CN106423261A - Hydrofining catalyst - Google Patents

Hydrofining catalyst Download PDF

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Publication number
CN106423261A
CN106423261A CN201610697137.6A CN201610697137A CN106423261A CN 106423261 A CN106423261 A CN 106423261A CN 201610697137 A CN201610697137 A CN 201610697137A CN 106423261 A CN106423261 A CN 106423261A
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China
Prior art keywords
catalyst
sapo
carrier
present
gasoline
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CN201610697137.6A
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Chinese (zh)
Inventor
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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Priority to CN201610697137.6A priority Critical patent/CN106423261A/en
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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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • 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

Abstract

The invention discloses a hydrofining catalyst. The catalyst comprises a carrier and an active component. The carrier is SAPO-5 formed by doping heteroatom Co2+ in a synthetic framework structure, and the doping amount of the heteroatom Co2+ accounts for 0.56-0.75% of the weight of the SAPO-5. The active component is a mixture of MO2N, W2N, Mo2C and WC. The total content of the active component is 1-15% of the weight of the carrier SAPO-5. The catalyst further contains a catalytic additive which is a mixture of Cr2O3, ZrO2, CeO2, V2O5 and NbOPO4. By means of the catalyst, the total sulfur content in FCC gasoline can be reduced to 10 ppm or below, and the gasoline national-IV standard is met. Meanwhile, by adopting the catalyst, the octane value of FCC gasoline is not remarkably reduced.

Description

A kind of Hydrobon catalyst
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of hydrodesulfurization catalyst for refining, is more preferably related to one Plant FCC gasoline hydrodesulfurization and reduce the catalyst that octane number reduces amplitude.
Background technology
Enter 21st century, the demand of fuel oil and use 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) it is discharged in the air, produce acid rain and the pollution of fumes of sulphuric acid type etc., cause atmospheric pollution.
Sulfur is that nature is present in one of gasoline harmful substance, and in gasoline product, more than 80% sulfur carrys out self-catalysis and splits Change (FCC) gasoline, with the continuous change weight of crude oil, the sulfur content in FCC gasoline also can be continuously increased.External gasoline is generally from FCC (34%), catalytic reforming (33%), and alkylation, the technique such as isomerization and etherificate (about totally 33%)；And home-produced fuel 80% is from FCC gasoline.Sulfur due in gasoline 85%～95% is derived from FCC gasoline so that sulfur content in China's gasoline A lot of more than external gasoline.A lot of experts have carried out the research that sulfur affects on motor vehicle exhaust emission, and result shows：If by gasoline In sulfur content from 450 μ g g-1It is reduced to 50 μ g g-1, NO in vehicle exhaustxAverage 9%, the CO that reduces averagely reduces 19%, HC averagely reduce 18%, and Toxic averagely reduces 16%.Thus, effective fuel oil hydrodesulfurization technology, to society, warp Ji, the development of environment play the role of important.
Most effective, the most economical sulfur method that hydrodesulfurization (HDS) technology is well recognized as at present, especially selective hydrogenation Desulfurization technology, the saturation of suppression alkene of trying one's best while removing gasoline a large amount of sulfur-containing compound is to reduce loss of octane number. This kind of technology has operating condition and relaxes, and yield of gasoline is high, and hydrogen consumes the features such as low and loss of octane number is little.Hydrodesulfurization technology Key is the selection of Hydrobon catalyst, and the cobaltmolybdate catalyst of support type is the important gasoline hydrodesulfurizationcatalyst catalyst of a class, Typically cobalt molybdenum is loaded on porous support (as aluminium oxide, silicon oxide, activated carbon or its complex carrier), be widely used in adding In hydrogen sweetening process, to obtain premium-type gasoline product.
Hydrodesulfurization (HDS) technology is to grow up the fifties, and the nineties, this technology welcome second improving and developing Individual peak period, its technical maturity, all the time, become sulfur, nitrogen, oxygen in removing distillate, improve oil product Practical Performance and clear The maximally efficient means of cleanliness.The activity and selectivity of catalyst is the key factor of impact hydrofinishing efficiency and depth, The economy that high performance catalyst is brought and environmental benefit are very significant, have therefore attracted numerous enterprises and researcher to put into To in efficient catalyst exploitation, the catalyst prod that develop many function admirables, differs from one another.Hydrogenation technique is sent out rapidly The basic reason of exhibition is the development of catalyst, but can cause alkene saturation and product octane number while routine techniquess desulfurization (RON) decline, therefore can desulfurization and the few selective hydrogenation new technique of loss of octane number to become HDS method in recent years improved Main way.
The RESOLVE technological development catalytic cracking of Akzo Nobel company exploitation reduces the RESOLVE of content of sulfur in gasoline Additive product series, using high hydrogen transfer activity component and ADM-20, can make cracking gasoline sulfur content reduce by 20%, RESOLVE-700 gasoline reduction sulfur additives are currently in industrial evaluation.
Containing Sulfur in Exxon research engineering company and Akzo Nobel company joint development selectively removing FCC gasoline The Scanfining technology of compound, and in 1998, this technology is pushed to industrialization.It adopts traditional hydrotreating flow process, leads to Cross meticulous selecting catalyst (RT-225), make loss of octane number and hydrogen consumption reach minimum.
The Prime-G technology of French IFP exploitation, this technology is developed by French studying and designing institute (IFP), using dual catalyst System.Its process conditions relaxes, and hydrogenation of olefins activity is low, alkene saturation and cracking reaction does not occur, liquid yield reaches 100%, Desulfurization degree is more than 95%, and loss of octane number is few, and hydrogen consumption is low.By FCC heavy petrol hydrodesulfurization, being in harmonious proportion the gasoline product obtaining can To realize the target of sulfur content 100～150 μ g g-1；By the hydrodesulfurization respectively of FCC petroleum benzin, achievable sulfur content 30 μ The target of g g-1.
For the feature of domestic FCC gasoline sulfur-bearing, Fushun Petrochemical Research Institute (FRIPP) develops FCC gasoline and selects Property hydrogen addition technology (OCT-M) and full distillation gasoline selective hydrogenation technology (FRS), device can produce sulfur nutrient and be not more than 150μg·g-1GB III gasoline.OCT-M technology, after Shijiazhuang Oil Refinery, China Petrochemical Corp. continuously runs 17 months, adopts Two kinds of prioritization schemes that FRIPP recommends, after FCC gasoline hydrogenation, sulfur nutrient reaches GB III and IV standard.
On May 5th, 2016, department of the Committee of Development and Reform, the Ministry of Finance, Chinese Ministry of Environmental Protection etc. seven issues with regard to printing and distributing《Accelerate finished product oil quality Upgrade job scheme》Notify, scheme clearly expands automobile-used vapour, diesel oil state five standard execution scope.From original Jing-jin-ji region, length three Angle, Pearl River Delta region key cities expand whole eastern region 11 provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, rivers to Soviet Union, Zhejiang, Fujian, Shandong, Guangdong and Hainan).Before 31 days October in 2015, eastern region is protected possesses manufacturing country five mark for enterprise Quasi- motor petrol (oil of blend component containing ethanol petrol), the ability of derv fuel.From 1 day January in 2016, eastern region supplies comprehensively Motor petrol (ethanol petrol containing E10), the derv fuel (biodiesel containing B5) of state five standard should be met.
At present, the main method reducing FCC gasoline sulfur content is catalytic desulfurhydrogenation.But hydrotreating method exists such as Lower deficiency：(1) equipment investment is big；(2) it is hydrogenated with the severe reaction conditions of de- thiophenic sulfur, operating cost is high；(3) alkene is de- in hydrogenation Easily there is saturation under the conditions of sulfur, not only consume a large amount of hydrogen, and lead to octane number to reduce.FCC gasoline desulfurization degree requires Higher, operating condition is harsher, and the loss of octane number is also bigger.
How a kind of Hydrobon catalyst is therefore provided, can effectively the sulfur content in gasoline be controlled in below 10ppm, To meet state five standard, octane number loss simultaneously is less or does not lose, and is the difficult problem that this area faces.
Content of the invention
It is an object of the invention to proposing a kind of Hydrobon catalyst, this catalyst can be by the total sulfur in FCC gasoline Content is reduced to below 10ppm, to meet gasoline state five standard.Meanwhile, this catalyst using the octane also making FCC gasoline Value significantly reduces.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of catalyst of hydrodesulfurization, described catalyst includes carrier and active component.
Described carrier is to mix hetero atom Co in synthesis framing 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 also contains catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4's Mixture.
SAPO-5 molecular sieve is one of 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 is constituted with hexatomic ring is constituted, and has macropore gauge 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 Property not only has the characteristic of aluminophosphate molecular sieve, and also the characteristic similar to Si-Al zeolite.Due to its have new Crystal structure, good heat stability and hydrothermal stability, in the reaction such as meta-xylene isomerization and normal hexane catalytic pyrolysiss Tool is widely used.But it is used for hydrofinishing rather than hydrocracking field, rarely seen document report.
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, find only have SAPO-5 can 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, the therefore present invention select to do modified for the SAPO-5 being used for being hydrocracked turning for hydrorefined carrier base Plinth.
Inventor finds through research, for the silica alumina ratio of impact silicoaluminophosphamolecular molecular sieves performance, phosphorus aluminum ratio, in the present invention In, modified after, 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.For ease of the present invention is described, typically it is defined to mol ratio and is respectively less than 1.
Because existing SAPO-5 molecular sieve catalytic temperature is high, and it is easily caused raw material hydrocracking, therefore, the present invention is to it It is modified, to increase its catalysis activity, reduce catalytic temperature and make it be applied to catalytic refining, minimizing is hydrocracked.This The bright approach modified to SAPO-5 mesopore molecular sieve be：Introduce to the total silicon SAPO-5 mesopore molecular sieve duct inner surface of finished product Cu2+, this approach can be by ion exchange by Cu2+It is supported on the inner surface of SAPO-5, thus improving on the whole The catalysis activity of SAPO-5 mesopore molecular sieve, absorption and Thermodynamically stable performance etc..
Although the method that SAPO-5 mesopore molecular sieve is modified or approach are a lot, inventor finds, the present invention urges Agent can only be using doping Cu2+SAPO-5 just enable sulfur content as carrier and control and the balance of loss of octane number, invention People has attempted doping in SAPO-5：Ca2+、Fe3+、Zn2+、Ti2+、Ga3+And alkali metal etc. produces anionic surface center Ion, finds not enabling described effect.Although described mechanism is not known at present, this has no effect on the reality of the present invention Apply, according to well-known theory and it is experimentally confirmed that it has cooperative effect and the active component of the present invention between to inventor.
Described Co2+Must control within specific content range in the doping in SAPO-5, its doping is with weight Meter, be the 0.56%-0.75% of SAPO-5 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%th, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%, 0.74 etc..
Inventor finds, outside this range, can lead to drastically reducing of octane number.More pleasurable, when Co2+When the doping in SAPO-5 controls in the range of 0.63%-0.72%, it is the strongest to the control of octane number, works as drafting With Co2+When doping is transverse axis, curve chart with target octane number as the longitudinal axis, in this content range, sulfur content can control extremely low Within the scope of, the desulfurized effect that it produces, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is 1%-15%, the preferably 3-12% of carrier S APO-5 weight, further preferably 5-10%.For example, described content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%th, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%th, 14%, 14.5% etc..
In the present invention, being particularly limited to active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Mixed proportion, inventor finds, 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 Should in the range of, can realize that in FCC gasoline, sulfur content controls in below 10ppm and octane number is not decreased obviously.? That is, four kinds of active components of the present invention are 1 only in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2) when, Just possesses cooperative effect.Outside this molar ratio range, or omit or replace any one component, do not enable to assist Same 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 third object of the present invention is to provide the promoter of described catalyst.Catalyst of the present invention also contains Catalyst aid, described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, there is a catalyst aid of maturation, such as P, F and B etc., its For adjusting the property of carrier, weaken strong interaction 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 sulphur 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, Find eventually to adopt Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The catalyst facilitation to the present invention for the mixture of (niobium phosphate) Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improving its service life.
Described Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between there is no the ratio of fixation that is to say, that Cr2O3、ZrO2、 CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention adopts2O3、ZrO2、 CeO2、V2O5And NbOPO4Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although not having specific proportion requirement between catalyst aid of the present invention, each auxiliary agent allows for reaching To the requirement of effective dose, the content of catalyst aid effect, the 1-7% of such as carrier quality can be played.The present invention is selecting During find, omitting or replacing one or more of described auxiliary agent, the technique effect all not reaching the present invention (improves water Heat stability, reduces coking and improves service life) close that is to say, that there is specific cooperation between the catalyst aid of the present invention 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 leading to catalyst duct to block, beds pressure drop rise is relatively Hurry up.The present invention also once attempted introducing other phosphate, although this attempt introducing phosphate anion, but equally existed hydro-thermal Stability is relatively slightly worse, and its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, the present invention should be noted that, introduces 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. Do not introduce the catalyst aid particularly niobium phosphate of the present invention,, compared to the scheme introducing catalyst aid, its defect is only phase for it To.I.e. this defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention, Institute mentioned by the present invention is advantageous 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 alternative methods of routine, people in the art The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
The catalyst of the present invention, can be used for the hydrodesulfurization of gasoline, is particularly suitable for the hydrodesulfurization of FCC gasoline.
The present invention passes through to choose specific incorporation hetero atom Co2+SAPO-5 as carrier, and the nitrogen choosing special ratios Change two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2, as active component, described catalyst also contains catalysis to be helped for C and tungsten carbide wc Agent, described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, The hydrodesulfurization of FCC gasoline can be controlled and is less than 5ppm in total sulfur content, simultaneously octane number reduce amplitude control 0.5-2% it Interior.
Specific embodiment
The present invention is illustrated to the catalyst of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is doping Co2+SAPO-5, doping in SAPO-5 for the Co2+ Control 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 carrier quality 10%, its mol ratio be 1:0.4:0.3:0.8.
Described Catalyst packing is entered fixed bed reactors, the reaction tube of described reactor is by the stainless steel of internal diameter 50mm Become, reaction bed temperature is measured with UGU808 type temp controlled meter, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory Plug micro pump continuous conveying, hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC D07-11A/ZM gas mass flow gauge control Flow velocity processed, loaded catalyst is 2kg.Reacted product carries out gas-liquid separation after the cooling of water-bath room temperature.
Raw materials used for full fraction FCC gasoline, it contains alkene 25.3m%, aromatic hydrocarbons 40.2m%, alkane 28.8m%, grinds Studying carefully method octane number is 94.2, total sulfur content 660 μ g/g.
Control reaction condition be：370 DEG C of temperature, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 3h-1.
Test final product, its research octane number (RON) still reaches 94.0, and total sulfur content is reduced to 3ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is the SAPO-5 of doping Co2+, doping in SAPO-5 for the Co2+ Amount controls 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 Example 1.
Test final product, its research octane number (RON) still reaches 93.8, and total sulfur content is reduced to 2ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Test final product, its research octane number (RON) is 82, total sulfur content is 21ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated SAPO-5, remaining condition is constant.
Test final product, its research octane number (RON) is 80, total sulfur content is 23ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Test final product, its research octane number (RON) is 82, total sulfur content is 27ppm.
Comparative example 4
Doping in SAPO-5 for the Co2+ in embodiment 1 is controlled the 0.5% of carrier quality, remaining condition is not Become.
Test final product, its research octane number (RON) is 86, total sulfur content is 29ppm.
Comparative example 5
By the Co in embodiment 12+Doping in SAPO-5 controls the 0.8% of carrier quality, and remaining condition is constant.
Test final product, its research octane number (RON) is 83, total sulfur content is 31ppm.
Embodiment 1 and comparative example 1-5 show, certain content scope and certain loads metal ions that the application adopts 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 Possess cooperative effect between component, create unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Test final product, its research octane number (RON) is 84, total sulfur content is 27ppm.
Comparative example 7
Omit the WC in embodiment 1, remaining condition is constant.
Test final product, its research octane number (RON) is 85, total sulfur content is 31ppm.
, between several active component of catalyst of the present invention, there is specific connection in above-described embodiment and the explanation of comparative example 6-7 System, being omitted or substituted one of which or several, all can not reaching the certain effects of the application it was demonstrated which creating cooperative effect.
Embodiment 3
Catalyst aid Cr is contained in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content be respectively 1%, 2%, 1.5%th, 1% and 3%, remaining is same as Example 1.
Test final product, after it uses 3 months, beds pressure drop is not any change, use compared to same The beds pressure drop of time embodiment 1 reduces 15.1%.
Comparative example 7
Compared to embodiment 3, by NbOPO therein4Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time The beds pressure drop applying example 1 only reduces 3.2%.
Comparative example 8
Compared to embodiment 3, by CeO therein2Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time The beds pressure drop applying example 1 only reduces 2.9%.
Embodiment 3 and comparative example 7-8 show, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted One of or several groups of timesharing, all can not reach the present invention and add minimizing coking during catalyst aid thus stoping catalyst bed The high technique effect of lamination falling-rising.That is, it demonstrates the service life that the catalyst aid of the present invention can improve described catalyst, And other catalyst aid effects are not so good as this specific catalyst aid.
Applicant states, the present invention illustrates the catalyst of the present invention by above-described embodiment, but the present invention does not limit to In above-mentioned catalyst, that is, do not mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.The skill of art Art personnel are it will be clearly understood that the adding of any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and auxiliary element Plus, the selection of concrete mode etc., all fall within protection scope of the present invention and open within the scope of.

Claims (6)

1. the de- refined agent of a kind of hydrogenation, described catalyst include carrier and active component it is characterised in that
Described carrier is to mix hetero atom Co in synthesis framing structure2+SAPO-5, its doping is SAPO-5 weight 0.56%-0.75%；
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described activity The total content of component is the 1%-15% of carrier S APO-5 weight；
Described catalyst also contains catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixing Thing.
2. Hydrobon catalyst as claimed in claim 1 is it is characterised in that hetero atom Co2+Doping be SAPO-5 weight The 0.63%-0.72% of amount.
3. Hydrobon catalyst as claimed in claim 1 is 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. Hydrobon catalyst as claimed in claim 1 is it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5):(0.35-0.45):(0.8-1.0), more preferably 1: (0.45-0.48):(0.4-0.45):(0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. Hydrobon catalyst as claimed in claim 1 is it is characterised in that described Hydrobon catalyst is used for FCC vapour The hydrodesulfurization of oil refines.
6. Hydrobon catalyst as claimed in claim 1 is it is characterised in that Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Respectively From content be respectively carrier quality 1-7%, preferably 2-4%.
CN201610697137.6A 2016-08-19 2016-08-19 Hydrofining catalyst Withdrawn CN106423261A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470327A (en) * 2002-07-24 2004-01-28 北京石油化工学院 Metal nitride catalyst preparing method and catalyst
CN101591560A (en) * 2008-05-29 2009-12-02 北京三聚环保新材料股份有限公司 A kind of diesel oil hydrofining catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1470327A (en) * 2002-07-24 2004-01-28 北京石油化工学院 Metal nitride catalyst preparing method and catalyst
CN101591560A (en) * 2008-05-29 2009-12-02 北京三聚环保新材料股份有限公司 A kind of diesel oil hydrofining catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
阙国和: "《石油组成与转化化学》", 31 December 2008, 中国石油大学出版社 *

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