CN106433756A - 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
CN106433756A
CN106433756A CN201610679197.5A CN201610679197A CN106433756A CN 106433756 A CN106433756 A CN 106433756A CN 201610679197 A CN201610679197 A CN 201610679197A CN 106433756 A CN106433756 A CN 106433756A
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catalyst
sapo
carrier
fixed bed
reaction
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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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • 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
    • 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (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, wherein the fixed-bed reactor is filled with a hydrogenation desulfurization and denitrification catalyst; the catalyst comprises a carrier and an active component; the carrier is SAPO-5 with a synthetic framework structure doped with heteroatoms Co<2+>; the active component is a mixture of molybdenum nitride MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide WC; the catalyst further contains a catalytic promoter; the catalytic promoter is a mixture of TiO2, CeO2, V2O5 and NbOPO4; reaction conditions of the fixed-bed reactor are as follows: a reaction temperature is 320 DEG C to 360 DEG C, reaction pressure is 6MPa to 8Mpa, a hydrogen to oil volume ratio is 300 to 600, and a volume space velocity is 1.0h<-1> to 2.5h<-1>. The process provided by the invention can be used for controlling the content of total sulfur in the diesel oil to be lower than 5ppm; meanwhile, the content of total nitrogen in the diesel oil is controlled to be no more than 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, be specifically related to a kind of hydrogenation using special catalyst to carry out and take off Sulphur 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 atmosphere pollution.
Sulphur is a kind of harmful substance that nature is present in gasoline, and Beijing rate in 1 day January in 2008 first carries 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 with regard to printing and distributing《Accelerate product oil quality upgrading programme of work》Notice, scheme clearly expand automobile-used vapour, Diesel oil state five standard performs scope.Expand whole eastern region from original Jing-jin-ji region, the Yangtze River Delta, region, Pearl River Delta key cities to 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 producing country five standard motor petrol (oil of blend component containing ethanol petrol), automobile-used bavin for enterprise The ability of oil.On January 1st, 2016 rises, and the motor petrol (ethanol vapor containing E10 meeting state five standard 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 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 discovery, in diesel oil The organic sulfur compound of difficult removing is 4 and (or) 4, the substituted oil-source rock correlation of 6 alkyl, this kind of sulfide due to On catalyst activity position adsorb when 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 WS2Nano particle, MoS2The appropriate stacking of nano particle 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, is less than 500 μ g/g；Use one section of ultra-deep hydrodesulfuration, be 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, has industrialized two kinds of catalyst on this basis, 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 below 50 μ g/g) of degree desulfurization de-virtue device, can make total aromatic hydrocarbons take off to 10% with Under, sulphur takes off to below 10 μ g/g.Typical operation conditions is：Reaction temperature 316 DEG C, pressure 6.18MPa, 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 the requirement to product Cetane number for the enterprise.Improve cetane number of inferior diesel oil, desulfurization 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 obtained commercial Application for the first time in 2000.The DN3110 hydrofinishing catalysis of Standard Co., Ltd Agent, Z5723 gas reversion catalyst are that the one using CENTINEL technology and actiCAT pre-curing technology to produce is 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 be metal sulfide by convert metal oxides.And actiCAT part pre-curing technology, it is at catalyst Sulfur-loaded in production, is opening the self-contained sulphur of utilization of hour catalyst and is realizing the sulfuration of catalyst, it is not necessary to catalyst It is dried, it is not necessary to additionally injecting vulcanizing agent, and soak time is shorter, so will make that device is quick, drive easily and safely.
How therefore 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, can effectively remove the nitride in diesel oil simultaneously, be the difficult problem that this area faces.
Content 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 is 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 Having hydrogenation catalyst, described catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+SAPO-5.Described active component is nitridation two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst, possibly together with catalyst aid, described is urged Changing auxiliary agent 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 oil Volume ratio 300-600, volume space velocity 1.0-2.5h-1.
SAPO-5 molecular sieve is the one in SAPO (SAPO) Series Molecules sieve, and its channel system is by six sides couple The twelve-ring that the four-membered ring of title property and hexatomic ring are constituted is constituted, and has large aperture structure, and its aperture is 0.8nm.SAPO-5 Acidic zeolite is gentle, and has faint controllability, also has cation exchange capacity (CEC).In a way, its materialization Character not only has the characteristic of aluminophosphate molecular sieve, and also is similar to the characteristic of Si-Al zeolite.Owing to it has novel Crystal structure, good heat endurance and hydrothermal stability, in the reaction such as meta-xylene isomerization and n-hexane catalytic pyrolysis Tool is widely used.But it is used for hydrofinishing rather than hydrocracking field, rarely seen document is reported.
The present invention through in numerous silicoaluminophosphamolecular molecular sieves, such as SAPO-11, SAPO-17, SAPO-20, SAPO-31, SAPO-34, SAPO-44, SAPO-46, SAPO-47 etc., carry out contrast test selection one by one, and discovery only has SAPO-5 to reach The goal of the invention of the present invention, other mesoporous materials have such-and-such defect, exist when being applied in the present invention and are difficult to gram The technical difficulty of clothes, therefore the present invention selects to do modified the turning of SAPO-5 being used for being hydrocracked for hydrorefined carrier base Plinth.
Inventor is through research discovery, for the silica alumina ratio, the phosphorus aluminum ratio that affect silicoaluminophosphamolecular molecular sieves performance, in the present invention In, after being modified, the change of silica alumina ratio and phosphorus aluminum ratio is less to hydrofinishing influential effect, and therefore the present invention is no longer to sial It is defined than with phosphorus aluminum ratio.It for ease of the explanation present invention, is typically defined to mol ratio and is respectively less than 1.
Owing to existing SAPO-5 molecular sieve catalytic temperature is high, and being easily caused raw material hydrocracking, therefore, the present invention is to it Being modified, to increase its catalysis activity, reducing catalytic temperature and make it be applicable to catalytic refining, minimizing is hydrocracked.This The bright approach to the modification of SAPO-5 mesopore molecular sieve is：Introduce to the total silicon SAPO-5 mesopore molecular sieve duct inner surface of finished product Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of SAPO-5, thus improve on the whole The catalysis activity of SAPO-5 mesopore molecular sieve, absorption and Thermodynamically stable performance etc..
Although the method be modified to SAPO-5 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges Agent can only use doping Cu2+SAPO-5 could realize sulfur content control and the balance of loss of octane number, invention as carrier People has attempted adulterating in SAPO-5：Ca2+、Fe3+、Zn2+、Ti2+、Ga3+And alkali metal etc. produces anionic surface center Ion, discovery all can not realize described effect.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 SAPO-5 must control within specific content range, and its doping is with weight Meter, is the 0.56%-0.75% of SAPO-5 weight, for example the 0.57%th, the 0.58%th, the 0.59%th, the 0.6%th, the 0.61%th, the 0.62%th, 0.63%th, the 0.64%th, the 0.65%th, the 0.66%th, the 0.67%th, the 0.68%th, the 0.69%th, the 0.7%th, the 0.71%th, the 0.72%th, the 0.73%th, 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 SAPO-5 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 map 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 producing, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier S APO-5 weight, preferably 3-12%, further preferably 5-10%.For example, the 2%th, the 2.5%th, the 3%th, the 3.5%th, the 4%th, the 4.5%th, the 5%th, the 5.5%th, the 6%th, the 6.5%th, described content can be 7%th, the 7.5%th, the 8%th, the 8.5%th, the 9%th, the 9.5%th, the 10%th, the 10.5%th, the 11%th, the 11.5%th, the 12%th, the 12.5%th, the 13%th, 13.5%th, the 14%th, 14.5% etc..
It in the present invention, 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), only control nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists In the range of Gai, can realize that in diesel oil, sulfur content controls at below 10ppm and denitrification ability notable.It is to say, the present invention Four kinds of active components be only 1 in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2), when, just possesses 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 three of the purpose of the present invention are to provide the co-catalyst of described catalyst.Catalyst of the present invention possibly together with 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 in application with the carrier of the present invention with active component when, 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, compounds, Discovery eventually uses 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 content of catalyst aid effect, the 1-7% of such as carrier quality i.e. can be played.The present invention is selecting During discovery, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat endurance, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and close specific cooperation 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 also once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is relatively 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 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 introducing 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, it is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of described catalyst can take infusion process and other alternatives, 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 carrying out hydrogenation desulfurization and denitrogenation, product separates through gas-liquid separation tower.Optionally, gas phase Returning and mixing with diesel oil and hydrogen, liquid phase can further be refined, and such as amine washes, strip and fractionation 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+SAPO-5 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, and described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5With NbOPO4Mixture so that this catalyst produces cooperative effect, can control the hydrodesulfurization of diesel oil and be less than at total sulfur content 5ppm, controls within 10ppm to the total nitrogen content in diesel oil simultaneously.
Detailed description of the invention
The present invention is illustrated by the hydrogenation desulfurization and denitrogenation technique to the present invention for the following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+SAPO-5, Co2+Doping in SAPO-5 Control 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 be the 10% of carrier quality, 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 that star manufactory manufactures carries continuously, and hydrogen is supplied and used by gas cylinder Beijing Sevenstar-HC D07-11A/ ZM gas mass flow gauge coutroi velocity, loaded catalyst is 2kg.Reacted product is through the laggard promoting the circulation of qi of water-bath room temperature cooling 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.
Control 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 8ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+SAPO-5, Co2+Doping in SAPO-5 Amount controls at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide The total content of WC is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45):1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 2ppm, and total alkaline nitrogen content is reduced to 4ppm.
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 33ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated SAPO-5, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 24ppm, and total alkaline nitrogen content is reduced to 37ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 39ppm.
Comparative example 4
By the Co in embodiment 12+Doping in SAPO-5 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 36ppm.
Comparative example 5
By the Co in embodiment 12+Doping in SAPO-5 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 35ppm, and total alkaline nitrogen content is reduced to 41ppm.
Embodiment 1 and comparative example 1-5 show, the certain content scope that the application uses and certain loads metal ion SAPO-5 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+When doping is different, all reach Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping SAPO-5 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 38ppm, and total alkaline nitrogen content is reduced to 49ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 40ppm, and total alkaline nitrogen content is reduced to 57ppm.
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
Catalyst contains catalyst aid TiO2、CeO2、V2O5And NbOPO4, the 1%th, its content be respectively the 1.5%th, 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 18%.
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 4.6%.
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 5.2%.
Embodiment 3 and comparative example 8-9 show, 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 high technique effect of lamination falling-rising.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst, And other catalyst aid effects are not so good 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 each raw material 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 Co in synthetic bone shelf structure2+SAPO-5；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 Co2+Doping be SAPO-5 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 SAPO-5 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.
CN201610679197.5A 2016-08-17 2016-08-17 Hydrogenation desulfurization and denitrification process of diesel oil Pending CN106433756A (en)

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