CN106221732A - A kind of coker gas oil hydrofining technology - Google Patents
A kind of coker gas oil hydrofining technology Download PDFInfo
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- CN106221732A CN106221732A CN201610873965.0A CN201610873965A CN106221732A CN 106221732 A CN106221732 A CN 106221732A CN 201610873965 A CN201610873965 A CN 201610873965A CN 106221732 A CN106221732 A CN 106221732A
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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
-
- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (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 complex or the mixture of MSU G, SBA 15 and HMS；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 NbOPO4Mixture, 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
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 complex or the mixture of MSU-G, SBA-15 and HMS.
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 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。
An object of the present invention is that, it is provided that the compound of a kind of 3 kinds of different mesopore molecular sieves works in coordination with effect to show
Should be with special catalytic performance, described cooperative effect shows that desulfuration purification aspect, special catalytic performance are then to show right
On the service life of catalyst and the raising of catalysis activity.
In catalyst field, according to the definition of IUPAC (IUPAC), the aperture title less than 2nm
For micropore；The aperture referred to as macropore more than 50nm；Aperture the most mesoporous (or claiming mesopore) between 2 to 50nm.Mesoporous material
Being a kind of aperture new material with huge specific surface area and three-dimensional open-framework between micropore and macropore, it has
The excellent specific property that other porous material does not has: there is the pore passage structure of high-sequential；The single distribution in aperture, and aperture size
Can change at relative broad range；Mesoporous various shapes, hole wall composition and character controllable；Height can be obtained by optimum synthesis condition
Heat stability and hydrothermal stability.
But in present applications ' the tail must be taken, described mesoporous material, when for catalytic field, is all single use, such as MCM system
Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU-
4, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA-
8, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Two kinds of carriers of a few studies literature research compound, such as Y/SBA-15, Y/SAPO-5 etc., majority is to be situated between
Hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve are main.Use the compound with performance of 3 kinds of different mesopore molecular sieves
Go out cooperative effect and the research of special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is complex or the mixture of MSU-G, SBA-15 and HMS.Described complex or mixed
In compound, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15):
(0.5-0.7)。
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention uses is all the existing molecular sieve of catalytic field, and it is
Through obtaining widely studied and application at catalytic field.
MSU-G is a kind of to have vesicle structure shape particle shape and the mesopore molecular sieve of layered framework structure, and it has height
Degree skeleton crosslinking and relatively thick skeleton wall and there is superpower heat stability and hydrothermal stability, its skeleton hole is with vertical
Being cross-linked with each other in layer and the hole being parallel to layer, diffusion path is the shortest because its vesicle shell is thick.The vesicle shape particle of MSU-G molecular sieve
Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is the highest.
SBA-15 belongs to the one of mesopore molecular sieve, has two-dimentional six square tube pore structures, has P3mm space group.At XRD
In diffracting spectrum, main peak is near about 1 °, for (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively
Weak, it is difficult to observe.Additionally, the silicon dioxide on SBA-15 skeleton is generally amorphous state, observe not in Radix Rumicis XRD diffraction
To obvious diffraction maximum.SBA-15 has a bigger aperture (maximum up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because of
And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the most unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S
Type mesoporous material is thicker, thus hydrothermal stability is more preferable, and short distance is the most unordered simultaneously organizational structure and aperture modulation scope are more
Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction
The heart.
The present invention, from each mesoporous material, carries out compound pairing, screens through widely, filter out MSU-G, SBA-15
With the compound of HMS or mixing.Inventor finds, in numerous complex/mixture, and only MSU-G, SBA-15 and HMS tri-
Compound or the mixing of person, could realize the collaborative lifting of hydrofinishing effect, and enables to catalysis activity and do not reduce for a long time, makes
Can be greatly increased with the life-span.In other words, the only specific compound or mixing of MSU-G, SBA-15 and HMS three of the present invention,
Solve collaborative and two technical problems in service life the most simultaneously.Other coordinate, or do not possess synergism, or use the longevity
Order shorter.
Described complex, can use being simply mixed of MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two
After mixing, such as MSU-G/SBA-15 complex, the mixing of MSU-G/HMS and SBA-15/HMS complex.Described being combined can
To use known electrostatic matching method, ion exchange, two step crystallization methods etc. to be prepared.These mesopore molecular sieves are combined with it
The preparation method of thing is the known method of catalyst field, and the present invention no longer repeats with regard to it.
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 total content of described active component is the 1%-15% of vehicle 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..
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.
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 choosing special ratios
MSU-G, SBA-15 and HMS complex/mixture is as carrier, and chooses the nitridation two molybdenum MO of special ratios2N, tungsten nitride
W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component, and described catalyst is possibly together with catalyst aid, and described catalyst aid is
Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrogenation to coker gas oil
Desulfurization can control at total sulfur content less than 5ppm, decreases the loss of catalyst active component and the formation of coke simultaneously so that
The service life of catalyst can reach 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 the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1:
1.1:0.5.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier
The 10% of quality, 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 2ppm, after plant running half a year, beds pressure drop without
Any change.
Embodiment 2
Preparing catalyst by infusion process, carrier is MSU-G/SBA-15 complex, MSU-G/HMS and SBA-15/
The mixing of HMS complex, wherein the ratio of MSU-G, SBA-15 and HMS is same as in Example 1.Described active component nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc 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 MSU-G, 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 2
The carrier of embodiment 1 is replaced with SBA-15, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 34ppm, and beds pressure drop is increased beyond 5%.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 40ppm, and beds pressure drop is increased beyond 5%.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and beds pressure drop is increased beyond 5%.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and beds pressure drop is increased beyond 5%.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 33ppm, and beds pressure drop is increased beyond 5%.
Embodiment 1 shows with comparative example 1-6, and the present invention uses MSU-G, SBA-15 and HMS complex of special ratios/mixed
Compound is as carrier, when replacing with single carrier or complex carrier two-by-two, does not all reach the technique effect of the present invention, therefore originally
MSU-G, SBA-15 and HMS complex/mixture of the special ratios of invention has as between carrier and other components of catalyst
Standby cooperative effect, described hydrofining technology creates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 30ppm, 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 48ppm, and beds pressure drop is increased beyond 5%.
Above-described embodiment and comparative example 7-8 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.
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 16.2%.
Comparative example 9
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 5.7%.
Comparative example 10
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 6.4%.
Embodiment 3 shows with comparative example 9-10, 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. 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 complex or the mixture of MSU-G, SBA-15 and HMS,
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 NbOPO4Mixing
Thing,
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 the weight ratio of MSU-G, SBA-15 and HMS is 1:
(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15): (0.5-0.7).
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is vehicle weight
3-12%, 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.
7. hydrofining technology as claimed in claim 1, it is characterised in that Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Each
Content be respectively the 1-7%, preferably 2-4% of carrier quality.
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|---|---|---|---|---|
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| US20160279609A1 (en) * | 2014-04-04 | 2016-09-29 | Tongji University | Low-temperature and highly efficient denitration catalyst and corresponding method of preparation |
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