 13MPa.The material outlet of air and liquid mixer
Internal diameter and the ratio of internal diameter of material inlet of tubular reactor be 1, the internal diameter of the material outlet of air and liquid mixer and connection
The ratio of the internal diameter of the pipeline of 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 residual oil raw material by air and liquid mixer（Wherein, the flow velocity and residual 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 residual oil raw material is with kgh-1·m-2
Meter）, obtain hydrogeneous residual oil.Hydrogeneous residual 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 1：4：3 volume ratio is loaded residual hydrogenation protective agent, residuum hydrogenating and metal-eliminating agent and residual hydrogenation and taken off successively
Sulphur agent, wherein, residual hydrogenation protective agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent are purchased from Sinopec catalyst
Chang Ling branch company, the trade mark are respectively RG-20, RDM-32 and RMS-1, and the filling ratio of height to diameter of catalyst is 14 in tubular reactor）
In, contacted under the conditions shown in Table 1 with hydrogenation catalyst, residual oil after being hydrogenated with, its property is listed in table 2.
Comparative example 1
Hydrotreating is carried out to residual 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 residual 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 1：4：3 volume ratio loads residual hydrogenation protective agent, the trade mark that the trade mark is RG-20 successively
The residuum hydrodesulfurization agent for being RMS-1 for RDM-32 residuum hydrogenating and metal-eliminating agent and the trade mark, wherein, the filling Gao Jing of catalyst
Than for 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, residual 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 residual oil using with the identical method of comparative example 2, unlike, reaction condition is as shown in table 1.
The property of residual oil is listed in table 2 after obtained hydrogenation.
Table 1
| Reaction condition | Embodiment 1 | Comparative example 2 | Comparative example 3 |
| Reaction pressure, MPa | 13.0 | 13.0 | 13.0 |
| Reaction velocity, h-1 | 2.0 | 2.0 | 0.8 |
| Reaction temperature, DEG C | 370 | 370 | 370 |
| Hydrogen to oil volume ratio, V/V | 75 | 75 | 500 |
Table 2
Embodiment 2
Hydrotreating is carried out to residual oil raw material using method same as Example 1, difference is as follows.
（1）The residual oil raw material used in the present embodiment is reduced crude, 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%）；7 are evenly distributed with to lead to
Road, the internal diameter of each fluid passage is 6mm；Using the passage in membrane tube as fluid passage, by the outer wall and housing of membrane tube
The space that wall is formed is as gas passage, and filling rate is 50% to membrane tube in the housing.
（3）The injection rate of hydrogen is 0.008 with the ratio of flowing velocity of the residual oil in fluid passage.
（4）The service condition of tubular reactor is listed in table 3.
The property of obtained hydrogenated residue is listed in table 4.
Table 3
| Reaction pressure, MPa | 13.0 |
| Reaction velocity, h-1 | 3.0 |
| Reaction temperature, DEG C | 370 |
| Hydrogen to oil volume ratio, V/V | 90 |
Table 4
Embodiment 3
Hydrotreating is carried out to residual oil raw material using method same as Example 1, difference is as follows.
（1）The residual oil raw material used in the present embodiment is decompression residuum, 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%）；7 are evenly distributed with to lead to
Road, the internal diameter of each fluid passage is 6mm；Using the passage in membrane tube as fluid passage, by the outer wall and housing of membrane tube
The space that wall is formed is as gas passage, and 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
0.62, 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 residual oil in fluid passage.
（5）The service condition of tubular reactor is listed in table 5.
The property of obtained hydrogenated residue is listed in table 6.
Table 5
| Reaction pressure, MPa | 13.0 |
| Reaction velocity, h-1 | 2.0 |
| Reaction temperature, DEG C | 380 |
| Hydrogen to oil volume ratio, V/V | 90 |
Table 6
Embodiment 1-3's as a result, it was confirmed that using the present invention method to residual oil carry out hydrotreating, even if with low hydrogen/gasoline ratio
And carried out under high-speed, it also can effectively remove sulphur, metal and the carbon residue in residual oil.On the contrary, using existing trickle bed
Hydrogenation technique is handled residual oil, it is necessary to run with higher hydrogen-oil ratio and under low-speed, could obtain preferably hydrogenation
Effect.Also can be to add even if the result of embodiment 2 and 3 is also shown that the method for the present invention does not apply to flux oil and/or recycle oil
Hydrogen reaction provides enough hydrogen, the hydrogenation effect obtained, so as to effectively improve the effective treating capacity of hydrogenation plant.
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 (12)
1. a kind of process for hydrogenating residual oil, this method include：It is by average pore size in a kind of air and liquid mixer by hydrogen
The hole of nano-scale is sent into the residual oil raw material that temperature is 330-450 DEG C and pressure is 4-20MPa, obtains hydrogeneous residual oil, hydrogen
The volume ratio of feeding amount and the residual oil raw material be 30-120；The hydrogeneous residual oil is sent into tubular type in a manner of flowing up
In reactor, contacted under liquid-phase hydrogenatin treatment conditions with the hydrogenation catalyst being seated in the tubular reactor, it is described to connect
Touch and carried out under conditions of in the absence of recycle oil.
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, the feeding amount of hydrogen and the volume ratio of the residual oil raw material are 70-
100。
4. according to the method described in any one in claim 1-3, wherein, the air and liquid mixer includes at least one be used for
Accommodate the residual oil raw material fluid passage and it is at least one be used to accommodating the gas passage of the hydrogen, the fluid passage and
Abutted between the gas passage by a component, the component at least partially has a porose area, and described to have porose area to have described
Average pore size is the hole of nano-scale, and the hydrogen is injected into the residual oil original by the average pore size for the hole of nano-scale
In material.
5. according to the method for claim 4, 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.
6. according to the method for claim 5, 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.
7. according to the method for claim 4, wherein, the air and liquid mixer is arranged on the entrance of the tubular reactor
End.
8. according to the method for claim 1, wherein, the residual oil in the residual oil raw material is reduced crude and/or decompression slag
Oil.
9. according to the method for claim 1, wherein, the ratio of height to diameter of the tubular reactor is 5-200：1.
10. according to the method for claim 1, wherein, the liquid-phase hydrogenatin treatment conditions include：Temperature is 330-450 DEG C,
Pressure is 4-20MPa, and the volume space velocity of the hydrogeneous residual oil is 0.5-5h-1。
11. according to the method described in any one in claim 1,3,8 and 10, wherein, the residual oil raw material is residual oil, or
The residual oil raw material contains residual oil and at least one flux oil, the flux oil be selected from coking wax slop, catalytic cracked oil pulp,
FCC recycle oil, visbreaking light oil, visbreaker tar and deasphalted oil.
12. according to the method for claim 11, wherein, on the basis of the total amount of the residual oil raw material, the residual oil contains
Measure as 50-98 weight %, the content of the flux oil is 2-50 weight %.
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| CN111523194B (en) * | 2019-02-04 | 2023-11-07 | 南京大学 | Modeling method of reaction rate and conversion rate regulation model under MIHA pure pneumatic operation condition |
| CN112705119B (en) * | 2019-10-25 | 2022-06-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation reactor and hydrogenation method |
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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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Patent 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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