CN106221738A - A kind of diesel hydrogenation for removal sulphur denitrification process - Google Patents
A kind of diesel hydrogenation for removal sulphur denitrification process Download PDFInfo
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- CN106221738A CN106221738A CN201610665059.1A CN201610665059A CN106221738A CN 106221738 A CN106221738 A CN 106221738A CN 201610665059 A CN201610665059 A CN 201610665059A CN 106221738 A CN106221738 A CN 106221738A
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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
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- 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
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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
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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 Co in synthetic bone shelf structure2+MCM 41；Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；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
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 Co in synthetic bone shelf structure2+MCM-41.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
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。
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time
The difference adding directed agents and synthetic parts changes between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g,
MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic
The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49,
MCM56, carries out contrast test selection, finds that only MCM-41 can reach the goal of the invention of the present invention, and other mesoporous materials are all
Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use
MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention
Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: in MCM-41 building-up process,
Add Co2+Saline solution, before MCM-41 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part skeleton unit
Element thus embed in the skeleton of molecular sieve, improve on the whole MCM-41 mesopore molecular sieve catalysis activity, absorption and heat
Mechanical stability can wait.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Co2+MCM-41 could realize sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted adulterating in MCM-41: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all can not
Realize described effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on MCM-41 inner surfaces of pores to compare,
The isomorphous substitution approach of the present invention is more stable.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention
Executing, inventor 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 MCM-41 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of MCM-41 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of diesel oil denitrogenation and desulfurized effect.More pleasurable
, work as Co2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, works as drafting
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 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 MCM-41 weight, preferably 3-12%, further preferably
5-10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, sulfur content in 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.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: 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
Co2+MCM-41 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and carbonization
Tungsten WC is as active component so that this catalyst produces cooperative effect, and the hydrodesulfurization to diesel oil can control at total sulfur content low
In 5ppm, the total nitrogen content in diesel oil is controlled within 10ppm 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 Co2+MCM-41, Co2+Doping in MCM-41
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material 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 5ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 2ppm, and total alkaline nitrogen content is reduced to 5ppm.
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 26ppm, and total alkaline nitrogen content is reduced to 45ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 43ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, 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 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, 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 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, 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 uses and certain loads metal ion
MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other
Possessing cooperative effect between component, 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 44ppm, and total alkaline nitrogen content is reduced to 51ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 41ppm, 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.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (7)
1. a 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 Co in synthetic bone shelf structure2+MCM-41；
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；
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 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 described active component is carrier
The 3-12% of MCM-41 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.
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