CN106635136A - Hydrogenation, desulfurization and denitrification process of diesel oil - Google Patents

Hydrogenation, desulfurization and denitrification process of diesel oil Download PDF

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Publication number
CN106635136A
CN106635136A CN201610689485.9A CN201610689485A CN106635136A CN 106635136 A CN106635136 A CN 106635136A CN 201610689485 A CN201610689485 A CN 201610689485A CN 106635136 A CN106635136 A CN 106635136A
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catalyst
fixed bed
hydrogenation
mcm
desulfurization
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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
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G2300/70—Catalyst aspects

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

Abstract

The invention discloses a hydrogenation, desulfurization and denitrification process of diesel oil. The process adopts a fixed bed reactor; the fixed bed reactor is internally filled with a hydrogenation, desulfurization and denitrification catalyst; the catalyst comprises a carrier and an active component; the catalyst further comprises a catalysis auxiliary agent; reaction conditions of the fixed bed reactor are as follows: a reaction temperature is 320 DEG C to 360 DEG C, the reaction pressure is 6MPa to 8MPa, the hydrogen to oil volume ratio is 300 to 600 and the volume hourly space velocity is 1.0h<-1> to 2.5h<-1>. According to the process disclosed by the invention, the total sulfur content of the diesel oil can be controlled to be lower than 5ppm; meanwhile, the total nitrogen content in the diesel oil is controlled to be within 10ppm.

Description

A kind of diesel hydrogenation for removal sulphur denitrification process
Technical field
The present invention relates to diesel hydrogenation for removal sulphur denitrification process, and in particular to the hydrogenation that a kind of employing special catalyst is carried out takes off Sulphur denitrification process.
Background technology
Into 21st century, the demand of fuel oil and using increasing substantially, and sulfur-containing compound therein is brought Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide Jing engine combustions in fuel oil are produced (SOx) air is discharged into, acid rain and the pollution of fumes of sulphuric acid type etc. are produced, cause atmosphere pollution.
Sulphur is a kind of harmful substance that nature is present in gasoline, and rate first carried out phase in 1 day January in 2008 in Beijing When in the capital IV of the Europe IV standard cleaning diesel oil standard (sulfur content≤50mg/g), on May 5th, 2016, the Committee of Development and Reform, the Ministry of Finance, ring Department of guarantor portion etc. seven is issued with regard to printing and distributing《Accelerate product oil quality upgrading programme of work》Notify, scheme clearly expand automobile-used vapour, The standard of diesel oil state five performs scope.Whole eastern region is expanded to from original Jing-jin-ji region, the Yangtze River Delta, Pearl River Delta region key cities 11 provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, Jiangsu, Zhejiang, Fujian, Shandong, Guangdong and Hainan).In October, 2015 Before 31 days, eastern region is protected possesses the standard motor petrol of producing country five (oil of blend component containing ethanol petrol), automobile-used bavin for enterprise The ability of oil.From 1 day January in 2016, the motor petrol (ethanol vapor containing E10 for meeting the standard of state five is supplied in eastern region comprehensively Oil), derv fuel (biodiesel containing B5).The Europe V diesel oil that total sulfur content is not more than 10ppm is carried out in 2009 in Europe Standard.So, production ultra-low sulfur diesel oil has become the domestic oil refining enterprises realistic problem to be faced.
At present, producing the method for ultra-low sulfur diesel oil mainly includes hydrofinishing, oxidation sweetening, selective absorption, life Thing desulfurization etc..But hydrodesulfurization (HDS) technology is generally acknowledged most effective, most economical sulfur method.Research finds, in diesel oil Be most difficult to remove organic sulfur compound be 4 and (or) 4,6 alkyl-substituted oil-source rock correlations, this kind of sulfide due to There is the sterically hindered of alkyl when adsorbing on catalyst activity position, hinder reactant molecule connecing on adsorption activity position Nearly property, so that its hydrodesulfurization activity is low；Theoretical research also finds that Ni, Co, Mo are mutually layers with the hydrogenation activity of W sulfide The MoS of shape stacking2And WS2Nano-particle, MoS2The appropriate stacking of nano-particle contributes to reactant molecule on adsorption activity position Accessibility and highly active II class activity phase formation.
At present foreign countries' diesel hydrogenation for removal sulphur technology commonly uses double base or multicomponent catalyst, belongs to middle pressure depth and ultra-deep One section or two-stage desulfurization process, the process is in addition to desulfurization, moreover it is possible to reduce nitrogen and polycyclic aromatic hydrocarbon, improves Cetane number.It can The raw material of processing can process straight run oil than wide, can also process cracking fraction oil.Product sulfur content is：Using depth Hydrodesulfurization, less than 500 μ g/g；Using one section of ultra-deep hydrodesulfuration, less than 30 μ g/g.If adopting two sections of technologies can be with Reduce polycyclic aromatic hydrocarbon and improve Cetane number.
Triumphant King Company of Japan develops STARS hydrogenation catalyst technologies, two kinds of catalyst has been industrialized on this basis, i.e., KF-757 Ultra-deep Desulfurization of Diesel Fuels catalyst and the KF-848 refining catalytics with high desulfurization, denitrogenation, Tuo Fang and hydrogenation activity Agent, is applicable not only to hydro-refining unit, and suitable for raw material prerefining, FCC feedstock weighted BMO spaces for being hydrocracked etc.. For high-pressure diesel hydrogenation plant, its diesel oil sulfur content can be removed to 50ppm or lower, to reduce refined diesel oil density and The de- virtue of depth has fabulous effect.
Rope company of Top of Denmark catalyst newly developed has TK-554 (deep desulfuration), TK-574 (ultra-deep desulfurization), TK- 573 (deep desulfurations), TK-907 (aromatic hydrocarbons saturation and raising Cetane number) and TK-908 (aromatic hydrocarbons saturation and raising Cetane number) Deng.Wherein TK-574 high activities cobaltmolybdate catalyst is ultra-deep desulfurization catalyst, than TK-544 deep desulfurization catalyst opposite banks Product activity improves 30%～40%, and TK-544 catalyst is adopted on the diesel device of the production μ g/g of sulfur content 500, can make product Product sulfur content is down to 350 μ g/g.
American Association catalyst Co. AS-AT desulfurization removing nitrics Porous deproteinized bone three function catalyst newly developed, for diesel oil depth The second reactor (first reactor desulfurization is taken off to below 50 μ g/g) of the de- virtue device of degree desulfurization, can make total aromatic hydrocarbons take off to 10% with Under, sulphur is taken off to below 10 μ g/g.Typical operation conditions are：316 DEG C of reaction temperature, pressure 6.18MPa, liquid hourly space velocity (LHSV) is less than 2h-1, Hydrogen-oil ratio 712.
The current poor ignition quality fuel modification means for generally adopting both at home and abroad are hydrofinishing and hydro-upgrading.Hydrofinishing can be bright The aobvious color and stability for improving product, but it is limited to be limited Cetane number increase rate by thermodynamics of reactions, thus by plus Hydrogen is refined far from meeting requirement of the enterprise to product Cetane number.Cetane number of inferior diesel oil, desulfurization are improved for oil plant The demand of denitrogenation Porous deproteinized bone, American Standard Inc. be proposed MHUG hydro-upgradings technology and DN3110 Hydrobon catalysts, Z5723 gas reversion catalyst, and obtained first time commercial Application in 2000.The DN3110 hydrofinishings catalysis of Standard Co., Ltd Agent, Z5723 gas reversion catalyst are the one kind for adopting CENTINEL technologies and the production of actiCAT pre-curing technologies with aluminum oxide For the nickel molybdenum pre-sulfide catalyst of carrier, CENTINEL key problem in technology is than general catalyst in terms of active metal dispersion More preferably, it is easier to by convert metal oxides be metal sulfide.And actiCAT parts pre-curing technology, it is in catalyst Sulfur-loaded in production, realizes the sulfuration of catalyst, it is not necessary to catalyst the self-contained sulphur of utilization of hour catalyst is opened It is dried, it is not necessary to additionally inject vulcanizing agent, and soak time is shorter, will so cause device quickly, easily and safely to drive.
Therefore how to provide a kind of diesel hydrogenation for removal sulphur technique, can effectively by the sulfur content control in diesel oil 10ppm with Under, it is the difficult problem that this area faces while the nitride in diesel oil can be removed effectively to meet the standard of state five.
The content of the invention
It is an object of the invention to propose a kind of diesel hydrogenation for removal sulphur denitrification process, the technique can will be total in diesel oil Sulfur content is reduced to below 10ppm, to meet the standard of diesel oil state five.Meanwhile, the catalyst that the technique is adopted also causes diesel oil The removing of middle nitride is than more significant.
It is that, up to this purpose, the present invention is employed the following technical solutions：
A kind of diesel hydrogenation for removal sulphur denitrification process, the technique adopts fixed bed reactors, loads in fixed bed reactors There is hydrogenation catalyst, the catalyst includes carrier and active component.
The carrier is incorporation hetero atom Co in synthesis skeleton structure2+MCM-41.
The active component is two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2The mixture of C and tungsten carbide wc.
Described catalyst also contains catalyst aid, and the catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing Thing；
The reaction condition of the fixed bed reactors is：Reaction temperature is 320-360 DEG C, reaction pressure 6-8MPa, hydrogen oil Volume ratio 300-600, volume space velocity 1.0-2.5h-1。
MCM-41 is ordered into mesoporous material, and in six side's ordered arrangements, uniform in size, aperture size can be with during synthesis in its duct Directed agents and the difference of synthetic parts is added to change between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g, MCM-41 uniform pore diameters, with higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), be conducive to 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 the goal of the invention for only having MCM-41 to reach the present invention, and other mesoporous materials are all There is such-and-such defect, there is the technical difficulty for being difficult to overcome when being applied in the present invention, therefore the present invention selects to use MCM-41 is used as carrier basis.
Silica MCM-41 itself is acid very weak, is directly used as catalyst activity relatively low.Therefore, the present invention changes to it Property, to increase its catalysis activity.It is of the invention to be to the approach that MCM-41 mesopore molecular sieves are modified：In MCM-41 building-up processes, Add Co2+Salting liquid, before MCM-41 framework of molecular sieve structure is formed, by same order elements by Co2+Replace part skeleton unit During element is so as to be embedded in the skeleton of molecular sieve, catalysis activity, absorption and the heat of MCM-41 mesopore molecular sieves is improved on the whole Mechanical stability can be waited.
Although the method being modified to MCM-41 mesopore molecular sieves or approach are a lot, inventor has found, the present invention's urges Agent can only be using doping Co2+MCM-41 could realize sulfur content control and the balance of loss of octane number, invention as carrier People has attempted being adulterated in MCM-41:Al3+、Fe3+、Zn2+、Ga3+Deng the ion for producing anionic surface center, discovery all can not Realize the effect.Modified approach another with inventor passes through ion exchange by Cu2+It is supported on MCM-41 inner surfaces of pores to compare, The same order elements approach of the present invention is more stable.Although the mechanism is not known at present, this has no effect on the reality of the present invention Apply, inventor is according to well-known theory and it is experimentally confirmed that it has cooperative effect and the active component of the present invention between.
The Co2+Doping in MCM-41 must be controlled within specific content range, and its doping is with weight Meter, is 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%th, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%, 0.74 etc..
Inventor has found, outside this range, can cause drastically reducing for diesel oil denitrogenation and desulfurized effect.It is more pleasurable , work as Co2+When doping in MCM-41 is controlled in the range of 0.63%-0.72%, its desulphurizing ability is most strong, works as drafting With Co2+Doping is transverse axis, and during curve map with target desulfurized effect as the longitudinal axis, sulfur content can be controlled in pole in the content range Within the scope of low, the desulfurized effect that it is produced belongs to unforeseeable technique effect far beyond expection.
The total content of the active component is 1%-15%, the preferred 3-12% of carrier MCM-41 weight, further preferably 5-10%.For example, the content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%th, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%th, 14%, 14.5% etc..
In the present invention, active component is particularly limited to for two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Mixed proportion, inventor has found that the effect that different mixed proportions reaches is entirely different.Inventor's discovery, 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), only two molybdenum MO of control nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists In the range of being somebody's turn to do, can realize that sulfur content control is in below 10ppm and denitrification ability is notable in diesel oil.That is, of the invention Four kinds of active components only mol ratio be 1:(0.4-0.6):(0.28-0.45):(0.8-1.2) when, just possesses collaboration effect Should.Outside except the molar ratio range, either omit or replace any one component, can not all 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), most It is preferred that 1:0.48:0.42:0.95.
The third object of the present invention is the co-catalyst for providing the catalyst.Catalyst of the present invention also contains Catalyst aid, the catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although being particularly hydrodesulfurization field in hydrofinishing, there are the catalyst aid of maturation, such as P, F and B etc., its For adjusting the property 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 is helped In carrier and active component of the application with the present invention, for high sulphur component, it promotes the effect of catalytic desulfurization/refined for agent .
The present invention is passed through in numerous conventional cocatalyst components, and is selected in amount of activated component, compounded, Finally found that and adopt TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, Its hydrothermal stability can be significantly improved, and improves its anti-coking deactivation, so as to improve its service life.
The TiO2、CeO2、V2O5And NbOPO4Between without fixed ratio, that is to say, that TiO2、CeO2、V2O5With NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention is adopted2、CeO2、V2O5And NbOPO4 Respective content is the 1-7% of (respectively) carrier quality, preferred 2-4%.
Although without specific proportion requirement between catalyst aid of the present invention, each auxiliary agent allows for reaching To the requirement of effective dose, i.e., can play the content of catalyst aid effect, the 1-7% of such as carrier quality.The present invention is being selected During find, omit or replace one or more in the auxiliary agent, do not reach the present invention technique effect (improve water Heat endurance, reduces coking and improves service life), that is to say, that exist specifically to coordinate between the catalyst aid of the present invention and close System.
In fact, the present invention was once attempted the niobium phosphate NbOPO in catalyst aid4Replace with the girl Nb of five oxidation two2O5, 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, and so as to cause catalyst duct to block, beds pressure drop rise is relatively Hurry up.The present invention also once attempted introducing other phosphate, although this trial introduces phosphate anion, but equally existed hydro-thermal Stability is relatively slightly worse, and its beds coking is relatively rapid, so as to cause catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, the present invention should be noted that, introduce catalysis Auxiliary agent is only one of preferred version, even if not introducing the catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. The catalyst aid for not introducing the present invention is particularly niobium phosphate, and, compared to the scheme for introducing catalyst aid, its defect is only phase for it To.I.e. the defect be relative to introduce catalyst aid after defect, its relative to other prior arts outside the present invention, Advantageous or new features mentioned by the present invention are yet suffered from.The catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, it is further optimization to technical solution of the present invention, solves new technical problem.
The preparation method of the catalyst can take conventional infusion process and other alternatives, people in the art The prior art unrestricted choice that member can be grasped according to it, the present invention is repeated no more.
Preferably, the reaction condition of the fixed bed reactors is：Reaction temperature is 340-350 DEG C, reaction pressure 6.5- 7.5MPa, hydrogen to oil volume ratio 400-600, volume space velocity 1.5-2.0h-1。
Preferably, the technological process includes, after diesel oil mixes with hydrogen, the optional heat exchanger heat exchange of Jing, then it is heated Hydrogenation desulfurization and denitrogenation is carried out into fixed bed reactors after stove heat, product Jing gas-liquid separation tower is separated.Optionally, gas phase Return mixes with diesel oil and hydrogen, and liquid phase can be refined further, and such as amine is washed, strips and is fractionated.
Preferably, the fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
, by choosing specific catalyst, the catalyst is by mixing hetero atom for the hydrogenation desulfurization and denitrogenation technique of the present invention Co2+MCM-41 as carrier, and choose special ratios the molybdenum MO of nitridation two2N, tungsten nitride W2N, molybdenum carbide Mo2C and carbonization Used as active component, described catalyst also contains catalyst aid to tungsten WC, and the catalyst aid is TiO2、CeO2、V2O5With NbOPO4Mixture so that the catalyst produces cooperative effect, and the hydrodesulfurization to diesel oil can control to be less than in total sulfur content 5ppm, while controlling within 10ppm the total nitrogen content in diesel oil.
Specific embodiment
The present invention is illustrated by following embodiments to the hydrogenation desulfurization and denitrogenation technique of the present invention.
Embodiment 1
Catalyst is prepared by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41 Control is the 0.65% of carrier quality.The active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content for carrier quality 10%, its mol ratio be 1:0.4:0.3:0.8.
The Catalyst packing is entered into fixed bed reactors, the reaction tube of the reactor by internal diameter 50mm stainless steel Into beds are set to 3 layers, and reaction bed temperature is measured with UGU808 types temp controlled meter, and raw material diesel oil is by Bei Jingwei The double plunger micro pump continuous conveying of star manufactory manufacture, hydrogen is supplied and with Beijing Sevenstar-HC D07-11A/ by gas cylinder ZM gas mass flow gauge coutroi velocities, loaded catalyst is 2kg.Reacted product Jing water-baths room temperature cools down laggard promoting the circulation of qi Liquid is separated.
It is raw materials used for straight-run diesel oil, its total sulfur content 788 μ g/g, basic n content is 499.8 μ g/g.
Controlling reaction condition is：350 DEG C of temperature, reaction pressure 7.0MPa, hydrogen to oil volume ratio 500, volume space velocity 2h-1。
The final product of test, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 5ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41 Control is the 0.7% of carrier quality.The active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content for carrier quality 10%, its mol ratio be 1:0.6:0.45):1.2.
Remaining condition is same as Example 1.
The final product of test, total sulfur content is reduced to 2ppm, and total alkaline nitrogen content is reduced to 5ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with into γ-Al2O3, remaining condition is constant.
The final product of test, total sulfur content is reduced to 26ppm, and total alkaline nitrogen content is reduced to 45ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with into unadulterated MCM-41, remaining condition is constant.
The final product of test, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 43ppm.
Comparative example 3
By the Co of embodiment 12+Replace with Zn2+, remaining condition is constant.
The final product of test, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 37ppm.
Comparative example 4
By the Co in embodiment 12+Doping in MCM-41 is controlled the 0.5% of carrier quality, and remaining condition is constant.
The final product of test, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 36ppm.
Comparative example 5
By the Co in embodiment 12+Doping in MCM-41 is controlled the 0.8% of carrier quality, and remaining condition is constant.
The final product of test, total sulfur content is reduced to 43ppm, and total alkaline nitrogen content is reduced to 55ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application is adopted and certain loads metal ion MCM-41 carriers, when other known carriers of this area are replaced with, or carrier is identical but Co2+When doping is different, reach Less than the technique effect of the present invention, therefore the Co of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other Possesses cooperative effect between component, the hydrogenation desulfurization and denitrogenation technique generates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
The final product of test, total sulfur content is reduced to 44ppm, and total alkaline nitrogen content is reduced to 51ppm.
Comparative example 7
The WC in embodiment 1 is omitted, remaining condition is constant.
The final product of test, total sulfur content is reduced to 41ppm, and total alkaline nitrogen content is reduced to 56ppm.
Above-described embodiment and comparative example 6-7 illustrate that several activearms of catalyst of the hydrodesulfurization of the present invention divide it Between there is specific contact, be omitted or substituted one of which or several, can not all reach the certain effects of the application, it was demonstrated that its product Cooperative effect is given birth to.
Embodiment 3
Contain catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and 3%, remaining is same as Example 1.
The final product of test, after it uses 3 months, beds pressure drop is not any change, compared to equally using The beds pressure drop of time embodiment 1 reduces 19%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omit, remaining condition is identical.
The final product of test, after it uses 3 months, beds pressure drop is raised, compared to same use time reality The beds pressure drop for applying example 1 only reduces 4%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omit, remaining condition is identical.
The final product of test, after it uses 3 months, beds pressure drop is raised, compared to same use time reality The beds pressure drop for applying example 1 only reduces 1%.
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 components, can not all reach the present invention and add reduction coking during catalyst aid so as to prevent catalyst bed The elevated technique effect of lamination drop.That is, its catalyst aid for demonstrating the present invention can improve the service life of the catalyst, And other catalyst aid effects are not so good as the specific catalyst aid.
Applicant states that the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in Above-mentioned technique, that is, do not 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, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, tool Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (8)

1. a kind of diesel hydrogenation for removal sulphur denitrification process, it is characterised in that the technique adopts fixed bed reactors, fixed bed reaction Hydrogenation desulfurization and denitrogenation catalyst is filled with device, the catalyst includes carrier and active component；
The carrier is incorporation hetero atom Co in synthesis skeleton structure2+MCM-41；
The active component is two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2The mixture of C and tungsten carbide wc；
Described catalyst also contains catalyst aid, and the catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture；
The reaction condition of the fixed bed reactors is：Reaction temperature is 320-360 DEG C, reaction pressure 6-8MPa, hydrogen oil volume Than 300-600, volume space velocity 1.0-2.5h-1。
2. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be MCM-41 The 0.63%-0.72% of weight.
3. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that the total content of the active component is carrier The 3-12% of MCM-41 weight, preferred 5-10%.
4. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that two molybdenum MO of nitridation2N, tungsten nitride W2N, carbonization Molybdenum 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. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that the reaction condition of the fixed bed reactors For：Reaction temperature is 340-350 DEG C, reaction pressure 6.5-7.5MPa, hydrogen to oil volume ratio 400-600, volume space velocity 1.5-2.0h-1, it is preferred that the reaction condition of the fixed bed reactors is：350 DEG C of temperature, reaction pressure 7.0MPa, hydrogen to oil volume ratio 500, Volume space velocity 2h-1。
6. hydrodesulfurization as claimed in claim 1, it is characterised in that the technological process includes that diesel oil is mixed with hydrogen After conjunction, the optional heat exchanger heat exchange of Jing, then carry out hydrodesulfurization, product into fixed bed reactors after heated stove heat Jing gas-liquid separation towers are separated.
7. hydrodesulfurization as claimed in claim 1, it is characterised in that the fixed bed reactors include 1-5 catalysis Agent bed, preferably includes 2-3 beds.
8. hydrodesulfurization as claimed in claim 1, it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective content The respectively 1-7% of carrier quality, preferred 2-4%.
CN201610689485.9A 2016-08-16 2016-08-16 Hydrogenation, desulfurization and denitrification process of diesel oil Pending CN106635136A (en)

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