CN106221802A - 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 PDF

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Publication number
CN106221802A
CN106221802A CN201610666817.1A CN201610666817A CN106221802A CN 106221802 A CN106221802 A CN 106221802A CN 201610666817 A CN201610666817 A CN 201610666817A CN 106221802 A CN106221802 A CN 106221802A
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catalytic cracking
hydrofinishing
oil
delayed coking
unit
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朱忠良
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Xishan Lvchun Plastic Products Factory
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Xishan Lvchun Plastic Products Factory
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Priority to CN201610666817.1A priority Critical patent/CN106221802A/en
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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
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (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

A kind of delayed coking-hydrofinishing-catalytic cracking combined technique
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 Co 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.
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: in MCM-41 building-up process, Add Co2+Saline solution, before MCM-41 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part skeleton unit Element thus embed in the skeleton of molecular sieve, improve on the whole MCM-41 mesopore molecular sieve catalysis activity, absorption and heat Mechanical stability can wait.
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 Co2+MCM-41 could realize sulfur content as carrier and control and the balance of loss of octane number, invention People has attempted adulterating in MCM-41: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all can not Realize described effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on MCM-41 inner surfaces of pores to compare, The isomorphous substitution approach of the present invention is more stable.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention Executing, inventor is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+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 Co2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when drawing with Co2 +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 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 Co2+ 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 so that this catalyst produces cooperative effect, and the hydrodesulfurization to product can control to be less than at total sulfur content 5ppm, the catalyst of catalytic hydrogenation unit can reach more than 2 years service life simultaneously.
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 Co2+MCM-41, Co2+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 Co2+MCM-41, Co2+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 3ppm, 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 55ppm, 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 54ppm, and beds pressure drop increases above 0.05%.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 58ppm, and beds pressure drop increases above 0.05%.
Comparative example 4
By the Co 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 55ppm, and beds pressure drop increases above 0.05%.
Comparative example 5
By the Co 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 47ppm, 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 Co2+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 Co 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 54ppm, 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 62ppm, 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.
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 (6)

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 Co 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,
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 Co2 +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.
CN201610666817.1A 2016-08-12 2016-08-12 A kind of catalytic cracking combined technique of delayed coking hydrofinishing Pending CN106221802A (en)

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WO2013149014A1 (en) * 2012-03-29 2013-10-03 Wayne State University Bimetal catalysts
CN105251527A (en) * 2015-11-11 2016-01-20 中国石油大学(北京) Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1262969A (en) * 2000-03-02 2000-08-16 南开大学 Catalyst using TiO2 as carrier to load metal nitride Mo2N
CN1470327A (en) * 2002-07-24 2004-01-28 北京石油化工学院 Metal nitride catalyst preparing method and catalyst
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