CN106244230A - A kind of catalytic cracking combined technique of delayed coking hydrofinishing - Google Patents
A kind of catalytic cracking combined technique of delayed coking hydrofinishing Download PDFInfo
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- CN106244230A CN106244230A CN201610680218.5A CN201610680218A CN106244230A CN 106244230 A CN106244230 A CN 106244230A CN 201610680218 A CN201610680218 A CN 201610680218A CN 106244230 A CN106244230 A CN 106244230A
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- catalytic cracking
- hydrofinishing
- delayed coking
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- coking
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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
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
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- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of catalytic cracking combined technique of delayed coking hydrofinishing, described process integration includes delayed coking unit, hydrofinishing unit and catalytic cracking unit, wherein, the heating of coking raw material heated stove enters coking tower, generating coke and lighter products, lighter products is fractionated into tower fractional distillation and obtains Petroleum, gasoline, diesel oil and wax tailings；Described wax tailings is removed by filtration the granule more than 25 μm, together with other high-sulfur straight-run gas oils optional after the heating of heated stove, it is mixed into hydro-refining unit with hydrogen, the treated return of gas phase obtained mixes with hydrogen, obtain hydrofined oil and enter catalytic cracking unit together with optional decompression residuum or reduced crude, obtaining cracking gas, catalytic gasoline, diesel oil and catalytic cracked oil pulp, catalytic cracked oil pulp and coking raw material are mixed together entrance delayed coking unit.This technique can effectively process CGO and VGO, and controls the sulfur content in product at below 5ppm, and makes Useful Time of Hydrogenation Catalyst reach more than 2 years.
Description
Technical field
The present invention relates to a kind of delayed coking-hydrofinishing-catalytic cracking combined technique, be specifically related to a kind of employing specific
Catalyst carries out hydrorefined delayed coking-hydrofinishing-catalytic cracking combined technique.
Background technology
Delayed coking is a kind of oil secondary operations technology, refers to the mink cell focus of lean hydrogen as raw material, at high temperature (about 500
DEG C) carry out thermal cracking and the condensation reaction of the degree of depth, produce gas, gasoline, diesel oil, wax oil and the technology of coke.So-called delay is
Refer to be brought rapidly up to pyrogenetic reaction temperature, coking oil (raw oil and recycle oil) through heating furnace heating in reaction boiler tube not
Green coke, and enter coke drum and carry out pyrogenetic reaction again, therefore have delay action, referred to as Delayed Coking Technology.
Along with heaviness, the in poor quality of world's crude oil are deepened day by day, crude oil sulfur content is more and more higher, and the lightweight of high-quality is former
Oil is constantly reducing.The crude oil of refinery's processing in recent years mostly is imported crude oil, and relative density increases year by year, in several years of the beginning of this century
The average density of whole world refinery processing crude oil rises to about 0.8633.The problem that sulfur content is high is the most extremely serious, the current world
The yield of upper sour crude oil and sour crude accounts for more than the 75% of world's crude oil total output.20th century the mid-90 whole world refinery
The crude oil average sulfur content of processing is 0.9%, and the beginning of this century has increased to 1.6%.
Processing sour crude, on the one hand easily causes the product of catalytic cracking, and the particularly sulfur content of gasoline exceeds standard, and reaches not
Cannot dispatch from the factory to environmental requirement so that qualified catalytically cracked material is not enough.On the other hand, the high-sulfur of delayed coking, high nitrogen
Wax oil (CGO) outlet difficulty.CGO has the feature that sulfur, nitrogen, condensed-nuclei aromatics and carbon granules content are high, basic nitrogen therein (total nitrogen one
As at 2500 more than μ g/g) and condensed-nuclei aromatics catalytic cracking catalyst can be caused seriously to be poisoned and carbon distribution, cause conversion ratio and vapour
Oil productivity is decreased obviously, carbon granule blocking and abrasion catalytic cracking riser reactor feed nozzle；If as hydrocracking raw material,
Also the activity of Cracking catalyst is affected because its nitrogen content is high；If being directly in harmonious proportion and making fuel oil, have lost the most again part secondary and add
The raw material that frock is put, affects the economic benefit of oil refining enterprise.
Therefore, how to utilize CGO and other high-sulfur straight-run gas oils (VGO), expand the raw material sources of catalytic cracking unit, right
The economic benefit tool of environmental conservation and raising oil refining enterprise is of great significance.
Summary of the invention
It is an object of the invention to propose a kind of delayed coking-hydrofinishing-catalytic cracking combined technique, can effectively process
CGO and VGO, and the sulfur content in product is controlled at below 5ppm.
For reaching this purpose, the present invention by the following technical solutions:
A kind of delayed coking-hydrofinishing-catalytic cracking combined technique, described process integration include delayed coking unit,
Hydrofinishing unit and catalytic cracking unit, wherein, the heating of coking raw material heated stove enters coking tower, generates coke and lightweight
Product, lighter products is fractionated into tower fractional distillation and obtains Petroleum, gasoline, diesel oil and wax tailings (CGO)；Described wax tailings passes through
Filter the granule more than 25 μm, together with other high-sulfur straight-run gas oils (VGO) optional after the heating of heated stove, mix with hydrogen
Closing and enter hydro-refining unit, the treated return of gas phase obtained mixes with hydrogen, obtains hydrofined oil and optional decompression
Residual oil or reduced crude enter catalytic cracking unit together, obtain cracking gas, catalytic gasoline, diesel oil and catalytic cracked oil pulp, urge
Change cracking slurry oil and be mixed together entrance delayed coking unit with coking raw material.
Described hydrofinishing uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, described
Hydrogenation catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Cu in synthetic bone shelf structure2+MCM-41.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing
Thing.
The reaction condition of described fixed bed reactors is: reaction temperature is 320-420 DEG C, and hydrogen dividing potential drop is 5-9MPa, hydrogen oil
Volume ratio 400-600, volume space velocity 1.0-2.0h-1。
In the present invention, described delayed coking unit, hydro-refining unit and catalytic cracking unit are all petrochemical industry necks
The device that territory is the most ripe, those skilled in the art can select concrete class according to raw material physical property, scale of investment and product requirement
Type and scale, the present invention is not specifically limited.
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time
The difference adding directed agents and synthetic parts changes between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g,
MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic
The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49,
MCM56, carries out contrast test selection, finds that only MCM-41 can reach the goal of the invention of the present invention, and other mesoporous materials are all
Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use
MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention
Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: be situated between to the Siliceous MCM-41 of finished product
Porous molecular sieve inner surfaces of pores introduces Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of MCM-41,
Thus improve catalysis activity, absorption and the Thermodynamically stable performance etc. of MCM-41 mesopore molecular sieve on the whole.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Cu2+MCM-41 as carrier could realize sulfur content control effect, inventor has attempted at MCM-
Adulterate in 41 Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize described effect.To the greatest extent
Manage described mechanism current and unclear, but this have no effect on the enforcement of the present invention, inventor according to well-known theory with it is experimentally confirmed that
Cooperative effect is there is between itself and the active component of the present invention.
Described Cu2+Doping in MCM-41 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of MCM-41 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of product desulfurized effect.It is more pleasurable,
Work as Cu2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when drawing with Cu2 +Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control extremely low
Within the scope of, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier MCM-41 weight, preferably 3-12%, further preferably
5-10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, in can realizing, in coalite tar, sulfur content controls at below 10ppm and denitrification ability notable.Namely
Saying, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just tool
Standby cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize collaborative effect
Should.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-
0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0),
Preferably 1:0.48:0.42:0.95.
The three of the purpose of the present invention are to provide the promoter of described catalyst.Catalyst of the present invention possibly together with
Catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its
For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal
Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps
Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined
?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding,
Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy
Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching
To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting
During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water
Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass
System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5,
Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it
Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively
Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal
Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis
Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase
To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid,
Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 350-375 DEG C, and hydrogen dividing potential drop is 6.0-
8.0MPa, hydrogen to oil volume ratio 450-500, volume space velocity 1.5-1.65h-1。
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrofining technology of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Cu2+
MCM-41 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
As active component, described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4's
Mixture so that this catalyst produces cooperative effect, the hydrodesulfurization to product can control at total sulfur content less than 5ppm, simultaneously
The catalyst of catalytic hydrogenation unit can reach more than 2 years service life.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+Doping in MCM-41
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material is by Beijing satellite system
The double plunger micro pump making factory's manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ZM gas by gas cylinder
Weight effusion meter coutroi velocity, hydrogenation catalyst loadings is 2kg.
Controlling reaction condition is: temperature 390 DEG C, hydrogen dividing potential drop 14.0MPa, hydrogen to oil volume ratio 800, volume space velocity 0.2h-1。
The heating of coking raw material heated stove enters coking tower, generates coke and lighter products, and lighter products is fractionated into tower and divides
Evaporate and obtain Petroleum, gasoline, diesel oil and wax tailings (CGO)；Described wax tailings is removed by filtration the granule more than 25 μm, with
After optional other high-sulfur straight-run gas oil wax oil (VGO) the most heated stoves heating, it is mixed into hydro-refining unit with hydrogen,
The treated return of gas phase obtained mixes with hydrogen, obtains hydrofined oil and enters together with optional decompression residuum or reduced crude
Enter catalytic cracking unit, obtain cracking gas, catalytic gasoline, diesel oil and catalytic cracked oil pulp, catalytic cracked oil pulp and coking raw material
It is mixed together entrance delayed coking unit.
Testing final product, total sulfur content is reduced to 3ppm, and beds pressure drop is unchanged.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+Doping in MCM-41
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 4ppm, and beds pressure drop is unchanged.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 57ppm, and beds pressure drop increases above 0.05%.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 59ppm, and beds pressure drop increases above 0.05%.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 53ppm, and beds pressure drop increases above 0.05%.
Comparative example 4
By the Cu in embodiment 12+Doping in MCM-41 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 61ppm, and beds pressure drop increases above 0.05%.
Comparative example 5
By the Cu in embodiment 12+Doping in MCM-41 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 63ppm, and beds pressure drop increases above 0.05%.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion
MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+During doping difference, all reach
Less than the present invention technique effect (desulfurization degree and beds change in pressure drop, change in pressure drop reflect catalyst inactivation speed
Degree), the therefore Cu of the certain content scope of the present invention2+Collaborative effect is possessed between doping MCM-41 carrier and other components of catalyst
Should, described hydrofining technology creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 64ppm, and beds pressure drop increases above 0.05%.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 66ppm, and beds pressure drop increases above 0.05%.
Above-described embodiment and the explanation of comparative example 6-7, hydrogenation catalyst several activity group of the hydrofining technology of the present invention
The specific contact an of/existence, is omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that
Which create cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and
3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same
The beds pressure drop of time embodiment 1 reduces 17%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 6%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 5%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed
The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst,
And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (7)
1. delayed coking-hydrofinishing-catalytic cracking combined technique, described process integration includes delayed coking unit, adds
Hydrogen refined unit and catalytic cracking unit, wherein, the heating of coking raw material heated stove enters coking tower, generates coke and lightweight is produced
Thing, lighter products is fractionated into tower fractional distillation and obtains Petroleum, gasoline, diesel oil and wax tailings (CGO)；Described wax tailings is through filtering
Remove the granule more than 25 μm, together with other high-sulfur straight-run gas oils (VGO) optional after the heating of heated stove, mix with hydrogen
Entering hydro-refining unit, the treated return of gas phase obtained mixes with hydrogen, obtains hydrofined oil and the slag that optionally reduces pressure
Oil or reduced crude enter catalytic cracking unit together, obtain cracking gas, catalytic gasoline, diesel oil and catalytic cracked oil pulp, catalysis
Cracking slurry oil and coking raw material are mixed together entrance delayed coking unit；Described hydrofinishing uses fixed bed reactors,
Being filled with hydrogenation catalyst in fixed bed reactors, described hydrogenation catalyst includes carrier and active component, it is characterised in that
Described carrier is incorporation hetero atom Cu in synthetic bone shelf structure2+MCM-41,
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc,
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture,
The reaction condition of described fixed bed reactors is: reaction temperature is 320-420 DEG C, and hydrogen dividing potential drop is 5-9MPa, hydrogen oil volume
Ratio 400-600, volume space velocity 1.0-2.0h-1。
2. delayed coking-hydrofinishing-catalytic cracking combined technique as claimed in claim 1, it is characterised in that hetero atom Cu2 +The 0.63%-0.72% that doping is MCM-41 weight.
3. delayed coking-hydrofinishing-catalytic cracking combined technique as claimed in claim 1, it is characterised in that described activity
The total content of component is the 3-12% of carrier MCM-41 weight, preferably 5-10%.
4. delayed coking-hydrofinishing-catalytic cracking combined technique as claimed in claim 1, it is characterised in that nitrogenize two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-
1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. delayed coking-hydrofinishing-catalytic cracking combined technique as claimed in claim 1, it is characterised in that described fixing
The reaction condition of bed reactor is: reaction temperature is 350-375 DEG C, and hydrogen dividing potential drop is 6.0-8.0MPa, hydrogen to oil volume ratio 450-
500, volume space velocity 1.5-1.65h-1。
6. delayed coking-hydrofinishing-catalytic cracking combined technique as claimed in claim 1, it is characterised in that described fixing
Bed reactor includes 1-5 beds, further preferred 2-3 beds.
7. delayed coking-hydrofinishing-catalytic cracking combined technique as claimed in claim 1, it is characterised in that TiO2、
CeO2、V2O5And NbOPO4Respective content is respectively the 1-7% of carrier quality, preferably 2-4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610680218.5A CN106244230A (en) | 2016-08-16 | 2016-08-16 | A kind of catalytic cracking combined technique of delayed coking hydrofinishing |
Applications Claiming Priority (1)
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