CN106311313A - Delayed coking-hydrofining-catalytic cracking combined technology - Google Patents

Delayed coking-hydrofining-catalytic cracking combined technology Download PDF

Info

Publication number
CN106311313A
CN106311313A CN201610674083.1A CN201610674083A CN106311313A CN 106311313 A CN106311313 A CN 106311313A CN 201610674083 A CN201610674083 A CN 201610674083A CN 106311313 A CN106311313 A CN 106311313A
Authority
CN
China
Prior art keywords
catalytic cracking
oil
delayed coking
coking
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610674083.1A
Other languages
Chinese (zh)
Inventor
朱忠良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xishan Lvchun Plastic Products Factory
Original Assignee
Xishan Lvchun Plastic Products Factory
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xishan Lvchun Plastic Products Factory filed Critical Xishan Lvchun Plastic Products Factory
Priority to CN201610674083.1A priority Critical patent/CN106311313A/en
Publication of CN106311313A publication Critical patent/CN106311313A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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

Landscapes

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

Abstract

The invention discloses a delayed coking-hydrofining-catalytic cracking combined technology. A delayed coking unit, a hydrofining unit and a catalytic cracking unit are involved in the combined technology. Coking raw materials are heated through a heating furnace and enter a coking tower, coke and light products are generated, the light products are fractionated through a fractionating tower, and naphtha, gasoline, diesel oil and coker gas oil are obtained; the coker gas oil is filtered to remove particles with the size larger than 25 micrometers, is heated through the heating furnace together with other optional high-sulfur vacuum gas oil and then is mixed with hydrogen, the mixture enters a hydrofining device, an obtained gas phase is returned after being treated and then is mixed with hydrogen, hydrofined oil is obtained and enters a catalytic cracking device together with optional vacuum residuum or atmospheric residuum, cracking gas, catalytic gasoline, diesel oil and catalytic cracking slurry oil are obtained, and the catalytic cracking slurry oil and coking raw materials are mixed and enter the delayed coking unit together. By means of the technology, CGO and VGO can be effectively treated, the sulfur content in a product can be controlled to be 5 ppm or lower, and the service life of a hydrogenation catalyst can reach 2 years or longer.

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.
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: 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 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 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, 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 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.
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 18%.
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 3%.
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, It is characterized in that, being 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 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 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 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.
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%.
CN201610674083.1A 2016-08-16 2016-08-16 Delayed coking-hydrofining-catalytic cracking combined technology Pending CN106311313A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610674083.1A CN106311313A (en) 2016-08-16 2016-08-16 Delayed coking-hydrofining-catalytic cracking combined technology

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610674083.1A CN106311313A (en) 2016-08-16 2016-08-16 Delayed coking-hydrofining-catalytic cracking combined technology

Publications (1)

Publication Number Publication Date
CN106311313A true CN106311313A (en) 2017-01-11

Family

ID=57739566

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610674083.1A Pending CN106311313A (en) 2016-08-16 2016-08-16 Delayed coking-hydrofining-catalytic cracking combined technology

Country Status (1)

Country Link
CN (1) CN106311313A (en)

Citations (5)

* 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
CN1895777A (en) * 2005-07-14 2007-01-17 北京化工大学 Porous molecular-sieve catalyst for assembling carbide and its preparation
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

Patent Citations (5)

* 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
CN1895777A (en) * 2005-07-14 2007-01-17 北京化工大学 Porous molecular-sieve catalyst for assembling carbide and its preparation
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

Non-Patent Citations (14)

* Cited by examiner, † Cited by third party
Title
F•维拉尼: "《稀土技术及其应用》", 31 July 1986, 烃加工出版社 *
中国石油化工集团公司人事部，等: "《加氢裂化装置操作工》", 30 September 2008, 中国石化出版社 *
何鸣元，等: "《石油炼制和基本有机化学品合成的绿色化学》", 31 January 2006, 中国石化出版社 *
姜琳琳: "全馏分FCC汽油加氢改质中改性MCM-41催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
崔克清，等: "《化工工艺及安全》", 31 May 2004, 化学工业出版社 *
张文成: "改性MCM-41 分子筛的制备及加氢催化性能研究", 《第十一届全国青年催化学术会议论文集（下）》 *
李静海，等: "《展望21世纪的化学工程》", 31 October 2004, 化学工业出版社 *
林世雄: "《石油炼制工程（第三版）》", 31 July 2000, 化学工业出版社 *
王基铭: "《石油炼制辞典》", 30 September 2013, 中国石化出版社 *
王海彦，等: "《石油加工工艺学》", 31 January 2014, 中国石化出版社 *
王福安，等: "《绿色过程工程引论》", 31 October 2002, 化学工业出版社 *
王雷，等: "《炼油工艺学》", 31 August 2011, 中国石化出版社 *
邝生鲁: "《现代精细化工高新技术与产品合成工艺》", 31 December 1997, 科学技术文献出版社 *
阎子峰: "《纳米催化技术》", 31 May 2003, 化学工业出版社 *

Similar Documents

Publication Publication Date Title
CN106221803A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106311313A (en) Delayed coking-hydrofining-catalytic cracking combined technology
CN106147859A (en) A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106244233A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106244230A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106244231A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106221802A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190297A (en) A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106118733A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190300A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106147861A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106147862A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106281456A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106244234A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106118742A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190302A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106281455A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN103773482B (en) A kind of method for hydrogen cracking producing high-quality industrial chemicals
CN106281451A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106281450A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190284A (en) A kind of residuum hydrodesulfurization RFCC group technology of sour crude
CN106118741A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190301A (en) A kind of catalytic cracking combined technique of delayed coking hydrofinishing
CN106190252A (en) A kind of straight-run naphtha hydrofining technology
CN106281454A (en) A kind of residuum hydrodesulfurization RFCC group technology of sour crude

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170111