CN106244210A - A kind of diesel hydrogenation for removal sulphur denitrification process - Google Patents

A kind of diesel hydrogenation for removal sulphur denitrification process Download PDF

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Publication number
CN106244210A
CN106244210A CN201610688811.4A CN201610688811A CN106244210A CN 106244210 A CN106244210 A CN 106244210A CN 201610688811 A CN201610688811 A CN 201610688811A CN 106244210 A CN106244210 A CN 106244210A
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catalyst
fixed bed
bed reactors
kit
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
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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

Abstract

The invention discloses a kind of diesel hydrogenation for removal sulphur denitrification process, 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+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 320 360 DEG C, reaction pressure 6 8MPa, hydrogen to oil volume ratio 300 600, volume space velocity 1.0 2.5h‑1.Diesel oil total sulfur content can be controlled, less than 5ppm, to control the total nitrogen content in diesel oil within 10ppm by this technique simultaneously.

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, be specifically related to a kind of hydrogenation using special catalyst to carry out and take off Sulfur denitrification process.
Background technology
Entering 21st century, demand and the use of fuel oil increase substantially, and sulfur-containing compound therein is brought Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide in fuel oil produces through engine combustion (SOx) be discharged in air, produce acid rain and fumes of sulphuric acid type pollution etc., cause atmospheric pollution.
Sulfur is a kind of harmful substance that nature is present in gasoline, Beijing in 1 day January in 2008 rate first carry out phase When diesel oil standard (sulfur content≤50mg/g), on May 5th, 2016, the Committee of Development and Reform, the Ministry of Finance, ring are cleaned in the capital IV in the Europe IV standard Department of guarantor portion etc. seven issues notice of " accelerating product oil quality upgrading programme of work " about printing and distributing, scheme clearly expand automobile-used vapour, Diesel oil state five standard performs scope.Whole eastern region is expanded to from original Jing-jin-ji region, the Yangtze River Delta, region, Pearl River Delta 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 manufacturing country five standard motor petrol (containing ethanol petrol blend component oil), automobile-used bavin for enterprise The ability of oil.On January 1st, 2016 rises, and eastern region is supplied comprehensively and met the motor petrol of state five standard (containing E10 ethanol vapor Oil), derv fuel (containing B5 biodiesel).The Europe V diesel oil that total sulfur content is not more than 10ppm was carried out in Europe in 2009 Standard.So, produce ultra-low sulfur diesel oil have become as domestic oil refining enterprises institute must faced by realistic problem.
At present, the method producing ultra-low sulfur diesel oil mainly includes hydrofinishing, oxidation sweetening, selective absorption, life Thing desulfurization etc..But most effective, the most economical sulfur method that hydrodesulfurization (HDS) technology is well recognized as.Research finds, in diesel oil The organic sulfur compound of difficult removing is 4 and (or) 4,6 substituted oil-source rock correlations of alkyl, this kind of sulfide due to On catalyst activity position absorption time there is the sterically hindered of alkyl, hinder reactant molecule on adsorption activity position can be close Property, so that its hydrodesulfurization activity is low；Theoretical research also finds, Ni, Co, Mo are stratiforms with the hydrogenation activity of W sulfide mutually The MoS of stacking2And WS2Nanoparticle, MoS2The appropriate stacking of nanoparticle contributes to reactant molecule on adsorption activity position Accessibility and the formation of highly active II class activity phase.
At present external diesel hydrogenation for removal sulphur technology commonly uses double base or multicomponent catalyst, belongs to the middle pressure degree of depth and ultra-deep One section or two-stage desulfurization process, this 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 ratio of processing is wide, can process straight run oil, also can process cracking fraction oil.Product sulfur content is: use the degree of depth Hydrodesulfurization, less than 500 μ g/g；Use one section of ultra-deep hydrodesulfuration, less than 30 μ g/g.If using two sections of technology all right Reduce polycyclic aromatic hydrocarbon and improve Cetane number.
Triumphant King Company of Japan develops STARS hydrogenation catalyst technology, on this basis two kinds of catalyst of industrialization, i.e. KF-757 Ultra-deep Desulfurization of Diesel Fuels catalyst and the KF-848 refining catalytic with high desulfurization, denitrogenation, Tuo Fang and hydrogenation activity Agent, is applicable not only to hydro-refining unit, and is applicable to raw material prerefining, the FCC feedstock weighted BMO spaces etc. being hydrocracked. 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 the degree 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 is saturated and improves Cetane number) and TK-908 (aromatic hydrocarbons is saturated and improves Cetane number) Deng.Wherein TK-574 high activity cobaltmolybdate catalyst is ultra-deep desulfurization catalyst, than TK-544 deep desulfurization catalyst opposite bank Long-pending activity improves 30%～40%, uses TK-544 catalyst, can make product on the diesel device producing sulfur content 500 μ g/g Product sulfur content is down to 350 μ g/g.
American Association catalyst Co. is newly developed AS-AT desulfurization removing nitric Porous deproteinized bone three function catalyst, deep for diesel oil Second reactor (the first reactor desulfurization takes off to 50 below μ g/g) of degree desulfurization de-virtue device, can make total aromatic hydrocarbons take off to 10% with Under, sulfur takes off to 10 below μ g/g.Typical operation conditions is: reaction temperature 316 DEG C, pressure 6.18MPa, and liquid hourly space velocity (LHSV) is less than 2h-1, Hydrogen-oil ratio 712.
The outer commonly used poor ignition quality fuel modification means of Present Domestic are hydrofinishing and hydro-upgrading.Hydrofinishing can be bright Aobvious color and the stability improving product, but it is limited to be limited Cetane number increase rate by thermodynamics of reactions, therefore by adding Hydrogen is refined far from meeting enterprise's requirement to product Cetane number.Cetane number of inferior diesel oil, desulfurization is improved for oil plant The demand of denitrogenation Porous deproteinized bone, American Standard Inc. be proposed MHUG hydro-upgrading technology and DN3110 Hydrobon catalyst, Z5723 gas reversion catalyst, and commercial Application for the first time was obtained in 2000.The DN3110 hydrofinishing catalysis of Standard Co., Ltd Agent, Z5723 gas reversion catalyst are to use CENTINEL technology and actiCAT？The one that pre-curing technology produces is with oxidation Aluminum is the nickel molybdenum pre-sulfide catalyst of carrier, and CENTINEL key problem in technology is than general catalysis in terms of active metal dispersion Agent is more preferable, it is easier to be metal sulfide by convert metal oxides.And actiCAT？Part pre-curing technology, is in catalysis Sulfur-loaded in agent production, is opening the self-contained sulfur of utilization of hour catalyst to realize the sulfuration of catalyst, it is not necessary to catalyst Be dried, it is not necessary to additionally inject vulcanizing agent, and soak time be shorter, so will make device quickly, open easily and safely Car.
A kind of diesel hydrogenation for removal sulphur technique is provided, can effectively the sulfur content in diesel oil be controlled 10ppm with Under, to meet state five standard, simultaneously can effectively remove the nitride in diesel oil, be a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of diesel hydrogenation for removal sulphur denitrification process, this technique can be by the total sulfur in diesel oil Content is reduced to below 10ppm, to meet diesel oil state five standard.Meanwhile, this technique use catalyst also make in diesel oil The removing ratio of nitride is more significant.
For reaching this purpose, the present invention by the following technical solutions:
A kind of diesel hydrogenation for removal sulphur denitrification process, 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+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 320-360 DEG C, reaction pressure 6-8MPa, hydrogen oil Volume ratio 300-600, volume space velocity 1.0-2.5h-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: to the total silicon KIT-1 mesoporous molecular of finished product Sieve inner surfaces of pores introduces Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of KIT-1, thus Improve catalysis activity, absorption and the Thermodynamically stable performance etc. of KIT-1 mesopore molecular sieve on the whole.
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 Cu2+KIT-1 could realize sulfur content control and denitrification effect as carrier, inventor has attempted KIT-1 adulterates: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize described effect Really.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, and inventor is according to well-known theory and experiment Confirm, between itself and the active component of the present invention, there is cooperative effect.
Described Cu2+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 diesel oil denitrogenation and desulfurized effect.More pleasurable , work as Cu2+When doping in KIT-1 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, works as drafting 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 in pole Within the scope of low, 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 diesel oil can be realized and control at below 10ppm and denitrification ability notable.It is to say, the present invention Four kinds of active components be only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just possess collaborative effect Should.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 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, described technological process includes, after diesel oil mixes with hydrogen, through optional heat exchanger heat exchange more heated Entering fixed bed reactors after stove heating and carry out hydrogenation desulfurization and denitrogenation, product separates through gas-liquid separation tower.Optionally, gas phase Returning and mix with diesel oil and hydrogen, liquid phase can further be refined, and such as amine washes, strip and fractional distillation etc..
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrogenation desulfurization and denitrogenation technique of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Cu2+KIT-1 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide WC is as active component so that this catalyst produces cooperative effect, and the hydrodesulfurization to diesel oil can control to be less than at total sulfur content 5ppm, controls within 10ppm the total nitrogen content in diesel oil simultaneously.
Detailed description of the invention
The hydrogenation desulfurization and denitrogenation technique of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Cu2+KIT-1, Cu2+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 diesel oil is by Bei Jingwei The double plunger micro pump of star maker manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ by gas cylinder ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product cools down laggard circulation of qi promoting through water-bath room temperature Liquid separates.
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: temperature 350 DEG C, reaction pressure 7.0MPa, hydrogen to oil volume ratio 500, volume space velocity 2h-1。
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 7ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Cu2+KIT-1, Cu2+Doping control in KIT-1 System is at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 3ppm, 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 28ppm, and total alkaline nitrogen content is reduced to 52ppm.
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 31ppm, and total alkaline nitrogen content is reduced to 43ppm.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 39ppm, and total alkaline nitrogen content is reduced to 56ppm.
Comparative example 4
By the Cu 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 29ppm, and total alkaline nitrogen content is reduced to 48ppm.
Comparative example 5
By the Cu 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 33ppm, and total alkaline nitrogen content is reduced to 45ppm.
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 Cu2+During doping difference, all reach not To the technique effect of the present invention, the therefore Cu of the certain content scope of the present invention2+Doping KIT-1 carrier and other components of catalyst Between possess cooperative effect, described hydrogenation desulfurization and denitrogenation technique 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 43ppm, and total alkaline nitrogen content is reduced to 52ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 56ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrodesulfurization 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 14%.
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 4.3%.
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 4.7%.
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 (8)

1. a diesel hydrogenation for removal sulphur denitrification process, it is characterised in that described technique uses fixed bed reactors, fixed bed reaction Being filled with hydrogenation desulfurization and denitrogenation catalyst in device, described catalyst includes carrier and active component；
Described carrier is incorporation hetero atom Cu 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 possibly together with catalyst aid, described catalyst aid For TiO2、CeO2、V2O5And NbOPO4Mixture；
The reaction condition of described 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。
2. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that hetero atom Cu2+Doping be KIT-1 weight The 0.63%-0.72% of amount.
3. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that the total content of described active component is carrier The 3-12% of KIT-1 weight, preferably 5-10%.
4. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, 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 described 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 described fixed bed reactors is: temperature 350 DEG C, 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 described technological process includes, diesel oil mixes with hydrogen After conjunction, through optional heat exchanger heat exchange, then after the heating of heated stove, entrance fixed bed reactors carry out hydrodesulfurization, product Separate through gas-liquid separation tower.
7. hydrodesulfurization 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.
8. hydrodesulfurization 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.
CN201610688811.4A 2016-08-17 2016-08-17 A kind of diesel hydrogenation for removal sulphur denitrification process Pending CN106244210A (en)

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Application publication date: 20161221