CN110117503A - The combinational processing method of FCC recycle oil - Google Patents
The combinational processing method of FCC recycle oil Download PDFInfo
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- CN110117503A CN110117503A CN201810116282.XA CN201810116282A CN110117503A CN 110117503 A CN110117503 A CN 110117503A CN 201810116282 A CN201810116282 A CN 201810116282A CN 110117503 A CN110117503 A CN 110117503A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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Abstract
The present invention relates to refining arts, disclose a kind of combinational processing method of FCC recycle oil, it is characterized in that, the combinational processing method includes: in the presence of hydrogenation catalyst, FCC recycle oil is contacted with hydrogen and carries out liquid-phase hydrogenatin, it will be in obtain plus hydrogen recycle oil incorporation residual hydrogenation raw material, catalytically cracked material, delayed coking raw material and catalytic cracking production.This method makes the abundant high value added utilization of FCC recycle oil resource, widens FCC recycle oil utilization ways, realizes efficient industrial production.
Description
Technical field
The present invention relates to refining arts, and in particular to a kind of combinational processing method of FCC recycle oil.
Background technique
FCC recycle oil is component relatively light in catalytic cracked oil pulp, 350 DEG C -500 DEG C of boiling range are a kind of components with
Based on condensed-nuclei aromatics, the inferior heavy oil comprising mixtures such as alkane, asphalitine, colloid and a small amount of catalyst powders.Currently, refinery is
Optimization production operation, directly returns it into riser recracking.Part monocycle, double ring arene are removed in fragrance point in recycle oil
Outside the cracking performance having had, mostly short-side chain condensed-nuclei aromatics, cracking performance is poor, is sent into FCC apparatus cracking, will increase device and add
Work difficulty increases gas and coke yield；Sulfur-containing compound in recycle oil will affect product quality, make under the octane number of gasoline
Drop increases SOx discharge in regenerator flue gas；Nitrogenate especially basic nitrogen compound can make the selectivity and activity drop of catalyst
It is low, cause coking yield to improve, conversion ratio reduces；The activity and selectivity that metal (Ni, V etc.) also will affect catalyst, makes coke
Increase with gas yield, FCC recycle oil is not particularly well suited for as catalytic cracking feeds.The recycle oil overwhelming majority is got rid of outside as weight
The burn-up of matter fuel oil, not only wastes petroleum resources, but also cause environmental pollution.Therefore, exploitation FCC recycle oil efficiently utilizes way
Diameter, reasonable utilization FCC recycle oil resource, helps to improve the economic benefit of oil refining enterprise.
CN104593059 A discloses a kind of FCC recycle oil hydrogenation method, including catalysis freshening is mixed with hydrogen
Enter hydrotreating reaction area afterwards, successively contacts progress with hydrogenation protecting agent, Hydrobon catalyst and catalyst for hydro-upgrading A
Hydrogenation reaction, hydrotreating outflow object enter the reaction of hydro-upgrading reaction zone, and hydro-upgrading reaction zone, which uses, contains unformed silicon
The catalyst for hydro-upgrading B of aluminium and modified Y zeolite, hydro-upgrading reaction effluent carry out hydrofining reaction, hydrogen are added to mend
It fills refined products and is isolated to transformer oil.Although the inventive method has widened FCC recycle oil utilization ways, can increase production change
Depressor oil product, but this method is to add the process conditions severity of hydrogen big to FCC recycle oil deep hydrogenation, and reaction heat is not easily-controllable
System and hydrogen consumption height, economic benefit is lower, is not suitable for for the refinery that hydrogen resources are not had more than needed.
CN105733670 A discloses a kind of FCC recycle oil and hydrogen is added to produce big specific gravity aviation kerosine method, including catalysis
Freshening mixed with hydrogen after enter hydrotreating reaction area, successively with hydrogenation protecting agent, Hydrobon catalyst and hydro-upgrading
Catalyst A contact carries out hydrogenation reaction, and hydrotreating outflow object enters the reaction of hydro-upgrading reaction zone, and hydro-upgrading reaction zone makes
With the catalyst for hydro-upgrading B containing amorphous silicon aluminium and modified Y zeolite, hydro-upgrading reaction effluent carries out plus hydrogen supplement essence
System reaction, hydrofining product are isolated to big specific gravity aviation kerosine.Although this method has widened that density is big, aromatic hydrocarbons contains
The raw material sources of the low good big specific gravity aviation kerosine product of cryogenic property are measured, but this method is added to FCC recycle oil depth
Hydrogen, largely plus hydrogen saturation, reaction heat is not easy to control and hydrogen consumption is high, and economic benefit is lower, to hydrogen resources for aromatic hydrocarbons in recycle oil
It is not suitable for for refinery more than needed.
CN104830366 A disclose it is a kind of raising crude oil distillation yield and improve residual oil property method, including to
It is added in crude oil plus hydrogen recycle oil, obtains miscella, by miscella atmospheric and vacuum distillation, improve crude oil extracting rate and improve and subtract
Press residual oil property.Though this method improves light oil yield and reduces the generation of colloid in decompression residuum, asphalitine, can widen
Recycle oil utilization ways, but what is mixed adds hydrogen recycle oil ratio lower, not can solve the low value-added utilization of most recycle oil
Status.
CN101519603 A discloses a kind of process for hydrogenating residual oil, residual oil raw material is mixed with FCC recycle oil and
The optional catalytic cracked oil pulp for isolating solid dust passes through concatenated 3-6 trickle bed reactor, reaction effluent gas-liquid
Separation, liquid phase material are blended in weighted BMO spaces in up-flow reactor as catalytically cracked material, gas phase and FCC recycle oil,
Solution after pretreatment is mutually used as the mixed component of residual oil raw material.Though this method can slow down the pressure drop rise of up-flow reactor, extend
Device operation cycle, although this method provides a kind of Land use systems of catalytic cracking recycle oil, but recycle oil incorporation residual oil is former
Material, which enters trickle bed reactor, can lead to the problem of non-uniform temperature, cause hot localised points, and contain a small amount of solid in recycle oil
Powder can accelerate catalyst bed pressure drop rise.
In conclusion the key of FCC recycle oil high value added utilization is hydrotreating, in the mistake of recycle oil hydrotreating
Cheng Zhong in traditional trickle bed hydroprocessing technique, in order to take away a large amount of reaction heat, inhibit catalyst carbon deposit green coke, needs
A large amount of recycle hydrogen and its corresponding circulatory system, on the one hand make the volume of hydrogenation reaction device more huge, on the other hand
Also improve the cost of investment and operation energy consumption of hydrogenation reaction device.
Summary of the invention
The purpose of the invention is to overcome existing FCC recycle oil resource high added value comprehensive utilization ratio is not high to ask
Topic, provides a kind of combinational processing method of FCC recycle oil.
To achieve the goals above, the present invention provides a kind of combinational processing method of FCC recycle oil, wherein the combination adds
Work method includes: to contact FCC recycle oil with hydrogen in the presence of hydrogenation catalyst and carry out liquid-phase hydrogenatin, is added what is obtained
Hydrogen recycle oil mixes in residual hydrogenation raw material, catalytically cracked material, delayed coking raw material and catalytic cracking production.
The present invention is available rich in naphthane, dihydroanthracene, dihydro phenanthrene etc. by carrying out liquid-phase hydrogenatin to FCC recycle oil
A variety of hydrogenation of aromatics add hydrogen recycle oil, and hydrogenation of aromatics can produce reactive hydrogen at 300-600 DEG C, which, which has, blocks
The ability of radical reaction can play the condensation reaction for preventing alkene, aromatic ring free radical, by this plus hydrogen recycle oil incorporation residual oil
In hydrogenating materials, catalytically cracked material, delayed coking raw material and catalytic cracking production, the heat that residual hydrogenation raw material can be improved is steady
It is qualitative, extend residual hydrogenation equipment operation cycle；The thermal stability that coking raw material can be improved slows down tube coking, reduces burnt
Change recycle ratio, extend coking plant on-stream time, reduce the yield of gas and coke, improves the yield of coking liquid product；It can
To improve the light oils liquid yield such as catalytic cracking unit liquefied gas, gasoline, diesel oil, catalytic heavy and coke yield are reduced；It can be with
Reduce catalytic cracking production in colloid, asphalitine generation, and then reduce subsequent catalyst Fractionator Bottom catalytic slurry in colloid,
Thus asphalt content reaches the abundant high value added utilization of FCC recycle oil resource, widens FCC recycle oil utilization ways.
Detailed description of the invention
Fig. 1 is the process flow chart of the combinational processing method of the FCC recycle oil of the embodiment of the present invention 1.
Description of symbols
1 FCC recycle oil；2 hydrogen；
3 liquid-phase hydrogenatin devices；4 strippers；
5 gaseous products；6 add hydrogen recycle oil；
7 residual hydrogenation equipments；8 catalytic cracking units；
9 delayed coking units；10 catalysis settler top main oil gas pipings；
11 catalytic fractionators.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of combinational processing method of FCC recycle oil, wherein the combinational processing method includes: to add hydrogen
In the presence of catalyst, FCC recycle oil is contacted with hydrogen and carries out liquid-phase hydrogenatin, by obtain plus hydrogen recycle oil incorporation residual oil
In hydrogenating materials, catalytically cracked material, delayed coking raw material and catalytic cracking production.
In the present invention, the catalytic cracking production refers to the catalytic cracking production in catalysis settler top main oil gas piping.
Method of the invention can process FCC recycle oil caused by all types of crude oil, the FCC recycle oil
It can include but is not limited to catalytic slurry clarified oil, coal direct liquefaction oil, washing oil in visbreaking light oil or high temperature coal-tar, carbolineum
One or more of mixed fraction.Preferably, in the FCC recycle oil weight content of the bicyclic and above aromatic hydrocarbons 50%
Or more.
In the present invention, in order to simplify hydroprocessing technique, cost of investment is reduced, it is preferable that the process of the contact is in film
It is carried out in mixer, the process of the liquid-phase hydrogenatin carries out in tubular fixed-bed reactor.The FCC recycle oil rises through pump
Pressure exchanges heat and reacts required temperature to liquid-phase hydrogenatin, mixes in film mixer with hydrogen, described under liquid-phase hydrogenatin treatment conditions
Oil-based system is satisfied at least two concatenated tubular fixed-bed reactors with having catalytic desulfurhydrogenation, nitrogen, arenes selectivity
It is contacted with the catalyst of effect, carries out liquid-phase hydrogenatin reaction.
In the present invention, the film mixer includes shell and membrane module.The film mixer is by least one film group
Part is placed in a shell, and makes between the outer wall of membrane module and the inner wall of shell that there are spaces.Make in channel on the membrane module
For the fluid passage for accommodating FCC recycle oil raw material, the space of the inner wall formation of the outer wall of the membrane module and the shell
As the gas passage for accommodating hydrogen；Alternatively, channel on the membrane module is as the gas passage for accommodating hydrogen,
The space that the inner wall of the outer wall of the membrane module and the shell is formed is logical as the liquid for accommodating FCC recycle oil raw material
Road.Preferably, the channel on membrane module is as the fluid passage for accommodating FCC recycle oil raw material, the outer wall of membrane module and institute
The space of inner wall formation of shell is stated as the gas passage for accommodating hydrogen.
The material for forming the membrane module can be inorganic material (such as inorganic ceramic), or organic material, as long as
With hydrogen and FCC recycle oil chemical interaction will not occur for the material for forming the component.The membrane module is by more
Porous materials are formed, and the average pore size in hole therein is nano-scale.The membrane module may also comprise matrix and be attached to described
Perforated membrane on matrix, described matrix have through-hole, the perforated membrane can be located at described matrix be contained in the liquid
In channel FCC recycle oil raw material reaction surface on, can also be located at described matrix be contained in the gas passage
Hydrogen reaction surface on.Preferably, the perforated membrane be located at described matrix be contained in urging in the fluid passage
On the surface for changing the reaction of recycle oil raw material.Hole in the perforated membrane is the hole that average pore size is nano-scale.In described matrix
The average pore size of through-hole be not particularly limited, as long as gas can be passed through.Preferably, the through-hole in described matrix is flat
Equal aperture is 1nm to 1000 μm (such as 50-200 μm).Hydrogen is the fenestra and FCC recycle oil of nano-scale by average pore size
It mixes, more hydrogen can be dissolved in FCC recycle oil, undissolved hydrogen then can be highly stable in film mixer
It is dispersed in feedstock oil, can ensure that hydrogenation reaction carries out in the liquid phase in this way, maintain hydrogen initial reactive concentration, " hydrogen is anti-for maintenance
Answer motive force ", hydrogenation reaction rate is improved, keeps exothermic heat of reaction uniform, the trend of catalyst green coke is reduced, even if with lower hydrogen
Oil than and at a high space velocity, can also be effectively reduced sulphur in FCC recycle oil, nitrogen content and carbon residue yield, selectively
The product rich in a variety of hydrogenation of aromatics such as naphthane, dihydroanthracene, dihydro phenanthrenes is obtained, preferable hydrotreating effect is obtained, makes to add
Hydrogen catalyst keeps higher catalytic activity, extends the service life of catalyst, simplifies hydroprocessing technique flow line, reduces
Cost of investment and operating cost
In the present invention, filling rate of the membrane module in the shell generally can be 10-90%, such as 50-70%.Institute
State the percent value of the total measurement (volume) in space and shell that filling rate refers to that membrane module occupies.
In the present invention, the average pore size in the hole of the membrane module can be generally 1nm to 1000nm, and preferably 30nm is extremely
1000nm, more preferably 30nm are to 800nm, further preferably 50nm to 500nm.The average pore size uses scanning electron microscope method
Measurement.From dispersion mixing of the hydrogen in the FCC recycle oil raw material is further increased, so that hydrogen can be faster
The angle spreaded more evenly across in the recycle oil raw material is set out, and the quantity Zhan that aperture is in the hole within the scope of 50-500nm is total
The ratio of hole number is 95% or more, such as 95-98%.
In the present invention, the channel on the membrane module is described as the fluid passage for accommodating FCC recycle oil raw material
When the space that the inner wall of the outer wall of membrane module and the shell is formed is as gas passage for accommodating hydrogen, hydrogen is passed through
Gas access is sent into shell, recycle oil raw material is sent into the channel of membrane module, under the action of pressure difference, is passed through hydrogen
Hole on tube wall enters in FCC recycle oil raw material, so that hydrogen be made to mix with FCC recycle oil cross-flow.
It can be that hydrogen injection can also be in flow regime in static feedstock oil for hydrogen injection in the present invention
Feedstock oil in.It is preferred that hydrogen injection is in the feedstock oil of flow regime, the hydrogen dispersion that can not only have been obtained in this way
Solute effect, and higher production efficiency can be obtained.
In the present invention, the amount for being mixed into the hydrogen in the FCC recycle oil can be according in the FCC recycle oil raw material
Impurity content is selected.In existing mink cell focus hydrogenation technique, the dosage of hydrogen is big, the volume ratio of hydrogen and heavy oil feed
Generally 700 or more.Hydrogen is sent into the FCC recycle oil by the hole of the nano-scale of average pore size by method of the invention
In, hydrogen high degree of dispersion can be made and be dissolved in the FCC recycle oil, to provide enough hydrogen sources for hydrogenation reaction；And
And in method of the invention, hydrogenation reaction carries out in the liquid phase, can take in time reaction heat out of.Therefore, method of the invention
Even if reducing the amounts of hydrogen being sent into the FCC recycle oil, good hydrotreating effect can be also obtained, and reduce catalyst
The trend of green coke.According to the method for the present invention, the amount for the hydrogen being passed through is that under the cited reaction conditions, hydrogen is the catalysis freshening
1-2 times of the consumption of oil plus hydrogen, that is, the amount for the hydrogen being passed through are the 2-8wt%, preferably 3- of the FCC recycle oil
5wt%.With the method for the invention it is preferred to hydrogen is sent into the FCC recycle oil of heating, hydrogen can be made preferably in this way
It dissolves and disperses in the feed.Preferably, hydrogen feeding temperature and pressure is in the freshening under hydrogenation temperature and hydrogenation pressure
In oil, the trend that hydrogen is escaped from hydrogeneous oil can be further decreased in this way.Specifically, hydrogen can be sent into temperature is
300-400 DEG C, pressure be 4-10MPa FCC recycle oil in.
In the present invention, the film mixer is arranged on the material inlet pipeline of the tubular fixed-bed reactor,
Flexible operation and conveniently.
In the present invention, hydrogeneous recycle oil can be sent into tubular fixed-bed reactor in a manner of flowing up, can also be with
It is sent into tubular fixed-bed reactor in a manner of flowing downward.Preferably, the side by the hydrogeneous recycle oil to flow up
Formula is sent into tubular fixed-bed reactor, so during the reaction, is dissolved and is dispersed in the hydrogen in recycle oil and substantially will not
Aggregation forms big bubble and evolution, and the hydrogen of reaction process consumption is replenished in time, provides enough " reactive hydrogens for hydrogenation reaction
Motive force " obtains preferable hydrotreating effect；Catalyst is fully immersed in material, and reactionless dead zone keeps catalyst
Higher catalytic activity；Exothermic heat of reaction is uniform, and the specific heat capacity of liquid is larger, can reduce the trend of catalyst green coke, and extension is urged
The service life of agent, to further extend the stable operation cycle of hydrogenation plant.
In the present invention, the condition of the liquid-phase hydrogenatin is preferably included: reaction temperature is 300-400 DEG C, reaction pressure 4-
10MPa, volume space velocity 0.2-5h-1(preferably 0.8-5.0h-1)。
In the present invention, the quantity of the tubular fixed-bed reactor is at least 2, or 2 or more.In the tubular type
When the quantity of fixed bed reactors is 2 or more, the tubular fixed-bed reactor is to be connected in series, or is connected two-by-two
It is connected in parallel combination again afterwards.Logistics is next after the series connection refers to previous tubular fixed-bed reactor exports plus hydrogen
The charging of a tubular fixed-bed reactor；Described be connected in parallel refers between tubular fixed-bed reactor do not have material exchange.
In the present invention, the hydrogenation catalyst can be common various de- with catalytic hydrogenation for mink cell focus field of hydrogenation
The catalyst of sulphur, nitrogen and arenes selectivity saturation.Generally, the hydrogenation catalyst contains carrier and is supported on institute
The vib metals and group VIII metal on carrier are stated, the vib metals are preferably molybdenum and/or tungsten, the Section VIII
Race's metal is preferably cobalt and/or nickel.The load capacity of the vib metals and group VIII metal on the carrier can root
It is selected according to the type of hydrogenation catalyst.Generally, on the basis of the total amount of the hydrogenation catalyst and in terms of oxide, institute
The content for stating vib metals can be 1-25 weight %, and the content of the group VIII metal can be 0.5-8 weight %.
The carrier can be the heat-resistant inorganic oxide of the various carriers for being suitable for hydrogenation catalyst, such as silica and/or oxygen
Change aluminium.Common various auxiliary agents can also have been loaded on the carrier of the hydrogenation catalyst, be no longer described in detail herein.
In the present invention, the combinational processing method can also include: that the product of the liquid-phase hydrogenatin is carried out gas-liquid separation,
Obtain gaseous product and plus hydrogen recycle oil.In the present invention, the gas-liquid separation can be implemented in stripper.
In the present invention, it is preferable that described plus incorporation of the hydrogen recycle oil in residual hydrogenation raw material is 10-20 weight %,
Described plus incorporation of the hydrogen recycle oil in catalytically cracked material is 10-20 weight %, and described plus hydrogen recycle oil is in delayed coking
Incorporation in raw material is 10-20 weight %, and described plus incorporation of the hydrogen recycle oil in catalytic cracking production is catalytic cracking
The 5-10 weight % of raw material.
In the present invention, described plus hydrogen recycle oil mixes residual hydrogenation raw material, can reduce viscosity, the carbon residue of residual oil raw material, subtract
The polymerization of alkene, reduces the generation of colloid, asphalitine in slow residual oil raw material.Under the conditions of residual hydrogenation, residual oil raw material can be improved
Thermal stability, extend residual hydrogenation equipment operation cycle.Preferably, the condition of the residual hydrogenation includes: that reaction temperature is
330-450 DEG C, reaction pressure 10-20MPa, volume space velocity 0.15-1h-1, total hydrogen to oil volume ratio is 300-2000.
In the present invention, described plus hydrogen recycle oil incorporation catalytically cracked material can be eliminated under the catalytic cracking condition
Basic nitrogen can be improved catalytic unit liquid product yield, reduce to the harm of catalysis acid centre and the formation of precursors of coke
Catalytic coke yield.Preferably, it is 480-550 DEG C that the condition of the catalytic cracking, which includes: reaction temperature, regeneration temperature 650-
750 DEG C, agent oil weight ratio is 4-10, is 0.5-5 seconds with catalytic cracking catalyst time of contact, pressure 0.1-0.5MPa.
In the present invention, described plus hydrogen recycle oil mixes delayed coking raw material, under the conditions of delayed coking, releases a large amount of
Reactive hydrogen, the reactive hydrogen can eliminate the macromolecule hydrocarbon aromatic ring that carbochain fracture generates under the high temperature conditions during pyrogenetic reaction
The condensation reaction that free radical, alkene isoreactivity group occur, improves the liquid yield of coking plant, coke yield drop
It is low.Preferably, the delayed coking carries out in the device for including heating furnace and coke drum, the condition packet of the delayed coking
Include: furnace outlet temperature is 495-505 DEG C, and top of coke tower temperature is 430-460 DEG C, and water injection rate accounts for the 1.5- of inlet amount weight
3%, recycle ratio 0.2-0.3, tower top operating pressure are 0.1-0.3MPa.
In general, the mixture of catalytic cracking catalyst and catalytic cracking production after reacting in catalytic cracking unit can be
Settlement treatment is carried out in catalysis settler, solid catalyst is separated and catalytic cracking production, obtained catalytic cracking production passes through
Catalysis settler top main oil gas piping enters subsequent fractionating column and carries out fractionation processing.In the present invention, described plus hydrogen recycle oil is mixed
Enter the mode of catalytic cracking production are as follows: the catalytic cracking production with plus hydrogen recycle oil catalysis settler top main oil gas piping in
Mixing.
Catalytic cracking reaction is essentially carbonium ion reaction, part unreacted completely active carbonium ion and partially catalyzed
Agent with high-temperature oil gas enters the main oil gas piping on catalytic cracking unit settler top, and the reaction was continued, and the incorporation of described plus hydrogen recycle oil is urged
Change in the main oil gas piping of settler top, under the catalysis settler operating condition, releases a large amount of reactive hydrogen, the reactive hydrogen
The condensation reaction of carbonium ion can be prevented, the generation of colloid, asphalitine in catalytic cracking production is reduced.The catalysis settler
Operating condition may include: catalysis settler top oil gas vent temperature be 490-535 DEG C, catalysis settler operating pressure be
0.1-0.3MPa。
In the present invention, the combinational processing method can also include: that will contain to add hydrogen recycle oil and catalytic cracking production
Mixture is fractionated.The fractionation carries out in catalytic fractionator, and described plus hydrogen recycle oil enters with catalytic cracking production
Catalytic fractionator, can also equally eliminating macromolecule hydrocarbon and alkene in catalytic cracking production, carbochain fracture produces under the high temperature conditions
The condensation reaction of raw aromatic ring free radical, the generation of alkene isoreactivity group makes colloid, the asphalitine yield drop of catalytic fractionator
It is low.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is implemented in technique as shown in Figure 1.
(1) liquid-phase hydrogenatin is carried out to FCC recycle oil
FCC recycle oil 1 (its property is shown in Table 1) and hydrogen 2 carry out liquid-phase hydrogenatin, liquid-phase hydrogenatin in liquid-phase hydrogenatin device 3
Device 3 includes film mixer and tubular fixed-bed reactor, and FCC recycle oil 1 enters after mixing in film mixer with hydrogen 2
Tubular fixed-bed reactor (two, series connection) carries out liquid-phase hydrogenatin under hydrogenation catalyst effect；
The average pore size in the hole of film mixer is 50nm, and aperture is in the total hole count of Zhan of the hole number within the scope of 50-55nm
The ratio of amount is 98%；The sky that channel on membrane module pipeline is formed as fluid passage, the outer wall of pipeline and the inner wall of shell
Between be used as gas passage, pipeline in the housing filling rate be 60 volume %；Filling is fragrant respectively in two tubular fixed-bed reactors
Hydrocarbon-selective saturation, desulfurization, denitrogenation business hydrogenation catalyst, the trade mark are respectively that HDD-2 and DC-201 (are purchased from Hunan Chang Ling stone
Change scientific and technological development company), the process conditions of hydro-upgrading are as follows: 320 DEG C of an anti-temperature, 360 DEG C, pressure 8.0MPa of two anti-temperature,
Single reactor mixes hydrogen amount 1.41wt% (hydrogen to oil volume ratio 150:1), total volume air speed 0.8h-1, obtained product is being stripped
Gas-liquid separation is carried out in tower 4, gaseous product 5 is discharged, and obtains adding hydrogen recycle oil 6, property is shown in Table 1.
(2) partial hydrogenation recycle oil incorporation decompression residuum is entered into residual hydrogenation equipment 7
Hydrogen recycle oil 6 and decompression residuum will be added to be made into mixed residue oil hydrogenating materials according to the weight ratio of 1:9, in 4MPa, 330
Under conditions of DEG C, constant temperature 6h, the material properties after heat treatment is shown in Table 2.Then mixed raw material is entered into residual hydrogenation equipment 7,
Reaction temperature is 375 DEG C, reaction pressure 17.4MPa, volume space velocity 0.2h-1, under the conditions of total hydrogen to oil volume ratio is 800:1,
Device can be with stable operation 12000h.
(3) partial hydrogenation recycle oil incorporation catalytically cracked material is entered into catalytic cracking unit 8
Hydrogen recycle oil 6 will be added to mix in catalytically cracked material, adding the incorporation of hydrogen recycle oil 6 is catalytically cracked material
20wt%, catalytic cracking catalyst are the catalyst that the trade mark of Sinopec catalyst Co. Chang Ling branch company production is DFC-1,
The operating condition of catalytic cracking unit 8 are as follows: 510 DEG C of reaction temperature, 650 DEG C of regeneration temperature, reaction pressure 0.1MPa, oil ratio
6.0, catalytic cracking the results are shown in Table 3.
(4) partial hydrogenation recycle oil incorporation delayed coking raw material is entered into delayed coking unit 9
Hydrogen recycle oil 6 will be added to mix in delayed coking raw material, adding the incorporation of hydrogen recycle oil 6 is delayed coking raw material
20wt%, the operating condition of delayed coking unit 9 are as follows: furnace outlet temperature is 500 DEG C, and top of coke tower temperature is 440 DEG C, note
Water accounts for the 2.0% of inlet amount weight, recycle ratio 0.2, tower top pressure 0.1MPa, and delayed coking the results are shown in Table 4.
(5) partial hydrogenation recycle oil is mixed into catalysis settler top main oil gas piping 10
It will add in the incorporation catalysis settler top main oil gas piping 10 of hydrogen recycle oil 6, and add the incorporation of hydrogen recycle oil 6 for catalysis
The 5wt% of cracked stock, mixed material enter catalytic fractionator 11, and settler top oil gas vent temperature is 500 DEG C, operating pressure
For 0.2MPa, catalytic fractionator column bottom temperature is 410 DEG C, and catalytic fractionator tower bottom catalytic slurry property is shown in Table 5.
Comparative example 1-2
According to the method for embodiment 1, unlike, in step (2), the material of heat treatment is respectively 100wt% decompression slag
Oil, 90wt% decompression residuum+10wt% FCC recycle oil.Material properties after heat treatment is shown in Table 2.100wt% is depressurized respectively
It is anti-that residual oil, 90wt% decompression residuum+10wt% FCC recycle oil carry out residual hydrogenation under the conditions of the residual hydrogenation of embodiment 1
It answers, device can run 168h and 200h respectively.
Comparative example 3-4
According to the method for embodiment 1, unlike, in step (3), the material of catalytic cracking is respectively catalytically cracked material
With add hydrogen recycle oil.Catalytic cracking the results are shown in Table 3.
Comparative example 4-5
According to the method for embodiment 1, unlike, in step (4), the material of delayed coking is respectively decompression residuum and adds
Hydrogen recycle oil.Delayed coking the results are shown in Table 4.
Comparative example 6
According to the method for embodiment 1, it unlike, in step (5), is catalyzed in settler top main oil gas piping 10 and does not mix
Add hydrogen recycle oil 6, i.e., will directly be catalyzed the catalytic cracking production in settler top main oil gas piping 10 and be sent into catalytic fractionator 11.
Catalytic fractionator tower bottom catalytic slurry property is shown in Table 5.
Table 1
| Project | FCC recycle oil | Add hydrogen recycle oil |
| Density, (20 DEG C) Kg/m3 | 1088.9 | 1046.8 |
| Viscosity, (50 DEG C) mm2/s | 118.6 | 75.5 |
| S content, ppm | 8213 | 2300 |
| N content, ppm | 4042 | 2873 |
| Ash content, m% | 0.004 | 0.001 |
| Carbon residue, % | 2.0 | 0.4 |
| Mass spectrum composition, w% | ||
| Alkane | 1.0 | 0.9 |
| Cycloalkane | 5.3 | 6.4 |
| Total mononuclear aromatics | 12.0 | 26.1 |
| Naphthalenes | 4.6 | 3 |
| Acenaphthene class | 5.7 | 6.1 |
| Fluorenes class | 6 | 11.5 |
| Total double ring arene | 16.3 | 20.6 |
| Luxuriant and rich with fragrance class | 7.2 | 9.8 |
| Cycloalkanes phenanthrene class | 8.9 | 8.5 |
| Total thrcylic aromatic hydrocarbon | 16.1 | 18.3 |
| Pyrene class | 18.2 | 12.1 |
| Bend class | 12.1 | 5.2 |
| Total four cycloaromatics | 30.3 | 17.3 |
| Total five cycloaromatics | 3.6 | 1.4 |
| Aromatic hydrocarbons is not identified | 8.0 | 4.6 |
| Total aromatic hydrocarbons | 93.7 | 92.7 |
Table 2
Table 2 the result shows that, decompression residuum is unstable, and viscosity, carbon residue, the heated easily condensation of colloid and asphalitine increase.It mixes
Enter after adding hydrogen recycle oil, carbon residue, colloid and asphalitine are greatly reduced by thermal condensation, and thermal stability improves.
Table 3
* theoretical value=catalytically cracked material value * 0.8+ adds the value * 0.2 of hydrogen recycle oil；Synergistic effect=experiment value-reason
By value.
Table 3 the result shows that, hydrogen recycle oil will be added to mix refining into catalytically cracked material, can increase that catalysis is light to receive, and increased
Mainly high added value gasoline component, reduce heavy oil yield.
Table 4
* it is kneaded synergy=80% and subtracts slag and with 20% add the value-of miscella of hydrogen recycle oil (the value * 0.8+ of decompression residuum adds
The value * 0.2 of hydrogen recycle oil).
Table 4 the result shows that, will add hydrogen recycle oil incorporation delayed coking raw material in, liquid yield can be increased, reduce
Low value-added coke yield.
Table 5
| Project | Catalytic slurry after incorporation plus hydrogen recycle oil | Catalytic slurry before incorporation plus hydrogen recycle oil |
| Density, kg/m3 | 1096.5 | 1132.8 |
| Viscosity, mm/s2 | 26.17 | 140.5 |
| Carbon residue, wt% | 19.2 | 26.36 |
| Ash content, wt% | 0.183 | 0.264 |
| Four compositions, wt% | ||
| Saturation point | 16.96 | 7.66 |
| Fragrance point | 67.58 | 62.46 |
| Colloid | 8.56 | 11.72 |
| Asphalitine | 6.16 | 17.63 |
As shown in Table 5, incorporation plus hydrogen recycle oil in catalysis settler top main oil gas piping, catalytic fractionator tower bottom gained
Catalytic slurry property improve, colloid, asphalt content are greatly reduced in slurry oil.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of combinational processing method of FCC recycle oil, which is characterized in that the combinational processing method includes: in hydrogenation catalyst
In the presence of, FCC recycle oil is contacted with hydrogen and carries out liquid-phase hydrogenatin, obtain plus hydrogen recycle oil incorporation residual hydrogenation is former
In material, catalytically cracked material, delayed coking raw material and catalytic cracking production.
2. combinational processing method according to claim 1, wherein the process of the contact carries out in film mixer, institute
The process for stating liquid-phase hydrogenatin carries out in tubular fixed-bed reactor.
3. combinational processing method according to claim 1 or 2, wherein the condition of the liquid-phase hydrogenatin includes: reaction temperature
It is 300-400 DEG C, reaction pressure 4-10MPa, volume space velocity 0.2-5h-1。
4. combinational processing method according to claim 1 or 2, wherein the combinational processing method further include: by the liquid
The product for being added hydrogen carries out gas-liquid separation, obtains gaseous product and plus hydrogen recycle oil.
5. combinational processing method according to claim 1 or 2, wherein described plus hydrogen recycle oil is in residual hydrogenation raw material
Incorporation be 10-20 weight %, described plus incorporation of the hydrogen recycle oil in catalytically cracked material is 10-20 weight %, institute
It states plus incorporation of the hydrogen recycle oil in delayed coking raw material is 10-20 weight %, described plus hydrogen recycle oil is produced in catalytic cracking
Incorporation in object is the 5-10 weight % of catalytically cracked material.
6. combinational processing method according to claim 1 or 2, wherein the condition of the residual hydrogenation includes: reaction temperature
It is 330-450 DEG C, reaction pressure 10-20MPa, volume space velocity 0.15-1h-1, total hydrogen to oil volume ratio is 300-2000.
7. combinational processing method according to claim 1 or 2, wherein the condition of the catalytic cracking includes: reaction temperature
It is 480-550 DEG C, regeneration temperature is 650-750 DEG C, and agent oil weight ratio is 4-10, is with catalytic cracking catalyst time of contact
0.5-5 seconds, pressure 0.1-0.5MPa.
8. combinational processing method according to claim 1 or 2, wherein the delayed coking is including heating furnace and coke
It is carried out in the device of tower, the condition of the delayed coking includes: that furnace outlet temperature is 495-505 DEG C, top of coke tower temperature
It is 430-460 DEG C, water injection rate accounts for the 1.5-3% of inlet amount weight, recycle ratio 0.2-0.3, and tower top operating pressure is 0.1-
0.3MPa。
9. combinational processing method according to claim 1 or 2, wherein described plus hydrogen recycle oil mixes catalytic cracking production
Mode are as follows: the catalytic cracking production with plus hydrogen recycle oil catalysis settler top main oil gas piping in mix；Described urges
It is 490-535 DEG C that the operating condition for changing settler, which includes: catalysis settler top oil gas vent temperature, is catalyzed settler operating pressure
For 0.1-0.3MPa.
10. combinational processing method according to claim 1 or 2, wherein the method for the Combined machining further include: will contain
There is the mixture for adding hydrogen recycle oil and catalytic cracking production to be fractionated.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881458A (en) * | 2021-11-09 | 2022-01-04 | 山东京博石油化工有限公司 | Recycle oil catalytic cracking treatment system and treatment method |
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| CN104927920A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Residue oil coking method |
| CN104927903A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Residual oil hydrotreatment method |
| CN104927899A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Hydroprocessing method of catalytic cracking heavy cycle oil, processing method of raw materials for producing needle coke, and method for producing needle coke |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927920A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Residue oil coking method |
| CN104927903A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Residual oil hydrotreatment method |
| CN104927899A (en) * | 2014-03-21 | 2015-09-23 | 中国石油化工股份有限公司 | Hydroprocessing method of catalytic cracking heavy cycle oil, processing method of raw materials for producing needle coke, and method for producing needle coke |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113881458A (en) * | 2021-11-09 | 2022-01-04 | 山东京博石油化工有限公司 | Recycle oil catalytic cracking treatment system and treatment method |
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