CN106221745A - A kind of aerial kerosene hydrofining technology - Google Patents

A kind of aerial kerosene hydrofining technology Download PDF

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Publication number
CN106221745A
CN106221745A CN201610685359.6A CN201610685359A CN106221745A CN 106221745 A CN106221745 A CN 106221745A CN 201610685359 A CN201610685359 A CN 201610685359A CN 106221745 A CN106221745 A CN 106221745A
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catalyst
fixed bed
kit
bed reactors
carrier
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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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    • 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
    • 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

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  • 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 aerial kerosene 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；Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors is: reaction temperature is 260 320 DEG C, and hydrogen dividing potential drop is 2.8 3.6MPa, hydrogen to oil volume ratio 150 250, volume space velocity 2.0 4.0h‑1.Aerial kerosene total sulfur content can be controlled, less than 5ppm, to control the total nitrogen content in aerial kerosene within 10ppm by this technique simultaneously.

Description

A kind of aerial kerosene hydrofining technology
Technical field
The present invention relates to aerial kerosene hydrodesulfurization process for refining, be specifically related to a kind of boat using special catalyst to carry out Empty kerosene hydrogenation desulfuration purification technique.
Background technology
Aerial kerosene is one of oil product.English name Jet fuel No.3, calls jet fuel.Main by difference The hydrocarbon compound composition of fraction.Aerial kerosene is mainly used as the fuel of aero-turbine.
Along with transportation is increasingly stronger to Economic Stimulus effect, China's transportation cause development in recent years is swift and violent. From the point of view of the consumption figure of State Statistics Bureau's statistics, China's jet fuel consumption figure the whole year in 2008 is 1279.9 ten thousand tons, with The consumption figure of the same period in 2007 is compared and has been gone up 3.6%, and from the point of view of the import volume of customs statistics, China fires 2008 years jets Expecting import altogether 647.8 ten thousand tons, increased by 23.5% on a year-on-year basis, monthly import volume reaches 540,000 tons.
In the world always according to the standard of JETA-1, the quality of jet fuel being come requirement, this also becomes jet combustion in the world The standard criterion of material trade deal.Its total acid number of this standard-required (mgKOH/g) is not more than 0.015, and total sulfur content maximum must not More than 0.30wt%, i.e. cannot be greater than 30ppm, corrosive nature is also required by aerial kerosene simultaneously.Analysis of experiments shows, impact The main cause of boat coal silver slice corrosion is the elementary sulfur in active sulfide, and when its content reaches 2 μ g/g, boat coal silver slice corrosion is the most not Qualified, silver slice corrosion can be promoted with elementary sulfur when mercaptan and disulphide etc. coexist.
Along with heaviness, the in poor quality of world's crude oil are deepened day by day, crude oil sulfur content is more and more higher, and the lightweight of high-quality is former Oil is constantly reducing.The crude oil of refinery's processing in recent years mostly is imported crude oil, and relative density increases year by year, in several years of the beginning of this century The average density of whole world refinery processing crude oil rises to about 0.8633.The problem that sulfur content is high is the most extremely serious, the current world The yield of upper sour crude oil and sour crude accounts for more than the 75% of world's crude oil total output.20th century the mid-90 whole world refinery The crude oil average sulfur content of processing is 0.9%, and the beginning of this century has increased to 1.6%.
For producing the cleaning jet fuel (aerial kerosene) of high-quality, desulfurization technology obtains huge attention.Current desulfurization Technology, divides from the angle whether being hydrogenated with, is divided into hydrodesulfurization and non-hydrodesulfurization.Hydrodesulfurization technology is intrinsic excellent due to it Gesture becomes the technology of processing high grade fuel oil the most ripe.Compared to conventional process for refining, kerosene hydrogenation Technique decreases alkaline residue and hargil exhaust emission, and it is the most higher for the adaptability of raw material, and therefore hydrogenation technique is future development Main way.
The hydrogenation technique of current jet fuel (aerial kerosene) is similar, and typical technique is as follows: virgin kerosene is certainly Raw material tank field is sent into raw material surge tank, with kerosene raffinate heat exchange after feed pump boosts to about 3.0MPa, then mixes with hydrogen Again with product heat exchange.Enter charging heating furnace after mixed hydrogen raw material and product heat exchange to be heated to reacting temperature required entrance Hydrogenation reactor.Mixed hydrogen raw material carries out hydrogenation reaction under the effect of catalyst, enters after product and mixed hydrogen raw material heat exchange High pressure hot separator is isolated major part and is generated oil, high-pressure separator top oil gas priority and recycle hydrogen, cold high pressure separator base oil After heat exchange inject desalted water, then enter air cooler, water cooler be cooled to 40 DEG C enter cold high pressure separators isolate hydrogen.Cold anticyclone It is combined into stripper with high pressure hot separator base oil after separator oil and high pressure hot separator gas heat exchange.
But existing hydrofining technology is all to arrange for former high-quality edible vegetable oil.For current high sulfur content The virgin kerosene that crude oil production obtains, owing to its high sulfur content, its catalyst used and hydroconversion condition are all difficult to be suitable for, produces The setting that meets the requirements be reduce sulfur content to below 10ppm, can not be suitable for.
A kind of jet fuel (aerial kerosene) hydrodesulfurization is provided, can be effectively by the aviation of high sulfur content Sulfur content in kerosene controls at below 10ppm, with satisfied discharge and Corrosion standards, is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of aerial kerosene hydrodesulfurization process for refining, this technique can be by aerial kerosene In total sulfur content be reduced to below 10ppm, with satisfied discharge and Corrosion standards.
For reaching this purpose, the present invention by the following technical solutions:
A kind of aerial kerosene 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.
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing Thing.
The reaction condition of described fixed bed reactors is: reaction temperature is 260-320 DEG C, and hydrogen dividing potential drop is 2.8-3.6MPa, Hydrogen to oil volume ratio 150-250, volume space velocity 2.0-4.0h-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 aerial kerosene 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 aerial kerosene 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.
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 TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined ?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding, Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4 Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5, Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid, Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.The typical but non-limiting example of the present invention As follows:
Sodium silicate, cetyl trimethylammonium bromide (CTAB), sodium ethylene diamine tetracetate (EDTA) and distilled water are massaged You mix the ratio than 1:0.25:1:60, load with in teflon-lined autoclave pressure, after stirring under 373K Constant temperature 24h, the pH of re-adjustments mixture are 10.5, after constant temperature 4 times, take out product, with distilled water cyclic washing to filtrate PH=7, then under 373K, constant temperature overnight, obtains the KIT-1 with surfactant.KIT-1 with surfactant is existed Roasting 1.5h under 523K, then roasting 6h in air atmosphere under 813K, obtains KIT-1 powder body.By this powder body 0.1mol/L Salpeter solution carry out pickling (control solid-to-liquid ratio is 1:10), under room temperature stir 0.5h, filter, be washed with distilled water to filtrate Dry under pH=7,373K and obtain matrix KIT-1 molecular sieve.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 280-300 DEG C, and hydrogen dividing potential drop is 3.0- 3.4MPa, hydrogen to oil volume ratio 180-220, volume space velocity 2.0-4.0h-1。
Preferably, described technological process includes, virgin kerosene, after filter, surge tank, is pumped into heat exchanger by feed pump With product boat coal heat exchange, after heat exchange, it is mixed to form hydrogen oil mixture with recycle hydrogen and new hydrogen, again laggard with product heat exchange Enter heating furnace, be heated to reaction temperature and enter hydrofining reactor (fixed bed reactors), hydrogen oil mixture in the reactor Under catalyst action, the reaction such as carry out that hydrodesulfurization, denitrogenation, deoxidation, alkene is saturated and aromatic hydrocarbons is saturated, product is through changing Heat, more water cooled to predetermined temperature, enter high-pressure separator, high-pressure separator top gas phase returns recycle hydrogen as recycle hydrogen and delays Rushing tank, oil phase enters low pressure separator, and the generation oil drawn bottom low pressure separator enters stripper after product heat exchange, Tower top oil gas enters separatory tank after air cooling, water-cooled and obtains Petroleum, and stripping tower bottom obtains aerial kerosene.
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, described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4's Mixture so that this catalyst produces cooperative effect, the hydrodesulfurization to aerial kerosene can control at total sulfur content less than 5ppm, Total nitrogen content in aerial kerosene is controlled within 10ppm simultaneously.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping 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 aerial kerosene 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 virgin kerosene, its total sulfur content 267ppm, basic n content is 299ppm.
Controlling reaction condition is: temperature 300 DEG C, hydrogen dividing potential drop 3.2MPa, hydrogen to oil volume ratio 200, volume space velocity 2h-1。
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 8ppm.
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 2ppm, and total alkaline nitrogen content is reduced to 6ppm.
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 38ppm, and total alkaline nitrogen content is reduced to 46ppm.
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 41ppm, and total alkaline nitrogen content is reduced to 52ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 49ppm.
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 46ppm, and total alkaline nitrogen content is reduced to 54ppm.
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 45ppm, and total alkaline nitrogen content is reduced to 57ppm.
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 52ppm, and total alkaline nitrogen content is reduced to 63ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 48ppm, and total alkaline nitrogen content is reduced to 66ppm.
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 TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and 3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same The beds pressure drop of time embodiment 1 reduces 16%.
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 5.3%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 4.8%.
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. an aerial kerosene 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,
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture,
The reaction condition of described fixed bed reactors is: reaction temperature is 260-320 DEG C, and hydrogen dividing potential drop is 2.8-3.6MPa, hydrogen oil Volume ratio 150-250, volume space velocity 2.0-4.0h-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: Reaction temperature is 280-300 DEG C, and hydrogen dividing potential drop is 3.0-3.4MPa, hydrogen to oil volume ratio 180-220, volume space velocity 2.0-4.0h-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 TiO2、CeO2、V2O5And NbOPO4Respective content It is respectively the 1-7%, preferably 2-4% of carrier quality.
CN201610685359.6A 2016-08-18 2016-08-18 A kind of aerial kerosene hydrofining technology Pending CN106221745A (en)

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Application publication date: 20161214