CN104927920B - A kind of residuum coking method - Google Patents
A kind of residuum coking method Download PDFInfo
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- CN104927920B CN104927920B CN201410108476.7A CN201410108476A CN104927920B CN 104927920 B CN104927920 B CN 104927920B CN 201410108476 A CN201410108476 A CN 201410108476A CN 104927920 B CN104927920 B CN 104927920B
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Abstract
The invention provides a kind of residuum coking method, the method includes contacting heavy catalytic cycle oil and hydrogen with hydrogenation catalyst, to carry out hydrogenation reaction, heavy catalytic cycle oil after being hydrogenated with；Heavy catalytic cycle oil after the hydrogenation is mixed with residual oil, the mixture for obtaining is carried out coking.Residuum coking method according to the present invention is mixed with residual oil after heavy catalytic cycle oil is hydrogenated with carries out coking, can significantly improve liquid product yield.
Description
Technical field
The present invention relates to a kind of residuum coking method.
Background technology
At present, in order to reduce heavy, poor residuum processing cost, increase oil refining enterprise's profit, coking process be still plus
Work inferior heavy oil（Particularly residual oil）Main Means.Delayed coking has as a kind of ripe scheme of Residual cracking route
Raw material wide accommodation, conversion ratio are higher, and project investment is few, and work flow is short, are provided simultaneously with the multiple sump oils of freshening, operating cost
Low advantage, through the technological improvement of decades and perfect, has obtained significant progress, it has also become oil plant balance heavy oil production
Important process.
In coking plant production, the main target of operation and design is that liquid yield is maximized, and reduces coke output, production
Gasoline, diesel oil and wax oil that suitable downstream unit is processed.But, the liquid yield of existing coking process is generally 70 weight %
Left and right, needs further to improve, and the coke value for obtaining is low.Therefore, constantly employ new technology, optimize operation, do
Good residual oil deep processing, increases liquid product yield, and there is weight to the overall economic efficiency for lifting coking plant or even whole refinery
The meaning that wants.
CN1560198A discloses a kind of additive for improving delayed coking unit yield of light oil, and the additive is by as follows
Group is grouped into：
Wherein, the thermal cracking active substance is that molecular weight is common with oxypropylene block for the Polyethylene oxide of 5000-12000
Poly- block polyether, C8-C12Any one in alkylphenol polyoxyethylene sulphonic acid ester, anhydrous sorbitol APEO sulphonic acid ester
Kind；
The radical chain reaction inhibitor is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propanoic acid] tetramethylolmethane
Ester, β-(3,5- di-tert-butyl-hydroxy phenyls) propanoic acid octadecanol ester, N- phenyl-a-naphthylamine, double dodecyl diphenylamines,
Any one in styryl octyl diphenylamine, phenyl phosphites；
The antiscorching is sulfenic acids amide-type（Wherein, R1、R2、R3It is C8-C12Alkane
Base）、C6-C10Any in alkylated phenol, DBPC 2,6 ditertiary butyl p cresol, styrenated phenol, N- nitroso-groups-Phenyl beta naphthylamine
A kind of；
The solvent is kerosene or diesel oil.
The method adopts pure chemicals as the additive for improving yield of light oil, relatively costly.
Content of the invention
It is an object of the invention to overcoming the not high technical problem of liquid yield of existing slag oil coking process, there is provided one
Residuum coking method is planted, the method can obtain the liquid yield for improving without using relatively costly additive.
The invention provides a kind of residuum coking method, the method is included heavy catalytic cycle oil and hydrogen and hydrogenation
Catalyst is contacted, to carry out hydrogenation reaction, heavy catalytic cycle oil after being hydrogenated with；Catalytic cracking after the hydrogenation is followed again
Ring oil is mixed with residual oil, and the mixture for obtaining is carried out coking.
Residuum coking method according to the present invention is mixed with residual oil after heavy catalytic cycle oil is hydrogenated with carries out coking, energy
Liquid product yield is enough significantly improved.
Description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.
Fig. 1 is used for the structure for schematically illustrating to adjoin fluid passage and gas passage in the air and liquid mixer for using of the invention
A kind of preferred implementation of part.
A kind of cross-sectional view of components of the Fig. 2 shown in Fig. 1.
Another kind of cross-sectional view of components of the Fig. 3 shown in Fig. 1.
Fig. 4 is the structural representation of the air and liquid mixer that the present invention is used.
Fig. 5 is a kind of preferred implementation for carrying out hydrotreating in the method for the present invention to heavy catalytic cycle oil.
Fig. 6 is the another kind side of being preferable to carry out for carrying out hydrotreating in the method for the present invention to heavy catalytic cycle oil
Formula.
Fig. 7 is another side of being preferable to carry out for carrying out hydrotreating in the method for the present invention to heavy catalytic cycle oil
Formula.
Fig. 8 is used for the annexation between air and liquid mixer and tubular reactor to be described.
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：Heavy catalytic cycle oil 4：Tubular reactor
5：Ring flange 6：Ring flange
7：Ring flange 8：Ring flange
9：Heavy catalytic cycle oil after hydrogenation
Specific embodiment
The invention provides a kind of residuum coking method, the method is included heavy catalytic cycle oil and hydrogen and hydrogenation
Catalyst is contacted, to carry out hydrogenation reaction, heavy catalytic cycle oil after being hydrogenated with；Catalytic cracking after the hydrogenation is followed again
Ring oil is mixed with residual oil, and the mixture for obtaining is carried out coking.
After conventional various methods can be adopted by heavy catalytic cycle oil and hydrogen mixing, in common various reactions
Contact with hydrogenation catalyst in device, to carry out hydrogenation reaction.For example：Can by heavy catalytic cycle oil and hydrogen mixing after with
Hydrogenation catalyst is contacted in fixed bed reactors, suspended-bed reactor, fluidized bed reactor or moving-burden bed reactor, from
And carry out hydrogenation reaction.
The present invention a kind of preferred embodiment in, by average pore size for nano-scale hole by hydrogen send into urge
Change in cracking heavy-cycle oil, obtain hydrogeneous heavy-cycle oil；The hydrogeneous heavy-cycle oil is sent in tubular reactor, and is seated in
Hydrogenation catalyst in the tubular reactor is contacted under liquid-phase hydrogenatin treatment conditions.Using this preferred embodiment, energy
Enough more hydrogen are dissolved in heavy catalytic cycle oil, undissolved hydrogen can then be highly dispersed at catalytic cracking and follow again
In ring oil, enough hydrogen is provided for hydrogenation reaction so that hydrogenation reaction is carried out in the liquid phase, on the one hand improve hydrogenation reaction
Speed and efficiency, on the other hand reduce the trend of catalyst coking, extend the service life of catalyst.The liquid-phase hydrogenatin is processed
Refer to that continuous phase under hydroprocessing conditions is liquid phase, whole or substantially all gas phase is disperseed in the liquid phase as dispersion phase.
According to this preferred embodiment, hydrogeneous heavy-cycle oil can send into tubular reactor in the way of flowing up
In, it is also possible to sent in tubular reactor in the way of flowing downward.Preferably, by the hydrogeneous heavy-cycle oil flowing up
Mode send in tubular reactor, so during the course of the reaction, dissolve and be dispersed in the hydrogen in heavy-cycle oil and substantially will not
Aggregation forms big bubble and escapes, even if under relatively low hydrogen-oil ratio, also can provide enough hydrogen sources for hydrogenation reaction, obtains
Preferably hydrotreating effect, and the further trend of reduction catalyst green coke, makes catalyst keep higher catalysis activity, enters
One step extends the service life of catalyst, so as to further extend the stable operation cycle of hydrogenation plant.
In the present invention, the average pore size can typically be 1nm to 1000nm for the average pore size in the hole of nano-scale, excellent
Elect 30nm to 1000nm, more preferably more preferably 30nm to 800nm, 50nm to 500nm as（Such as 50nm to 300nm）.
The average pore size is determined using scanning electron microscope method.
From further raising dispersion mixing of the hydrogen in the heavy catalytic cycle oil, and then enable hydrogen
The angle faster spreaded more evenly across in the heavy catalytic cycle oil is set out, hole of the aperture in the range of 50-500nm
Quantity account for total hole number ratio be more than 95%, such as 95-98%.
Can be in static heavy catalytic cycle oil by hydrogen injection, it is also possible to which hydrogen injection is in flow regime
Heavy catalytic cycle oil in.It is preferred that hydrogen injection so can in the heavy catalytic cycle oil of flow regime
While heavy catalytic cycle oil is transported, by hydrogen injection heavy catalytic cycle oil, so as to further be improved
Production efficiency.
Can adopt various methods that hydrogen is injected the catalytic cracking by average pore size for the hole of nano-scale to follow again
In ring oil.
In the preferred embodiment of the present invention, hydrogen is injected into the catalytic cracking by a kind of air and liquid mixer
In heavy-cycle oil, the air and liquid mixer include at least one for accommodate the heavy catalytic cycle oil fluid passage and
At least one for accommodating the gas passage of the hydrogen, adjacent by a component between the fluid passage and the gas passage
Connect, the component at least partially has a porose area, the hole for having porose area that there is the average pore size to be nano-scale, the hydrogen
Hole of the gas by the average pore size for nano-scale is injected in the heavy catalytic cycle oil.
In the present invention, term " fluid passage " is the space for referring to accommodate heavy catalytic cycle oil；" gas leads to term
Road " is the space for referring to housing hydrogen gas.
The component at least partially has a porose area, and described have porose area to extend along the length direction of the component.Preferably,
Described have porose area to cover whole component（That is, by with the average pore size between described fluid passage and the gas passage
Component for the hole of nano-scale is adjoined, and the hydrogen is injected in the heavy catalytic cycle oil by the hole）.
Described have porose area have the average pore size be nano-scale hole so that hydrogen by described with average pore size be nanometer chi
Very little hole is injected in the heavy catalytic cycle oil.The porosity for having porose area is preferably 5-75%, so can be by foot
The hydrogen of amount is preferably dispersed and dissolved in heavy catalytic cycle oil.The porosity for having porose area is more preferably 25-
45%.The porosity refers to that the pore volume in porose area occupies the percent of the cumulative volume of porose area, is surveyed using nitrogen adsorption methods
Fixed.
The component for the various hydrogen that can make to be contained in the gas passage by the average pore size can be
The hole of nano-scale and the component that enters in the heavy catalytic cycle oil being contained in the fluid passage.In an example
In, the component has loose structure, and the average pore size in hole therein is nano-scale.In another example, the component
Including matrix and attachment perforated membrane on the matrix, described matrix has through hole, and the perforated membrane may be located at described
On the surface contacted with the heavy catalytic cycle oil being contained in the fluid passage of matrix, it is also possible to positioned at described matrix
The surface contacted with the hydrogen being contained in the gas passage on.Preferably, the perforated membrane be located at described matrix with
It is contained on the surface of the heavy catalytic cycle oil contact in the fluid passage.Hole in the perforated membrane is described previously
Average pore size for nano-scale hole.The average pore size of the through hole in described matrix is not particularly limited, as long as can pass through
Gas.Preferably, the average pore size of the through hole in described matrix 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 the component is adjacent.
In one embodiment of the invention, the component is the pipeline with least one passage.The pipeline
There is on tube wall hole, and the average pore size in the hole is previously described nano-scale.
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 through hole, on the perforated membrane
Hole be average pore size for nano-scale hole, 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.The membrane tube has the pipeline of through hole using on tube wall 101 as base
Body, pipeline have at least one passage 102, are attached with porous on the outer wall of the inwall and/or pipeline 101 of the passage 102 of pipeline
Film 103.The average pore size of the through hole on tube wall is not particularly limited, as long as pass through can hydrogen, typically can be for 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 passage on the pipeline or 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, deposits between the inwall for being internally provided with pipeline described at least one, the outer wall of the pipeline and the housing 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 component 10 outer wall and housing 14 inwall between Existential Space.Passage on the component is used as holding
Receive the fluid passage of heavy catalytic cycle oil, the space conduct that the inwall of the outer wall of the component and the housing is formed
For accommodating the gas passage of hydrogen；Or, the passage on the component leads to as the gas for accommodating hydrogen
Road, the space that the inwall of the outer wall of the component and the housing is formed is used as accommodating described in heavy catalytic cycle oil
Fluid passage.Preferably, the passage on the component is used as the fluid passage for being used for accommodating heavy catalytic cycle oil, institute
The space of inwall formation of the outer wall and the housing of component is stated as the gas passage for being used for accommodating hydrogen.
Filling rate of the component in the housing can typically be 10-75%（Such as 30-60%）.The filling rate is referred to
Space and the percent value of the total measurement (volume) of housing that component is occupied.
Passage on the members is used as the fluid passage for being used for accommodating heavy catalytic cycle oil, the component
Outer wall and the housing the space that formed of inwall as accommodate hydrogen the gas passage when, as shown in figure 4, can
To arrange gas access 11, liquid inlet 12 and liquid outlet 13 on housing 14, the two ends of the fluid passage respectively with liquid
Body entrance 12 is connected with liquid outlet 13, and the gas passage is connected with gas access 11.Hydrogen is sent by gas access 11
Enter in housing 14, heavy catalytic cycle oil is sent in the passage of component 10, in the presence of pressure differential, hydrogen is made by pipe
Hole on wall is entered in the heavy catalytic cycle oil, so as to obtain hydrogeneous heavy-cycle oil.
The material for forming the component can be inorganic material（Such as inorganic ceramic）, or organic material, as long as shape
Material into the component will not occur chemical interaction with hydrogen and heavy catalytic cycle oil.
With the method for the invention it is preferred to hydrogen be sent in the heavy catalytic cycle oil of heating, can so make hydrogen
Gas preferably dissolves and is dispersed in heavy catalytic cycle oil, and is also beneficial to transporting for heavy catalytic cycle oil.Excellent
Selection of land, hydrogen is sent in the heavy catalytic cycle oil that temperature and pressure is under hydrogenation temperature and hydrogenation pressure, such energy
The trend that enough further reduction hydrogen is escaped from hydrogeneous heavy-cycle oil.Specifically, it is 280-400 that hydrogen can be sent into temperature
℃（Such as 320-380 DEG C）And pressure is 4-20MPa（Such as 6-12MPa）Heavy catalytic cycle oil in.
The tubular reactor is referred to the reactor compared with larger ratio of height to diameter.Specifically, the height of the tubular reactor
Ratio with internal diameter（That is, ratio of height to diameter）Can be 15-200：1（Such as 20-120：1）.The internal diameter of the tubular reactor can be
Conventional selection, for example, can be 20-2000mm.Compared with tank reactor, on the one hand can be reduced using tubular reactor anti-
The volume of device is answered, is 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, flexible operation and side
Just.
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 it is connected in parallel, may be used also
Think to connect and combine with parallel.Described be connected in series the hydrogenation for referring to the output of previous tubular reactor after logistics be the next one
The charging of tubular reactor；Described being connected in parallel is referred between tubular reactor without material exchange.
Using previously described air and liquid mixer by hydrogen injection heavy catalytic cycle oil, to obtain hydrogeneous recirculating
Oil, and when hydrogeneous heavy-cycle oil is sent into tubular reactor, be used for exporting going out for hydrogeneous heavy-cycle oil on the air and liquid mixer
The internal diameter of mouth is r1, on the reactor be used for be input into hydrogeneous heavy-cycle oil entrance internal diameter be r2, r1/r2=0.6-1.Connection
The internal diameter of the pipe of the outlet and the entrance is r3, r1/r3=0.85-1.5（Such as 0.9-1.2）.So hydrogeneous heavy-cycle oil exists
More stable in transport process such that it is able to obtain preferably hydrogenation effect.
The method according to the invention, the amount for sending into the hydrogen in heavy catalytic cycle oil can be according to specific hydrogenation work
Skill is selected.Usually, hydrogen can be 60-1000 with the volume ratio of heavy catalytic cycle oil：1.In hydrogen and catalysis
When cracking heavy-cycle oil is carried out in conventional fixed bed reactors with the contact of catalyst, hydrogen and heavy catalytic cycle oil
Volume ratio can be 800-1000：1.Hydrogen is being sent into by heavy catalytic cycle oil using previously described preferred implementation
In and when contacting with hydrogenation catalyst, as hydrogen preferably can dissolve and be dispersed in heavy catalytic cycle oil, be plus
Hydrogen reaction provides enough hydrogen sources and can be effectively prevented catalyst green coke, even if therefore also can under relatively low hydrogen usage
Good hydrotreating effect and longer catalyst service life are enough obtained.Usually, it is preferable to carry out using previously described
Send in heavy catalytic cycle oil and contact with hydrogenation catalyst in hole of the mode by hydrogen by average pore size for nano-scale
When, hydrogen can be 60-600 with the volume ratio of heavy catalytic cycle oil：1, preferably 120-280：1（Such as 200-250：1）.
The method according to the invention, the degree of the hydrogenation reaction can be carried out according to the source of heavy catalytic cycle oil
Select.Preferably, total chemical hydrogen consumption amount of the hydrogenation reaction be 0.5-4 weight %, aromatic hydrogenation reaction chemical hydrogen consumption amount be
0.3-3.6 weight %.It is highly preferred that total chemical hydrogen consumption amount of the hydrogenation reaction is 1-2 weight %, the chemistry of aromatic hydrogenation reaction
Hydrogen consumption is 0.9-1.95 weight %, is so obtained in that the liquid product yield for further improving.In the present invention, hydrogenation reaction
Total chemical hydrogen consumption amount for hydrodesulfurization hydrogen consumption, hydrodenitrogeneration hydrogen consumption, aromatic hydrogenation hydrogen consumption and cracking hydrogen consumption total
With conventional various methods can be adopted to determine.
The hydrogen consumption of hydrogenation reaction can be made by the condition of adjustment hydrogenation reaction to be within above range.Specifically
Ground, is obtained in that the hydrogen consumption for meeting above-mentioned requirements under the following conditions：Temperature can be 280-400 DEG C, preferably 320-380
℃；In terms of gauge pressure, pressure can be 4-20MPa, preferably 6-12MPa；Air speed can be 0.1-3h-1.Herein, such as not special
Illustrate, pressure is gauge pressure.Hydrogen and heavy catalytic cycle oil with the contact of catalyst in conventional fixed bed reactors
When carrying out, air speed can be 0.1-0.4h-1.Hole feeding catalytic cracking by hydrogen by average pore size for nano-scale is recirculated
In oil and send into when carrying out hydrogenation reaction in tubular reactor, even if hydrogeneous heavy-cycle oil is with higher volume space velocity, such as 0.5-
3h-1, hydrotreating effect expected from acquisition is also ensured that by hydrogenation catalyst bed, the volume of the hydrogeneous heavy-cycle oil is empty
Speed is preferably 0.5-1.5h-1（Such as 1-1.5h-1）.
The heavy catalytic cycle oil refers to that catalytic cracking generates the component that boiling range in oil is more than 350 DEG C.Preferably,
The heavy catalytic cycle oil is that boiling range is 350-450 DEG C in catalytic cracking generation oil（1 standard atmosphere is depressed）Component, will
There is the heavy catalytic cycle oil of the boiling range mix with residual oil after being hydrogenated with carries out coking and is obtained in that higher liquid product
Thing yield.
The hydrogenation catalyst can be the conventional various Hydrobon catalysts in hydrocarbon oil hydrogenation field.Usually, described
Hydrogenation catalyst contains carrier and loads vib metals on the carrier and group VIII metal, the vib
Metal is preferably molybdenum and/or tungsten, and the group VIII metal is preferably cobalt and/or nickel.The vib metals and group VIII
Metal load capacity on the carrier can be selected according to the species of hydrogenation catalyst.Usually, urged with the hydrogenation
On the basis of the total amount of agent and in terms of oxide, the content of the vib metals can be 1-15 weight %, the VIII
The content of race's metal can be 0.5-8 weight %.The carrier can be the heat-resisting of the various carriers for being adapted as hydrogenation catalyst
Inorganic oxide, such as silicon oxide and/or aluminium oxide.Can also be loaded with the carrier of the hydrogenation catalyst conventional various
Auxiliary agent, is no longer described in detail herein.
Fig. 5 show in the method for the present invention one kind side of being preferable to carry out for carrying out hydrotreating to heavy catalytic cycle oil
Formula.In the preferred implementation, hydrogen 2 is injected in heavy catalytic cycle oil 3 in air and liquid mixer 1, obtained hydrogeneous
Heavy-cycle oil.Hydrogeneous heavy-cycle oil is entered and is contacted with hydrogenation catalyst in tubular reactor 4, so as to carry out hydrogenation reaction.According to
The embodiment, can arrange multiple tubular reactors, can be to be connected in series between multiple tubular reactors, or and
Connection connection, can also be combined with parallel for series connection.When multiple tubular reactors are for being connected in series, along the flowing side of material
To air and liquid mixer can be arranged on the arrival end of first tubular reactor；Can also be as shown in fig. 6, in each tubular type
The arrival end of reactor 4 is respectively provided with air and liquid mixer 1.When multiple tubular reactors are for being connected in parallel, one can be only arranged
Individual air and liquid mixer, heavy catalytic cycle oil is mixed with hydrogen, is then respectively fed to simultaneously the hydrogeneous heavy-cycle oil for obtaining
In multiple tubular reactors of connection connection；Gas-liquid can also be respectively provided with as shown in Figure 7 in the arrival end of each tubular reactor 4
Blender 1.
Can adopt and in various manners air and liquid mixer is connected on the entrance pipe of tubular reactor, for example：Can be
The two ends of air and liquid mixer 1 respectively arrange a ring flange（Fig. 8 is shown in which a ring flange 5）, each with corresponding entrance
Flangeseal connection on pipeline（As shown in figure 8, the ring flange 6 on the ring flange 5 and entrance pipe of air and liquid mixer one end
It is tightly connected）；The other end of entrance pipe is connected with the ring flange 8 of the arrival end of tubular reactor 4 by ring flange 7.
The residual oil can be the residual oil in various sources, can be reduced crude and/or decompression residuum.
The method according to the invention, after hydrogenation, the consumption of heavy catalytic cycle oil can be selected according to the species of residual oil
Select.Usually, relative to residual oil described in 100 weight portions, after the hydrogenation, the content of heavy catalytic cycle oil can be 0.5-
30 weight portions.Preferably, relative to residual oil described in 100 weight portions, after the hydrogenation, the content of heavy catalytic cycle oil is 1-5
Weight portion（Such as 1-3 weight portions）, the yield of gasoline and diesel oil can be so greatly improved, in reduction product liquid, wax oil contains
Amount, so that obtain the product liquid with more high added value.
The method of the present invention is not particularly limited for the method and condition of coking, can be the conventional selection of this area.
Preferably, the coking is delayed coking.The condition of the coking can be selected according to specific coking method.According to this
Heavy catalytic cycle oil after hydrogenation is mixed by the method for invention with residual oil carries out coking, on the one hand can be at a higher temperature
Coking is carried out, on the other hand can reduce the recycle ratio of coking, so can effectively extend the stable operation week of coking plant
Phase.Specifically, when coking is carried out using delay coking process, the temperature of the delayed coking can be 495-510 DEG C, pressure
Can be 0.1-0.3MPa, recycle ratio can be 0-0.3.
Describe the method for the present invention with reference to embodiments in detail, but be not so limited the scope of the present invention.
The method of testing that uses in following examples and comparative example is as shown in table 1 below.
Table 1
In following examples and comparative example, be compare incorporation heavy catalytic cycle oil or hydrogenation after catalytic cracking follow again
Impact before and after ring oil to dry gas yield, liquid product yield or coking yield during coking, introduces contribution rate Δ, and which defines
For：
ΔR=(MR- TR× α)/(1- α)-ZR
Wherein, R：Dry gas yield, liquid product yield or coking yield；
Δ：Contribution rate；
M：Yield during coking is carried out after mixing heavy catalytic cycle oil or hydrogenation after heavy catalytic cycle oil；
Z：Residual oil individually carries out yield during coking；
T：Yield when heavy catalytic cycle oil individually carries out coking after heavy catalytic cycle oil or hydrogenation；
α：The incorporation of heavy catalytic cycle oil after heavy catalytic cycle oil or hydrogenation.
Contribution rate（Δ）Numerical value bigger, the raising of the yield for showing to be conducive to the product.
Embodiment 1-13 is used for the method for the present invention to be described.
Embodiment 1-5
The property of the heavy catalytic cycle oil used in embodiment 1-5 is listed in table 3, the hydrogenation catalyst for using by
Hunan Changling Petrochemical S＆T Development Co., Ltd. produces, and the trade mark is DC-301.
（1）The hydrogenation reaction of heavy catalytic cycle oil
In embodiment 1-5, by heavy catalytic cycle oil and hydrogen in SV type static mixers（Purchased from Shanghai Shanghai dragon petrochemical industry
Engineering Co., Ltd）Middle mix homogeneously.The mixture for obtaining is sent into by tubular fixed-bed reactor（Internal diameter is 28mm, highly
For 1500mm, the filling of catalyst is highly 800）Top send into, contact with hydrogenation catalyst under conditions of table 2 is listed,
Hydrogenation reaction is carried out, the hydrogenated oil that obtains and the property as the heavy catalytic cycle oil of raw material are listed in table 3.
（2）Pyrogenetic reaction
By 5 weight portion steps（1）After the hydrogenation for obtaining, heavy catalytic cycle oil is mixed with 100 weight portion decompression residuum,
After the mixture for obtaining is heated in heating furnace, sending in coking tower carries out coking, obtains oil gas product and coke, and oil gas is produced
Thing is entered and is separated in fractionating column, obtains gaseous product and product liquid.Wherein, the temperature in coking tower is 500 DEG C, pressure
For 0.1MPa, scorch time is 2h, and the recycle ratio in coking tower is 0.The result of the test of pyrogenetic reaction is listed in table 4.
Comparative example 1
Using with 1 step of embodiment（2）Identical method carries out coking, except for the difference that, uses the catalysis as raw material to split
Change heavy-cycle oil and replace heavy catalytic cycle oil after hydrogenation.
The result of the test of pyrogenetic reaction is listed in table 4.
Table 2
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Pressure（MPa） | 8 | 6 | 8 | 12 | 14 |
| Temperature（℃） | 350 | 360 | 370 | 360 | 380 |
| Total air speed（h-1） | 0.4 | 0.1 | 0.15 | 0.2 | 0.25 |
| Hydrogen to oil volume ratio | 800 | 1200 | 600 | 600 | 1000 |
Table 3
Table 4
| Project | Decompression residuum | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Gas recovery ratio, w% | 11.66 | 10.43 | 10.01 | 9.97 | 9.86 | 10.76 | 10.64 |
| Liquid yield, w% | 59.49 | 62.45 | 64.76 | 65.12 | 65.68 | 63.99 | 60.58 |
| Coking yield, w% | 28.85 | 27.12 | 25.23 | 24.91 | 24.46 | 25.25 | 28.78 |
| Δ gas, w% | - | -0.77 | -1.22 | -1.26 | -1.37 | -0.43 | -0.52 |
| Δ liquid, w% | - | 1.25 | 3.68 | 4.06 | 4.65 | 2.87 | 1.22 |
| Δ coke, w% | - | -0.48 | -2.47 | -2.80 | -3.28 | -2.45 | -0.69 |
From the results shown in Table 4, mixing with residual oil after be hydrogenated with heavy catalytic cycle oil carries out coking, can obtain
The liquid yield of get Geng Gao.Wherein, the total chemical hydrogen consumption in hydrogenation reaction is the chemical hydrogen that 1-2 weight % and aromatic hydrogenation react
When consumption is 0.9-1.95 weight %, higher liquid yield is obtained in that.
Embodiment 6-9
After hydrogenation prepared by embodiment 4, heavy catalytic cycle oil is mixed in decompression residuum in the ratio that table 5 is listed,
Table 5 carries out coking under conditions of listing.The result of coking experiment is listed in table 5.
Table 5
From the results shown in Table 5, carrying out coking to residual oil using the method for the present invention can reduce Jiao in product
Carbon content, obtains higher liquid product yield.As can also be seen from Table 5, after hydrogenation heavy catalytic cycle oil interpolation
Measure for 1-3 weight % when, the higher product liquid of petrol and diesel oil content can be obtained.
Embodiment 10
The property of the heavy catalytic cycle oil used in the present embodiment is listed in table 6.
Hydrogenation catalyst used in the present embodiment is the trade mark the adding for RDA-32 of sinopec Chang Ling catalyst plant production
Hydrogen catalyst.
（1）The hydrogenation reaction of heavy catalytic cycle oil
The present embodiment carries out hydrotreating using the method shown in Fig. 6 to heavy catalytic cycle oil.
Wherein, the structure of air and liquid mixer is as shown in figure 4, be used for adjoining fluid passage and gas passage in air and liquid mixer
The structure of component be the pipeline formed by porous material（Commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd；Pipeline
On be evenly distributed with 19 passages, the internal diameter of each passage is 3.3mm, and the average pore size in the hole on tube wall is 50nm, at aperture
The ratio for accounting for total hole number of the hole number in the range of the 50-55nm is 98%, and the porosity of tube wall is 20%）；By on pipeline
, used as fluid passage, the space that the inwall of the outer wall of pipeline and housing is formed is used as gas passage for passage；The pipeline is in shell
Filling rate in body is 45%.
In the present embodiment, the temperature in the fluid passage of air and liquid mixer is 280 DEG C, and pressure is 16MPa.
In the present embodiment, the internal diameter of the material inlet of the internal diameter and tubular reactor of the liquid material outlet of air and liquid mixer
Ratio be 1, the internal diameter and the material outlet and pipe reaction for being connected air and liquid mixer of the outlet of the liquid material of air and liquid mixer
The ratio of the internal diameter of the pipeline of the material inlet of device is 1.
Concrete operations are as follows.
Hydrogen is injected by air and liquid mixer in heavy catalytic cycle oil, hydrogeneous heavy-cycle oil is obtained.Will be hydrogeneous heavy
Recycle oil sends into tubular fixed-bed reactor by bottom（Internal diameter is 28mm, and length is 3000mm）In, under the conditions shown in Table 6
With hydrogenation catalyst（Catalyst filling in the reactor is highly 1300mm）Contact, at the top of tubular fixed-bed reactor
Heavy catalytic cycle oil after being hydrogenated with, its property are listed in table 7.
（2）Pyrogenetic reaction
By 5 weight portion steps（1）After the hydrogenation for obtaining, heavy catalytic cycle oil is mixed with 100 weight portion decompression residuum,
After the mixture for obtaining is heated in heating furnace, sending in coking tower carries out coking, obtains oil gas product and coke, and oil gas is produced
Thing is entered and is separated in fractionating column, obtains gaseous product and product liquid.Wherein, the temperature in coking tower is 505 DEG C, pressure
For 0.12MPa, scorch time is 2.0h, and the recycle ratio in coking tower is 0.The result of the test of pyrogenetic reaction is listed in table 8.
Embodiment 11
（1）Heavy catalytic cycle oil hydrogenation reaction
Heavy catalytic cycle oil is hydrogenated with using method same as in Example 10, except for the difference that：Will be hydrogeneous heavy
Recycle oil is sent into by the top of tubular fixed-bed reactor, is contacted with hydrogenation catalyst under conditions of same as in Example 10,
Hydrogenation reaction is carried out, heavy catalytic cycle oil after the bottom of fixed bed reactors is hydrogenated with, its property are arranged in table 7
Go out.
（2）Pyrogenetic reaction
Using method same as in Example 10 by step（1）After the hydrogenation for obtaining, heavy catalytic cycle oil mixing is laggard
Row coking.The result of the test of pyrogenetic reaction is listed in table 8.
Embodiment 12
（1）The hydrogenation reaction of heavy catalytic cycle oil
Heavy catalytic cycle oil is hydrogenated with using method same as in Example 10, except for the difference that, gas-liquid mixed
Component in device is the pipeline formed by porous material, and the average pore size in the hole on the tube wall of the pipeline is 5 μm, and porosity is
35%, the ratio for accounting for total hole in hole of the aperture in 5-5.5 μ ms is 95%（Commercially available from Tianyuan environment engineering finite in Beijing
Responsible company）.After the hydrogenation for obtaining, the property of heavy catalytic cycle oil is listed in table 7.
（2）Using method same as in Example 10 by step（1）Heavy catalytic cycle oil mixing after the hydrogenation for obtaining
After carry out coking.The result of the test of pyrogenetic reaction is listed in table 8.
Embodiment 13
（1）The hydrogenation reaction of heavy catalytic cycle oil
Heavy catalytic cycle oil is hydrogenated with using method same as in Example 10, except for the difference that, in air and liquid mixer
Component be membrane tube as shown in Figure 3（Commercially available from Tianyuan Genie et Environnement in Beijing；The average pore size in the hole on matrix
For 100 μm；The average pore size in the hole on perforated membrane is 250nm, and on perforated membrane, hole of the aperture in the range of 250-260nm accounts for
The ratio in total hole is 95%；The porosity of perforated membrane is 25%）；Perforated membrane is located on the outer wall of membrane tube；It is evenly distributed with 37 to lead to
Road, the internal diameter of each fluid passage is 3.8mm, and membrane tube filling rate in the housing is 50%.
In the present embodiment, the temperature in the fluid passage of air and liquid mixer is 320 DEG C, and pressure is 16.0MPa.
In the present embodiment, the ratio of the internal diameter of the material outlet of air and liquid mixer and the internal diameter of the material inlet of tubular reactor
Be worth for 0.77, the internal diameter of the material outlet of air and liquid mixer be connected the material outlet of air and liquid mixer and the thing of tubular reactor
The ratio of the internal diameter of the pipeline of material entrance is 1.
Concrete operations are as follows.
Hydrogen is injected by air and liquid mixer in heavy catalytic cycle oil, hydrogeneous heavy-cycle oil is obtained.Will be hydrogeneous heavy
Recycle oil sends into tubular fixed-bed reactor by bottom（With embodiment 10）In, under the conditions shown in Table 6 with hydrogenation catalyst
Contact, heavy catalytic cycle oil after being hydrogenated with the top of tubular fixed-bed reactor, its property are listed in table 7.
（2）Pyrogenetic reaction
Using method same as in Example 10 by step（1）After the hydrogenation for obtaining, heavy catalytic cycle oil mixing is laggard
Row coking.The result of the test of pyrogenetic reaction is listed in table 8.
Table 6
| Project | Embodiment 10 | Embodiment 13 |
| Pressure（MPa） | 16 | 16 |
| Temperature（℃） | 375 | 365 |
| Total air speed（h-1） | 1.5 | 1.5 |
| Hydrogen to oil volume ratio | 200 | 240 |
Table 7
Table 8
| Project | Decompression residuum | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Gas recovery ratio, w% | 11.66 | 10.01 | 11.51 | 11.2 | 10.67 |
| Liquid yield, w% | 59.49 | 64.76 | 61.37 | 62.68 | 63.42 |
| Coking yield, w% | 28.85 | 25.23 | 27.12 | 26.12 | 25.91 |
| Δ gas, w% | - | -1.22 | 0.36 | 0.04 | -0.52 |
| Δ liquid, w% | - | 3.68 | 0.64 | 1.49 | 2.27 |
| Δ coke, w% | - | -2.47 | -0.92 | -1.45 | -1.75 |
Embodiment 10 and embodiment 11 are compared as can be seen that by the side by hydrogeneous heavy-cycle oil to flow up
Formula is sent in tubular reactor, is obtained in that the liquid product yield of preferably hydrogenation effect and Geng Gao.
Claims (13)
1. a kind of residuum coking method, the method include contacting heavy catalytic cycle oil and hydrogen with hydrogenation catalyst, with
Hydrogenation reaction is carried out, heavy catalytic cycle oil after being hydrogenated with, total chemical hydrogen consumption amount of the hydrogenation reaction is 0.5-4 weights
Amount %, the chemical hydrogen consumption amount of aromatic hydrogenation reaction is 0.3-3.6 weight %, and the heavy catalytic cycle oil is that catalytic cracking is given birth to
Into in oil, boiling range is more than 350 DEG C of component；Heavy catalytic cycle oil after the hydrogenation is mixed with residual oil, mixed by obtained
Compound carries out coking, and relative to residual oil described in 100 weight portions, after the hydrogenation, the content of heavy catalytic cycle oil is 1-3 weights
Amount part.
2. method according to claim 1, wherein, total chemical hydrogen consumption amount of the hydrogenation reaction is 1-2 weight %, aromatic hydrocarbons
The chemical hydrogen consumption amount of hydrogenation reaction is 0.9-1.95 weight %.
3. method according to claim 1, wherein, heavy catalytic cycle oil and hydrogen is contacted with hydrogenation catalyst
Method includes：Hydrogen is sent in heavy catalytic cycle oil by hole of the average pore size for nano-scale, obtain hydrogeneous heavy follow
Ring oil；The hydrogeneous heavy-cycle oil is sent in tubular reactor, with the hydrogenation catalyst being seated in the tubular reactor
Contact under liquid-phase hydrogenatin treatment conditions.
4. hydrogen wherein, is injected the catalytic cracking weight by a kind of air and liquid mixer by method according to claim 3
In recycle oil, so as to obtain the hydrogeneous heavy-cycle oil, the air and liquid mixer includes that at least one is used for accommodating the catalysis
The fluid passage of cracking heavy-cycle oil and at least one is used for accommodating the gas passage of the hydrogen, the fluid passage and described
Adjacent by a component between gas passage, the component at least partially has porose area, and described to have the porose area to have described average
Hole of the aperture for nano-scale, hole of the hydrogen by the average pore size for nano-scale are injected into the catalytic cracking weight
In recycle oil.
5. method according to claim 4, wherein, the component is the pipeline with least one passage, the pipeline
Tube wall on have through hole, the through hole be average pore size for nano-scale hole；Or the inwall of the passage of the pipeline and/
Or perforated membrane on the outer wall of pipeline, is attached with, the tube wall of the pipeline has through hole, and the hole on the perforated membrane is average pore size
Hole for nano-scale.
6. method according to 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 pipeline described at least one, the outer wall of the pipeline with
Existential Space between the inwall of the housing, the 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 two ends of the fluid passage respectively with the liquid inlet
Connect with the liquid outlet, the gas passage is connected with the gas access.
7. the method according to any one in claim 4-6, wherein, it is anti-that the air and liquid mixer is arranged on the tubular type
Answer the arrival end of device.
8. the method according to any one in claim 3-6, wherein, the average pore size is the flat of the hole of nano-scale
Aperture is 1-1000nm.
9. method according to claim 3, wherein, the ratio of height to diameter of the tubular reactor is 15-200：1.
10. the method according to any one in claim 1-6 and 9, wherein, hydrogen and the heavy catalytic cycle oil
Volume ratio be 60-600；1, the contact is carried out under conditions of temperature is 280-400 DEG C and pressure is 4-20MPa, during liquid
Volume space velocity is 0.1-3h-1.
11. methods according to claim 1, wherein, the residual oil is reduced crude and/or decompression residuum.
12. methods according to claim 1, wherein, the coking is delayed coking.
13. methods according to claim 12, wherein, the condition of the delayed coking includes：Temperature is 495-510 DEG C,
Pressure is 0.1-0.3MPa, and recycle ratio is 0-0.3.
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| EP0462823A1 (en) * | 1990-06-21 | 1991-12-27 | MOBIL OIL CORPORATION (a New York corporation) | Resid desulfurization and demetalation |
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Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: CHANGLING BRANCH, CHINA PETROLEUM CHEMICAL Corp. Patentee after: Hunan Changlian New Material Technology Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: CHANGLING BRANCH, CHINA PETROLEUM CHEMICAL Corp. Patentee before: HUNAN CHANGLING PETROCHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. |