CN106281418A - A kind of coker gas oil hydrofining technology - Google Patents

A kind of coker gas oil hydrofining technology Download PDF

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Publication number
CN106281418A
CN106281418A CN201610657088.3A CN201610657088A CN106281418A CN 106281418 A CN106281418 A CN 106281418A CN 201610657088 A CN201610657088 A CN 201610657088A CN 106281418 A CN106281418 A CN 106281418A
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oil
kit
fixed bed
bed reactors
hydrogen
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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 CN201610657088.3A priority Critical patent/CN106281418A/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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • C10G2400/04—Diesel oil

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

Abstract

The invention discloses a kind of coker gas oil hydrofining technology, described technique uses fixed bed reactors, is filled with hydrogenation desulfurization and denitrogenation catalyst in fixed bed reactors, and described catalyst includes carrier and active component；Described carrier is incorporation hetero atom Co 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；The reaction condition of described fixed bed reactors is: reaction temperature is 300 450 DEG C, and hydrogen dividing potential drop is 6 9MPa, hydrogen to oil volume ratio 450 700, volume space velocity 1.5 3h‑1.Coker gas oil total sulfur content can be controlled less than 5ppm by this technique, and service life catalyst is brought up to more than 8a.

Description

A kind of coker gas oil hydrofining technology
Technical field
The present invention relates to coker gas oil hydrodesulfurization process for refining, be specifically related to a kind of Jiao using special catalyst to carry out Change Model of Diesel Hydrogenation Refining.
Background technology
Delay coking process is with mink cell focus, and such as decompression residuum, cracked residue etc. are raw material, at high temperature (about 500 DEG C) Under the conditions of the thermal cracking that carries out and condensation reaction, produce gas, gasoline, diesel oil, wax oil and petroleum coke.
The sulfur content of coker gas oil, olefin(e) centent are high, and Cetane number is higher than catalytic diesel oil, but the most unstable, (oxygen easy to change Change), impurity is many, and the coker gas oil after stable, only as semi-finished product, typically need to remove wherein contain through hydrofinishing Nitrogen, sulfur-containing compound and alkadienes, just can be used as derv fuel blending component or use as petrochemical materials.
The sulfur content of coker gas oil is typically the highest about 1.0%, namely more than 10000ppm, and the highest contains Sulfur content seriously limits the use of coker gas oil.Therefore coker gas oil must be processed, contain with the highest sulfur of removing Amount.
In existing desulfurization process, hydrofinishing is ripe because of environmentally-friendly technique, has been widely used, but existing Hydrogenation process for raw material in, sulfur content is many in hundreds of ppm rank, for the sulfur content of up to 10,000 ppm, existing adds The catalyst that hydrogen subtractive process uses, it is difficult to adapt to the highest sulfur content, typically can there are two problems: one is catalyst Activity decrease is fast, and device use cycle of catalyst under the operating mode processing other raw materials can reach 6a (6 years) even more Long, but after processing coker gas oil, the use cycle of catalyst only has 1-2a.Serious have impact on of the most more catalyst changeout The economic benefit of device.Two is that device reaction device pressure drop of column raises quickly, fills after processing coker gas oil 3-6 month Put the upper limit just touched the mark due to reactor pressure fall and be forced to stop work.By the investigation of same device is found, in coking The high too fast phenomenon of reactor pressure falling-rising is there is the most to some extent during diesel oil hydrofining.
The analysis found that, when the catalyst that existing hydrofinishing uses is used for coker gas oil hydrofinishing, catalyst Metal component loss relatively big, illustrate that activity over catalysts component reduces, pore volume diminishes much simultaneously, causes reactant and catalysis Agent contact area declines, and this all direct reaction is in the decline of catalyst activity.Meanwhile, coker gas oil is producing feed ethylene, weight When material all in one piece and synthesis ammonia material, being required to higher operating severity, hydrogenation depth is high, causes beds carbon distribution to aggravate, pressure Power fall rises rapidly.And when pressure drop rises to upper limit 0.38MPa that equipment allows, be necessary for beds Reason.
The most how coker gas oil process for refining is provided, uses the catalyst improved effectively to be contained by the sulfur in coker gas oil Amount controls at below 5ppm, to meet state five requirement, and improves service life, is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of coker gas oil hydrodesulfurization process for refining, this technique can be by coker gas oil In total sulfur content be reduced to below 5ppm, and catalyst is brought up to more than 8a service life.
For reaching this purpose, the present invention by the following technical solutions:
A kind of coker gas oil hydrofining technology, described technique uses fixed bed reactors, loads in fixed bed reactors Hydrogenation catalyst, described catalyst is had to include carrier and active component.
Described carrier is incorporation hetero atom Co 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.
The reaction condition of described fixed bed reactors is: reaction temperature is 300-450 DEG C, and hydrogen dividing potential drop is 6-9MPa, hydrogen oil Volume ratio 450-700, volume space velocity 1.5-3h-1。
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: in KIT-1 building-up process, adds Co2+ Saline solution, before KIT-1 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part backbone element thus embedding Enter in the skeleton of molecular sieve, improve catalysis activity, absorption and the thermodynamic stability of KIT-1 mesopore molecular sieve on the whole Can etc..
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 Co2+KIT-1 could realize sulfur content as carrier and control and the balance of loss of octane number, inventor tastes Try to adulterate in KIT-1: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize institute State effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on KIT-1 inner surfaces of pores to compare, the present invention Isomorphous substitution approach more stable.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, invention People 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 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 coker gas oil desulfurized effect.More pleasurable It is to work as Co2+When doping in KIT-1 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when draw 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 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, sulfur content in coker gas oil can be realized and control at below 10ppm and denitrification ability notable.It is to say, this Four kinds of active components of invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just possess association Same effect.Outside this molar ratio range, or omit or replace any one component, all can not realize cooperative effect.
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.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: 320-350 DEG C, and hydrogen dividing potential drop is 7.8-8.3MPa, hydrogen oil Volume ratio 450-550, volume space velocity 1.5-2h-1。
Preferably, described technological process includes, device mainly includes raw material prefractionation part (dehydration and back-end crop), reacting part Divide and fractionating section.
1, raw material prefractionation part
The raw oil come from tank field removes the solid particle more than 25 μm through raw oil filter, changes with prefractionation tower top vapour After heat heats up, heat up with the backflow heat exchange of prefractionator stage casing, then with prefractionator at the bottom of heavy oil heat exchange heat up, after through pre-point Evaporate tower charging heating furnace heating and enter raw oil prefractionator (dehydration), after tower top vapour is condensed, enter prefractionator top return tank And it being separated into diesel oil and oil-polluted water, a part of diesel oil is made overhead reflux and is used, and a part of diesel oil is made hydrogenation unit raw material and used； The tops of prefractionator (dehydration) is discharged by the bottom of tower, then enters prefractionator (back-end crop) after heat exchange and heating furnace are heated, Prefractionator (back-end crop) end heavy oil, goes out device as Colophonium, and other is made hydrogenation unit raw material after distillating fraction mixing and use.
2, reactive moieties
Hydrogenation raw oil surge tank, raw oil surge tank fuel gas sealing gland is entered through pretreated coal tar.From Raw oil surge tank come raw oil hydrogenated feed pump supercharging after, under flow-control with mix hydrogen mix, reacted outflow After thing/reaction feed heat exchanger heat exchange, the most reacted charging heating furnace is heated to reacting temperature required, enters hydro-upgrading anti- Answer device, between reactor, be provided with note quenching hydrogen facility.
The reacted effluent of autoreactor reaction effluent out/reaction feed heat exchanger, reaction effluent/low point of oil Heat exchanger, reaction effluent/reaction feed heat exchanger successively with reaction feed, low point of oil, reaction feed heat exchange, the most reacted Effluent air cooler and water cooler cooling, enter high-pressure separator.In order to prevent the ammonium salt in reaction effluent at low temperature position Separate out, by water injecting pump flushing water noted in the pipeline of reaction effluent air cooler upstream side.
Reaction effluent after cooling carries out oil, gas and water three phase separation in high-pressure separator.High score gas (recycle hydrogen) warp After circulating hydrogen compressor entrance separatory tank separatory, enter circulating hydrogen compressor boosting, then divide two-way: a road is entered as quenching hydrogen Reactor；One tunnel mixes with the new hydrogen from make-up hydrogen compressor, and mixing hydrogen mixes as reaction feed with raw oil.Sulfur-bearing, contain Ammonia sewage is expelled to acidic water stripping device bottom high-pressure separator and processes.High score oil phase regulates through decompression under Liquid level Valve enters low pressure separator, and its flash gas drains into factory's fuel gas pipe network.
Low point of oil enters fractionating column after heat exchange.Enter tower temperature reaction effluent/low point of oil heat exchanger bypass regulation control System.
New hydrogen enters make-up hydrogen compressor through make-up hydrogen compressor entrance separatory tank after separatory, with recycle hydrogen after two-stage is boosted Mixing.
3, fractionating section
The low point of oil come from reactive moieties enters fractionating column through heat exchanger heat exchange.Setting reboiler furnace at the bottom of tower, tower top oil gas is through tower Head space cooler and water cooler are cooled to 40 DEG C, enter fractional distillation return tank of top of the tower and carry out gas, oil, water three phase separation.Flash off Gas drain into fuel gas pipe network.Sulfur-bearing carrying device together with high score sewage in ammonia sewage.Oil phase is fractionated into overhead reflux pump Boosting rear portion removes stabilizer as overhead reflux, a part as gas-oil.
The gas-oil come from fractional distillation return tank of top of the tower enters diesel oil after stablizing diesel oil (refined Petroleum)/gas-oil heat exchange Stabilizer.Stabilizer tower top oil gas is cooled to 40 DEG C through stablize tower top water cooler, entrance stablize return tank of top of the tower carry out gas, Oil, water three phase separation.The gas flashed off drains into fuel gas pipe network.Sulfur-bearing carrying device together with high score sewage in ammonia sewage. Oil phase is mostly as overhead reflux after stablizing the boosting of overhead reflux pump, and fraction enters as light oil and goes out dress in slops Put.Stablize diesel oil at the bottom of tower and go to tank field as Petroleum.
In order to suppress hydrogen sulfide to tower top pipeline and the corrosion of cold exchange device, use at fractionating column and stabilizer tower top pipeline Inject corrosion inhibiter measure.Corrosion inhibiter enters tower top pipeline from corrosion inhibiter tank through corrosion inhibiter infusion.
Refined oil at the bottom of fractionation column after refined oil pump supercharging with low point of oily heat exchange, be cooled to subsequently into diesel oil air cooler Go out device after 50 DEG C and go to tank field as high-grade fuel oil.
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+ 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 so that this catalyst produces cooperative effect, and the hydrodesulfurization to coker gas oil can control at total sulfur content low In 5ppm, decrease the loss of catalyst active component and the formation of coke so that the service life of catalyst can reach simultaneously To more than 8a.
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+KIT-1, Co2+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 coker gas oil is by north The double plunger micro pump of capital satellite manufactory manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-by gas cylinder 11A/ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product is laggard through the cooling of water-bath room temperature Row gas-liquid separation.
Raw materials used for Venezuela's coker gas oil, its sulfur content is up to 10300ppm.
Controlling reaction condition is: 340 DEG C, hydrogen dividing potential drop is 8.0MPa, hydrogen to oil volume ratio 500, volume space velocity 2h-1。
Testing final product, total sulfur content is reduced to 3ppm, after plant running half a year, beds pressure drop without Any change.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+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 3ppm, after plant running half a year, beds pressure drop without Any change.
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 43ppm, and beds pressure drop is increased beyond 5%.
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 47ppm, and beds pressure drop is increased beyond 5%.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 46ppm, and beds pressure drop is increased beyond 5%.
Comparative example 4
By the Co 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 39ppm, and beds pressure drop is increased beyond 5%.
Comparative example 5
By the Co 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 40ppm, and beds pressure drop is increased beyond 5%.
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 Co2+During doping difference, all reach not To the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping KIT-1 carrier and other components of catalyst Between possess cooperative effect, 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 57ppm, and beds pressure drop is increased beyond 5%.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 54ppm, and beds pressure drop is increased beyond 5%.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrofining technology of the present invention it Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces Give birth to 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. a coker gas oil hydrofining technology, described technique uses fixed bed reactors, is filled with in fixed bed reactors Hydrogenation catalyst, described catalyst includes carrier and active component, it is characterised in that
Described carrier is incorporation hetero atom Co 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,
The reaction condition of described fixed bed reactors is: reaction temperature is 300-450 DEG C, and hydrogen dividing potential drop is 6-9MPa, hydrogen oil volume Ratio 450-700, volume space velocity 1.5-3h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be KIT-1 weight 0.63%-0.72%.
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is carrier KIT- The 3-12% of 1 weight, preferably 5-10%.
4. hydrofining technology as claimed in claim 1, it is characterised in that nitrogenize two molybdenum 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. hydrofining technology as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is: 320-350 DEG C, hydrogen dividing potential drop is 7.8-8.3MPa, hydrogen to oil volume ratio 450-550, volume space velocity 1.5-2h-1。
6. hydrofining technology as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis Agent bed, preferably includes 2-3 beds.
CN201610657088.3A 2016-08-11 2016-08-11 A kind of coker gas oil hydrofining technology Pending CN106281418A (en)

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