CN106221803A - 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
CN106221803A
CN106221803A CN201610708793.1A CN201610708793A CN106221803A CN 106221803 A CN106221803 A CN 106221803A CN 201610708793 A CN201610708793 A CN 201610708793A CN 106221803 A CN106221803 A CN 106221803A
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China
Prior art keywords
catalytic cracking
hydrofinishing
delayed coking
oil
coking
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CN201610708793.1A
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Chinese (zh)
Inventor
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 CN201610708793.1A priority Critical patent/CN106221803A/en
Publication of CN106221803A publication Critical patent/CN106221803A/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
    • B01J29/03—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
    • 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

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 Cu in synthetic bone shelf structure2+KIT-1.
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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4's Mixture.
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.
KIT-1 molecular sieve has one-dimensional channels and crosses each other to form three-dimensional disordered structure, and this structure is conducive to catalysis, absorption During material transmission.Pure silicon mesopore molecular sieve KIT-1 has heat stability more more preferable than MCM-241, HMS and hydrothermally stable Property.The present invention through in numerous mesoporous materials, such as KIT-1, KIT-6, MCM-22, MCM-36, MCM-48, MCM-49, MCM56 etc., carry out contrast test selection, find that only KIT-1 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 KIT-1 is as carrier basis.
Although pure silicon KIT-1 mesopore molecular sieve hydro-thermal performance is outstanding, but inventor's research is later discovered that, it adds Hetero atom or surface are after chemical modification, and its hydrothermal stability obtains bigger raising.Therefore, it is modified by the present invention, with Increase its catalysis activity.The approach that KIT-1 mesopore molecular sieve is modified is by the present invention: to the total silicon KIT-1 mesoporous molecular of finished product Sieve inner surfaces of pores introduces Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of KIT-1, thus Improve catalysis activity, absorption and the Thermodynamically stable performance etc. of KIT-1 mesopore molecular sieve on the whole.
Although the method being modified KIT-1 mesopore molecular sieve or approach are a lot, inventor finds, the catalysis of the present invention Agent can only use doping Cu2+KIT-1 as carrier could realize sulfur content control effect, inventor has attempted in KIT-1 Doping Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize described effect.Although institute State 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 its with Cooperative effect is there is between the active component of the present invention.
Described Cu2+Doping in KIT-1 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of KIT-1 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 KIT-1 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 KIT-1 weight, preferably 3-12%, further preferred 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.
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains Having catalyst aid, described catalyst aid is Cr2O3、ZrO2、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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) the catalyst facilitation to the present invention Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improve its service life.
Described Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that Cr2O3、ZrO2、 CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention uses2O3、ZrO2、 CeO2、V2O5And NbOPO4Respective 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.The typical but non-limiting example of the present invention As follows:
Sodium silicate, cetyl trimethylammonium bromide (CTAB), sodium ethylene diamine tetracetate (EDTA) and distilled water are massaged You mix the ratio than 1:0.25:1:60, load with in teflon-lined autoclave pressure, after stirring under 373K Constant temperature 24h, the pH of re-adjustments mixture are 10.5, after constant temperature 4 times, take out product, with distilled water cyclic washing to filtrate PH=7, then under 373K, constant temperature overnight, obtains the KIT-1 with surfactant.KIT-1 with surfactant is existed Roasting 1.5h under 523K, then roasting 6h in air atmosphere under 813K, obtains KIT-1 powder body.By this powder body 0.1mol/L Salpeter solution carry out pickling (control solid-to-liquid ratio is 1:10), under room temperature stir 0.5h, filter, be washed with distilled water to filtrate Dry under pH=7,373K and obtain matrix KIT-1 molecular sieve.
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+ KIT-1 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 Cr2O3、ZrO2、CeO2、V2O5With NbOPO4Mixture so that this catalyst produce cooperative effect, 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 Cu2+KIT-1, Cu2+Doping control in KIT-1 System is 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 the 10% of carrier quality, and 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+KIT-1, Cu2+Doping control in KIT-1 System is 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 the 10% of carrier quality, and 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 52ppm, and beds pressure drop increases above 0.05%.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated KIT-1, 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
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 59ppm, and beds pressure drop increases above 0.05%.
Comparative example 4
By the Cu in embodiment 12+Doping in KIT-1 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 58ppm, and beds pressure drop increases above 0.05%.
Comparative example 5
By the Cu in embodiment 12+Doping in KIT-1 controls at the 0.8% 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%.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion KIT-1 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+During doping difference, all reach not To 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 KIT-1 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 63ppm, 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 67ppm, 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 Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 2%, 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 18.3%.
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 4.6%.
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 4.4%.
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+KIT-1, described active component for nitridation two molybdenum MO2N、 Tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst possibly together with catalyst aid, described catalyst aid For Cr2O3、ZrO2、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 KIT-1 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 KIT-1 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 Cr2O3、 ZrO2、CeO2、V2O5And NbOPO4Respective content is respectively the 1-7% of carrier quality, preferably 2-4%.
CN201610708793.1A 2016-08-23 2016-08-23 A kind of catalytic cracking combined technique of delayed coking hydrofinishing Pending CN106221803A (en)

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