CN106244202A - A kind of coking gasoline hydrogenation refining technique - Google Patents
A kind of coking gasoline hydrogenation refining technique Download PDFInfo
- Publication number
- CN106244202A CN106244202A CN201610694715.0A CN201610694715A CN106244202A CN 106244202 A CN106244202 A CN 106244202A CN 201610694715 A CN201610694715 A CN 201610694715A CN 106244202 A CN106244202 A CN 106244202A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- fixed bed
- bed reactors
- mcm
- carrier
- 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
Links
Classifications
-
- 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
- C10G45/06—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 nickel or cobalt metal, or compounds thereof
- C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of coking gasoline hydrogenation refining technique, 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 Cu 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors is: reaction temperature is 240 350 DEG C, and hydrogen dividing potential drop is 2 3.5MPa, hydrogen to oil volume ratio 450 700, volume space velocity 1 2h‑1.Coker gasoline 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 Hydrogenation of Coker Gasoline desulfuration purification technique, be specifically related to a kind of Jiao using special catalyst to carry out
Change gasoline hydrofinishing technique.
Background technology
Coker gasoline coker naphtha, also known as coking naphtha, is that delayed coking produces the initial boiling point obtained extremely
The fraction of 180 (205 DEG C).The sulfur content of coker gasoline, olefin(e) centent are high, motor octane number relatively low (about about 60), peace
Qualitative difference (bromine valency 40～60gBr/100g), the coker gasoline after stable, typically need to be through hydrogenation only as semi-finished product
Refined, remove the most nitrogenous, sulfur-containing compound and alkadienes, just can be used as motor petrol blending component or former as petrochemical industry
Material (light oil) produces ethylene, as synthetic ammonia feedstock or as catalytic reforming raw material.
The sulfur content of coker gasoline typically at 0.6%-1.0%, namely 6000 to 10000ppm, the highest sulfur content
Seriously limit the use of coker gasoline.Therefore coker gasoline must be processed, to remove the highest sulfur content.
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 6000ppm-1 ten thousand ppm,
The catalyst that existing unifining process uses, it is difficult to adapt to the highest sulfur content, typically can there are two problems: one is
The activity decrease of catalyst is fast, and device use cycle of catalyst under the operating mode processing other raw materials can reach 6a (6
Year) the most longer, but after processing coker gasoline, the use cycle of catalyst only has 1-2a.The most more catalyst changeout is tight
The economic benefit that have impact on device of weight.Two is that device reaction device pressure drop of column raises quickly, is processing coker gasoline 3-6
After individual month, device is just forced owing to the upper limit touched the mark drops in reactor pressure to stop work.By the investigation of same device is sent out
Existing, during coking gasoline hydrogenation refining, there is the high too fast phenomenon of reactor pressure falling-rising the most to some extent.
The analysis found that, when the catalyst that existing hydrofinishing uses is used for coking gasoline hydrogenation refining, 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 gasoline 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 gasoline process for refining is provided, uses the catalyst improved effectively to be contained by the sulfur in coker gasoline
Amount controls at below 5ppm, 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 Hydrogenation of Coker Gasoline desulfuration purification technique, this technique can be by coker gasoline
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 coking gasoline hydrogenation refining technique, 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 Cu 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4's
Mixture.
The reaction condition of described fixed bed reactors is: reaction temperature is 240-350 DEG C, and hydrogen dividing potential drop is 2-3.5MPa, hydrogen
Oil volume is than 450-700, volume space velocity 1-2h-1。
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: be situated between to the Siliceous MCM-41 of finished product
Porous molecular sieve inner surfaces of pores introduces Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of MCM-41,
Thus improve catalysis activity, absorption and the Thermodynamically stable performance etc. of MCM-41 mesopore molecular sieve on the whole.
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 Cu2+MCM-41 as carrier could realize sulfur content control effect, inventor has attempted at MCM-
Adulterate in 41 Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize described effect.To the greatest extent
Manage described mechanism current and unclear, but this have no effect on the enforcement of the present invention, inventor according to well-known theory with it is experimentally confirmed that
Cooperative effect is there is between itself and the active component of the present invention.
Described Cu2+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 coker gasoline desulfurized effect.More pleasurable
It is to work as Cu2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when draw with
Cu2+Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control extremely low
Within the scope of, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier 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, sulfur content in coker gasoline 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 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 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: 280-300 DEG C, and hydrogen dividing potential drop is 2.5-3.0MPa, hydrogen oil
Volume ratio 500-650, volume space velocity 1-1.5h-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 gasoline and oil-polluted water, a part of gasoline is made overhead reflux and is used, and a part of gasoline 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 raw gasoline.
The raw gasoline come from fractional distillation return tank of top of the tower enters gasoline after stable gasoline (refined Petroleum)/raw gasoline 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.At the bottom of tower, stable gasoline goes 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 Cu2+
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 Cr2O3、ZrO2、CeO2、V2O5With
NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization to coker gasoline can control at total sulfur content
Less than 5ppm, decrease the loss of catalyst active component and the formation of coke so that the service life of catalyst can simultaneously
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 doping Cu2+MCM-41, Cu2+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 coker gasoline 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 gasoline, its sulfur content is up to 8900ppm.
Controlling reaction condition is: 300 DEG C, hydrogen dividing potential drop is 3.0MPa, hydrogen to oil volume ratio 500, volume space velocity 1h-1。
Testing final product, total sulfur content is reduced to 5ppm, after plant running half a year, beds pressure drop without
Any change.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+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 4ppm, 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 28ppm, and beds pressure drop is increased beyond 5%.
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 26ppm, and beds pressure drop is increased beyond 5%.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 38ppm, and beds pressure drop is increased beyond 5%.
Comparative example 4
By the Cu 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 23ppm, and beds pressure drop is increased beyond 5%.
Comparative example 5
By the Cu 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 25ppm, 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
MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Cu of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other
Possessing cooperative effect between component, 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 44ppm, 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 42ppm, 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.
Embodiment 3
Containing catalyst aid Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 2%,
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 14.9%.
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 2.2%.
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 2.7%.
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. a coking gasoline hydrogenation refining technique, 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 Cu 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixing
Thing,
The reaction condition of described fixed bed reactors is: reaction temperature is 240-350 DEG C, and hydrogen dividing potential drop is 2-3.5MPa, hydrogen oil body
Long-pending ratio 450-700, volume space velocity 1-2h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that hetero atom Cu2+Doping be MCM-41 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 MCM-
The 3-12% of 41 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:
280-300 DEG C, hydrogen dividing potential drop is 2.5-3.0MPa, hydrogen to oil volume ratio 500-650, volume space velocity 1-1.5h-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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610694715.0A CN106244202A (en) | 2016-08-19 | 2016-08-19 | A kind of coking gasoline hydrogenation refining technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610694715.0A CN106244202A (en) | 2016-08-19 | 2016-08-19 | A kind of coking gasoline hydrogenation refining technique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106244202A true CN106244202A (en) | 2016-12-21 |
Family
ID=57593205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610694715.0A Pending CN106244202A (en) | 2016-08-19 | 2016-08-19 | A kind of coking gasoline hydrogenation refining technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106244202A (en) |
Citations (5)
| 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 |
-
2016
- 2016-08-19 CN CN201610694715.0A patent/CN106244202A/en active Pending
Patent Citations (5)
| 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)
| 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 |
|---|---|---|
| CN106244202A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106118725A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106118728A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106190251A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106118722A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106190246A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106221769A (en) | A kind of coker gas oil hydrofining technology | |
| CN106281422A (en) | A kind of coker gas oil hydrofining technology | |
| CN106244214A (en) | A kind of coker gas oil hydrofining technology | |
| CN106281424A (en) | A kind of coker gas oil hydrofining technology | |
| CN106118730A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106221784A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106221747A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106118726A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106244218A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106190258A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106281423A (en) | A kind of coker gas oil hydrofining technology | |
| CN106221782A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106221740A (en) | A kind of coker gas oil hydrofining technology | |
| CN106281426A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106221735A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106190242A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106281413A (en) | A kind of coking gasoline hydrogenation refining technique | |
| CN106190270A (en) | A kind of coker gas oil hydrofining technology | |
| CN106244222A (en) | A kind of coker gas oil hydrofining technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |
Application publication date: 20161221 |
|
| WD01 | Invention patent application deemed withdrawn after publication |