CN106433758A - HDS (hydrodesulfurization) technology of FCC (fluid catalytic cracking) gasoline - Google Patents

HDS (hydrodesulfurization) technology of FCC (fluid catalytic cracking) gasoline Download PDF

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CN106433758A
CN106433758A CN201610879650.7A CN201610879650A CN106433758A CN 106433758 A CN106433758 A CN 106433758A CN 201610879650 A CN201610879650 A CN 201610879650A CN 106433758 A CN106433758 A CN 106433758A
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hydrodesulfurization
catalyst
fixed bed
gasoline
hydrogen
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过冬
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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
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • C10G2400/02—Gasoline

Abstract

The invention discloses an HDS (hydrodesulfurization) technology of FCC (fluid catalytic cracking) gasoline. According to the technology, a fixed bed reactor is adopted and filled with an HDS catalyst which comprises a carrier and an active component; the carrier is a compound or a mixture of MSU-G, SBA-15 and HMS; the active component is a mixture of MO2N, W2N, Mo2C and WC; the catalyst further contains a catalytic promoter which is a mixture of Cr2O3, ZrO2, CeO2, V2O5 and NbOPO4; the reaction conditions of the fixed bed reactor are as follows: the reaction temperature is 300-420 DGE C, the hydrogen pressure is 2.5-3.5 MPa, the hydrogen oil volume ratio is 500-800, and the volume airspeed is 1.5-4 h<-1>. The total sulfur content in the FCC gasoline can be reduced to 5 ppm or below to meet national five gasoline standards with the technology. Meanwhile, the octane number of the FCC gasoline is not reduced obviously with the technology.

Description

A kind of FCC gasoline hydrodesulfurization
Technical field
The present invention relates to gasoline hydrodesulfurizationmethod technique, and in particular to a kind of FCC gasoline hydrodesulfurization, more preferably it is related to A kind of FCC gasoline hydrodesulfurization simultaneously reduces the technique that octane number reduces amplitude.
Background technology
Enter 21st century, the demand of fuel oil and using increasing substantially, and sulfur-containing compound therein is brought Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide in fuel oil is produced through engine combustion (SOx) in the air is discharged into, acid rain and the pollution of fumes of sulphuric acid type etc. is produced, causes atmospheric pollution.
Sulfur is a kind of harmful substance that nature is present in gasoline, 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 can also be continuously increased.External gasoline is generally from FCC (34%), catalytic reforming (33%), and the technique such as alkylation, isomerization and etherificate (about totally 33%)；And home-produced fuel 80% be from FCC gasoline.Sulfur due in gasoline 85%～95% is from FCC gasoline so that the 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, as a result show：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 of reducing averagely is reduced 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.
Hydrodesulfurization (HDS) technology is generally acknowledged most effective, most economical sulfur method, especially selective hydrogenation at present Desulfurization technology, i.e., the saturation of suppression alkene of trying one's best while removing gasoline a large amount of sulfur-containing compounds is to reduce loss of octane number. This kind of technology has an operating condition mitigation, yield of gasoline height, the features such as the hydrogen low and loss of octane number of consumption 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 load on porous support (as aluminium oxide, silicon oxide, activated carbon or its complex carrier), be widely used in plus In hydrogen sweetening process, to obtain premium-type gasoline product.
Hydrodesulfurization (HDS) technology is to grow up the fifties, and the nineties, the technology welcome second for 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 for affecting hydrofinishing efficiency and depth, The economy brought by high performance catalyst 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 the few selective hydrogenation new technique of desulfurization and 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.
Exxon research engineering company Containing Sulfur in selectively removing FCC gasoline with Akzo Nobel company joint development The Scanfining technology of compound, and in 1998, the technology is pushed to industrialization.It adopts traditional hydrotreating flow process, leads to Meticulous selecting catalyst (RT-225) is crossed, reaches loss of octane number and hydrogen consumption minimum.
The Prime-G technology of French IFP exploitation, the 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, and alkene saturation and cracking reaction do not occur, and 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 for obtaining can To realize the target of 100～150 μ g g-1 of sulfur content；By the hydrodesulfurization respectively of FCC petroleum benzin, 30 μ of achievable sulfur content The target of g g-1.
For the feature of domestic FCC gasoline sulfur-bearing, Fushun Petrochemical Research Institute (FRIPP) develops FCC gasoline selection 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-1III gasoline of GB.OCT-M technology is adopted after Shijiazhuang Oil Refinery, China Petrochemical Corp. continuously runs 17 months Two kinds of prioritization schemes that FRIPP recommends, after FCC gasoline hydrogenation, sulfur nutrient reaches GB III and IV standard.
On May 5th, 2016, seven department such as the Committee of Development and Reform, the Ministry of Finance, Chinese Ministry of Environmental Protection is issued with regard to printing and distributing《Accelerate finished product oil quality Upgrade job scheme》Notify, scheme clearly expands automobile-used vapour, five standard of diesel oil state and executes scope.From original Jing-jin-ji region, length three Angle, Pearl River Delta region key cities expand 11, whole eastern region provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, river to Soviet Union, Zhejiang, Fujian, Shandong, Guangdong and Hainan).Before 31 days October in 2015, eastern region is protected possesses five mark of manufacturing country 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 five standard of state should be met.
At present, the main method for reducing FCC gasoline sulfur content is catalytic desulfurhydrogenation.But hydrotreating method is present such as Lower deficiency：(1) equipment investment is big；(2) severe reaction conditions for taking off thiophenic sulfur, operating cost height are hydrogenated with；(3) alkene is de- in hydrogenation Easily there is saturation under the conditions of sulfur, a large amount of hydrogen are not only consumed, and causes octane number to reduce.FCC gasoline desulfurization degree is required Higher, operating condition is harsher, and the loss of octane number is also bigger.
How therefore a kind of hydrodesulfurization be provided, effectively can be controlled the sulfur content in gasoline in below 5ppm, with Meet five standard of state, while octane number loss is less or does not lose, it is the difficult problem that this area faces.
Content of the invention
It is an object of the invention to proposing a kind of hydrodesulfurization, the technique can be by the total sulfur content in FCC gasoline Below 5ppm is reduced to, to meet five standard of gasoline state.Meanwhile, the employing of the catalyst also causes the octane number of FCC gasoline not Substantially reduce.
For reaching this purpose, the present invention is employed the following technical solutions：
A kind of FCC gasoline hydrodesulfurization, the technique adopts fixed bed reactors, is filled with fixed bed reactors Hydrobon catalyst, the catalyst includes carrier and active component.
The carrier is complex or the mixture of MSU-G, SBA-15 and HMS.
The active component is two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst also contains catalyst aid, and the catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4's Mixture.
The reaction condition of the fixed bed reactors is：Reaction temperature is 300-420 DEG C, Hydrogen Vapor Pressure 2.5-3.5MPa, Hydrogen to oil volume ratio 500-800, volume space velocity 1.5-4h-1.
An object of the present invention is that, provides the compound to show collaboration effect of a kind of 3 kinds different mesopore molecular sieves Should be with special catalytic performance, in terms of the cooperative effect shows desulfuration purification, and special catalytic performance is then to show right In the raising of the service life and catalysis activity of catalyst.
In catalyst field, according to the definition of IUPAC (IUPAC), title of the aperture less than 2nm For micropore；Referred to as macropore of the aperture more than 50nm；Aperture is 2 to referred to as mesoporous (or the claiming mesopore) between 50nm.Mesoporous material It is a kind of new material with huge specific surface area and three-dimensional open-framework of aperture between micropore and macropore, it has The excellent specific property that other porous materials do not have：Pore passage structure with high-sequential；The single distribution in aperture, and aperture size Can change in relative broad range；Mesoporous various shapes, hole wall composition and property controllable；Height can be obtained by optimum synthesis condition Heat stability and hydrothermal stability.
But in present applications ' the tail must be taken, the mesoporous material is all single use, such as MCM system when for catalytic field Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU- 4th, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA- 8th, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Compound, such as Y/SBA-15, Y/SAPO-5 etc. of two kinds of carriers of a few studies literature research, majority be to be situated between Based on hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve.Adopt the compound with performance of 3 kinds of different mesopore molecular sieves Go out the research of cooperative effect and special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is the complex of MSU-G, SBA-15 and HMS or mixture.The complex or mixed In compound, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2):(0.4-0.7), preferably 1:(1-1.15): (0.5-0.7).
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention is adopted is all the existing molecular sieve of catalytic field, and which is Through obtaining widely studied and application in catalytic field.
MSU-G is a kind of mesopore molecular sieve with vesicle structure shape particle shape and layered framework structure, and which has height Degree skeleton crosslinking and relatively thick skeleton wall and with superpower heat stability and hydrothermal stability, its skeleton hole with vertical It is cross-linked with each other in layer and parallel to the hole of layer, diffusion path is very short because its vesicle shell is thick.The vesicle shape particle of MSU-G molecular sieve Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is very high.
SBA-15 belongs to one kind of mesopore molecular sieve, with two-dimentional six sides through-hole structure, with P3mm space group.In XRD In diffracting spectrum, main peak near about 1 °, is (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively Weak, it is difficult to observe.Additionally, the silicon dioxide on SBA-15 skeleton is generally amorphous state, observe not in Radix Rumiciss XRD diffraction To obvious diffraction maximum.SBA-15 has a larger aperture (maximum is up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the relatively unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S Type mesoporous material is thicker, thus hydrothermal stability is more preferable, while the relatively unordered organizational structure of short distance and aperture modulation scope are more Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction The heart.
The present invention carries out being combined pairing from each mesoporous material, screens through extensive, filters out MSU-G, SBA-15 Compound or mixing with HMS.Inventor has found, in numerous complex/mixture, only MSU-G, SBA-15 and HMS tri- Person compound or mix, could realize the collaboration lifting of hydrofinishing effect, and enable to catalysis activity and do not reduce for a long time, make Can be greatly increased with the life-span.In other words, the specific compound or mixing of only MSU-G, SBA-15 and HMS three of the present invention, Just while solving collaboration and two technical problems of service life.Other coordinate, or not possessing synergism, or using the longevity Life is shorter.
The complex, can adopt being simply mixed for MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two Mixing afterwards, such as MSU-G/SBA-15 complex, the mixing of MSU-G/HMS and SBA-15/HMS complex.Described being combined can To be prepared using known electrostatic matching method, ion exchange, two step crystallization methods etc..These mesopore molecular sieves are combined with which The preparation method of thing is the known method of catalyst field, and the present invention is no longer repeated with regard to which.
The second object of the present invention is to provide the cooperation of catalyst activity component, and the cooperation can form collaboration and make With raising catalytic effect.In the present invention, active component is particularly limited to for two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2C and The mixed proportion of tungsten carbide wc, inventor has found, the effect that different mixed proportions reaches is entirely different.Inventor has found, nitrogen Change two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-0.45):(0.8-1.2), only two molybdenum MO of control nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2The rubbing of C and tungsten carbide wc Your ratio within the range, can realize in FCC gasoline sulfur content control in below 10ppm and under octane number is obvious Drop.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 the molar ratio range, or omit or any one component is replaced, not Cooperative effect can be realized.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45- 0.5):(0.35-0.45):(0.8-1.0), more preferably 1:(0.45-0.48):(0.4-0.45):(0.9-1.0), most It is preferred that 1:0.48:0.42:0.95.
The total content of the active component is the 1%-15%, preferably 3-12%, further preferred 5-10% of vehicle weight. For example, the content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%th, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%th, 14.5% etc..
An object of the present invention also resides in the promoter for providing the catalyst.Catalyst of the present invention also contains There is catalyst aid, the catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although hydrofinishing be particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its For the property of carrier is adjusted, 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 is helped Agent in application with the carrier of the present invention with active component when, for high sulphur component, which promotes the effect of catalytic desulfurization/refined ?.
The present invention is passed through in numerous conventional cocatalyst component, and is carried out in amount of activated component selecting, compounded, most Find eventually to adopt Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Catalyst facilitation of the mixture of (niobium phosphate) to the present invention Substantially, its hydrothermal stability can be significantly improved, and its anti-coking deactivation is improved, so as to improve its service life.
The Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between do not have fixation ratio, that is to say, that Cr2O3、ZrO2、 CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention is adopted2O3、ZrO2、 CeO2、V2O5And NbOPO4Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although without specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allows for reaching To the requirement of effective dose, i.e., can play the content of catalyst aid effect, the 1-7% of such as carrier quality.The present invention is being selected During find, omit or replace one or more in the auxiliary agent, all do not reach the present invention technique effect (improve water Heat stability, reduces coking and improves service life), that is to say, that there is specific cooperation between the catalyst aid of the present invention and close System.
It is true that the present invention was once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidations, two girl Nb2O5, Have found that while in auxiliary agent and Nb is have also been introduced, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for which Difference, its beds coking is relatively rapid, and so as to cause catalyst duct to block, beds pressure drop rise is relatively Hurry up.The present invention also once attempts introducing other phosphate, but this trial although introduces phosphate anion, but equally exists hydro-thermal Stability is relatively slightly worse, and its beds coking is relatively rapid, so as to cause catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, but the present invention should be noted that, introduce catalysis Auxiliary agent is only one of preferred version, even if not introducing the catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. The catalyst aid for not introducing the present invention is particularly niobium phosphate, and which is compared to the scheme for introducing catalyst aid, and its defect is only phase To.I.e. the defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention, Advantageous or new features mentioned by the present invention are yet suffered from.The catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, which is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of the catalyst can take conventional infusion process and other alternative methods, people in the art The prior art unrestricted choice that member can be grasped according to which, the present invention is repeated no more.
Preferably, the reaction condition of the fixed bed reactors is：Reaction temperature is 320-400 DEG C, Hydrogen Vapor Pressure 2.8- 3.2MPa, hydrogen to oil volume ratio 550-750, volume space velocity 1.8-3.5-1.
Preferably, the technological process includes, after FCC gasoline is mixed with hydrogen, through optional heat exchanger heat exchange, then through adding Entering fixed bed reactors after hot stove heat carries out hydrodesulfurization, and product is separated through gas-liquid separation tower.Optionally, gas phase is returned Return and mix with FCC gasoline and hydrogen, liquid phase further can be refined, such as amine washes, strip and fractional distillation etc..
Preferably, the fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrodesulfurization of the present invention is by MSU-G, SBA-15 and HMS complex/mixture of selection special ratios As carrier, and the two molybdenum MO of nitridation for choosing special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are used as activity Composition, described catalyst also contains catalyst aid, and the catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixed Compound so that the catalyst produces cooperative effect, the hydrodesulfurization to FCC gasoline can control in total sulfur content less than 5ppm, same When octane number reduce amplitude control within 0.5-2%.
Specific embodiment
The present invention is illustrated to the hydrodesulfurization of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1: 1.1:0.5.The active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier The 10% of quality, its mol ratio is 1:0.4:0.3:0.8.
The Catalyst packing is entered fixed bed reactors, the reaction tube of the 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, which contains alkene 25.3m%, aromatic hydrocarbons 40.2m%, alkane 28.8m%, grinds Method octane number is studied carefully for 94.2,660 μ g/g of total sulfur content.
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.
The final product of test, its research octane number (RON) still reaches 94.1, and total sulfur content is reduced to 2ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is MSU-G/SBA-15 complex, MSU-G/HMS and SBA-15/ The ratio of the mixing of HMS complex, wherein MSU-G, SBA-15 and HMS is same as Example 1.The active component nitrogenizes two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide 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.
The final product of test, its research octane number (RON) still reaches 94, and total sulfur content is reduced to 3ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with MSU-G, remaining condition is constant.
The final product of test, it is 33ppm that its research octane number (RON) is 82, total sulfur content.
Comparative example 2
The carrier of embodiment 1 is replaced with SBA-15, remaining condition is constant.
The final product of test, it is 46ppm that its research octane number (RON) is 81, total sulfur content.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, remaining condition is constant.
The final product of test, it is 42ppm that its research octane number (RON) is 84, total sulfur content.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 complex, remaining condition is constant.
The final product of test, it is 29ppm that its research octane number (RON) is 87, total sulfur content.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS complex, remaining condition is constant.
The final product of test, it is 24ppm that its research octane number (RON) is 85, total sulfur content.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS complex, remaining condition is constant.
The final product of test, it is 31ppm that its research octane number (RON) is 82, total sulfur content.
Embodiment 1 is shown with comparative example 1-6, and the application is using MSU-G, SBA-15 and HMS complex/mixed of special ratios Compound when single carrier or complex carrier two-by-two is replaced with, does not all reach the technique effect of the present invention as carrier, therefore originally MSU-G, SBA-15 and HMS complex/mixture of the special ratios of invention has as between carrier and catalyst other components Standby cooperative effect, generates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
The final product of test, it is 21ppm that its research octane number (RON) is 87, total sulfur content.
Comparative example 8
The WC in embodiment 1 is omitted, remaining condition is constant.
The final product of test, it is 26ppm that its research octane number (RON) is 82, total sulfur content.
Above-described embodiment and the explanation of comparative example 7-8, several activearms of the catalyst of the hydrodesulfurization of the present invention divide it Between exist specific contact, be omitted or substituted one of which or several, can not all reach the certain effects of the application, it was demonstrated that its product Cooperative effect is given birth to.
Embodiment 3
Contain catalyst aid Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content be respectively 1%, 1.5%, 2%th, 1% and 3%, remaining is same as Example 1.
The final product of test, after which uses 3 months, beds pressure drop is not any change, and uses compared to same The beds pressure drop of time embodiment 1 reduces 13.8%.
Comparative example 9
Compared to embodiment 3, by NbOPO therein4Omit, remaining condition is identical.
The final product of test, after which uses 3 months, beds pressure drop is raised, compared to same use time reality The beds pressure drop for applying example 1 only reduces 2.6%.
Comparative example 10
Compared to embodiment 3, by CeO therein2Omit, remaining condition is identical.
The final product of test, after which uses 3 months, beds pressure drop is raised, compared to same use time reality The beds pressure drop for applying example 1 only reduces 4.5%.
Embodiment 3 is shown with comparative example 9-10, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted One of them or several groups of timesharing, can not all reach the present invention and add minimizing coking during catalyst aid so as to prevent catalyst bed The elevated technique effect of lamination drop.That is, its catalyst aid for demonstrating the present invention can improve the service life of the catalyst, And other catalyst aid effects are not so good as the specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited inAbove-mentioned technique, that is, do not mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the artMember is it will be clearly understood that any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and interpolation, the selection of the tool of auxiliary element body mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (8)

1. a FCC gasoline hydrodesulfurizationmethod technique, is characterized in that, described process using fixed bed reactors, fixed bed reaction In device, be filled with Hydrobon catalyst, described catalyst comprises carrier and active component;
Described carrier is compound or the mixture of MSU-G, SBA-15 and HMS;
Described active component is nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixture of C and tungsten carbide wc;
Described catalyst also contains catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixing Thing;
The reaction condition of described fixed bed reactors is: reaction temperature is 300-420 DEG C, Hydrogen Vapor Pressure 2.5-3.5MPa, hydrogen to oil volume ratio 500-800, volume space velocity 1.5-4h-1.
2. hydrodesulfurization as claimed in claim 1, is characterized in that, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2): (0.4-0.7), be preferably 1:(1-1.15): (0.5-0.7).
3. hydrodesulfurization as claimed in claim 1, is characterized in that, the 3-12% that the total content of described active component is vehicle weight, preferably 5-10%.
4. hydrodesulfurization as claimed in claim 1, is characterized 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. hydrodesulfurization as claimed in claim 1, is characterized in that, the reaction condition of described fixed bed reactors is: reaction temperature is 320-400 DEG C, Hydrogen Vapor Pressure 2.8-3.2MPa, hydrogen to oil volume ratio 550-750, volume space velocity 1.8-3.5-1, preferred, the reaction condition of described fixed bed reactors is: 370 DEG C of temperature, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 3h-1.
6. hydrodesulfurization as claimed in claim 1, is characterized in that, described technological process comprises, after FCC gasoline mixes with hydrogen, through optional heat exchanger heat exchange, then after heating furnace heating, enter fixed bed reactors and carry out hydrodesulfurization, product separates through gas-liquid separation tower.
7. hydrodesulfurization as claimed in claim 1, is characterized in that, described fixed bed reactors comprise 1-5 beds, preferably includes 2-3 beds.
8. hydrodesulfurization as claimed in claim 1, is characterized in that, Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Content is separately respectively the 1-7% of carrier quality, preferably 2-4%.
CN201610879650.7A 2016-09-30 2016-09-30 HDS (hydrodesulfurization) technology of FCC (fluid catalytic cracking) gasoline Pending CN106433758A (en)

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