CN107974279A - A kind of vapour oil treatment process - Google Patents
A kind of vapour oil treatment process Download PDFInfo
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- CN107974279A CN107974279A CN201610921279.6A CN201610921279A CN107974279A CN 107974279 A CN107974279 A CN 107974279A CN 201610921279 A CN201610921279 A CN 201610921279A CN 107974279 A CN107974279 A CN 107974279A
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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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/16—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles according to the "fluidised-bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of vapour oil treatment process, which includes：Gasoline stocks are sent into fluidizing reactor and is contacted with mixed catalyst and desulfurization and aromatization is carried out under hydro condition, obtain desulfurization and aromatization products；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；The preparation process of the alkene aromatized catalyst includes：Fresh aromatized catalyst is subjected to burin-in process.Method provided by the invention can reduce sulphur and olefin(e) centent in gasoline, and can improve the octane number of gasoline at the same time and keep high yield of gasoline.
Description
Technical field
The present invention relates to a kind of vapour oil treatment process.
Background technology
Atmosphere pollution getting worse caused by motor vehicle exhaust emission.As people are to the pay attention to day by day of environmental protection, China
The paces of vehicle fuel quality upgrading are accelerated, standard GB/T 17930-2013 requires sulfur content in gasoline to be not more than 10 μ g/
G, volume fraction of olefins are not more than 24%.
Catalytically cracked gasoline is the chief component of China's motor petrol, and 75% or so is accounted in gasoline pool, and it is special
Point is that have higher alkene and sulfur content.The deep desulfuration of gasoline is realized using hydrogen addition technology and is reduced in catalytically cracked gasoline
Olefin(e) centent it is not difficult, but since alkene is antiknock component, being greatly reduced for its content will cause octane number
Heavy losses, so as to influence the automobile-used performance of gasoline and the economic benefit of oil plant, therefore realizing the deep desulfuration of gasoline
Octane number is kept to become the hot spot of China's clean gasoline production at the same time.
At present, the deep desulfuration of gasoline is mainly using hydrodesulfurization or the method for adsorbing desulfurization.
Selective hydrodesulfurization is one of major way of current removing thiophene-type sulfide, but the reaction such as alkene saturation is same
Sample largely occurs, and causes loss of octane number larger.In addition, the deep hydrogenation method for recovering octane number is similarly approved by people,
It is while deep desulfuration and alkene saturation is carried out, sets second reactor to promote the cracking hydrocarbon of low octane rating, isomery
Change and alkylated reaction, so as to achieve the purpose that to recover octane number.Chinese patent CN101845322A discloses a kind of reduction vapour
The method of sulphur and olefin(e) centent in oil, raw material catalytic cracking gasoline first pass through pre-hydrogenator removing alkadienes, subsequently into
Fractionating column cutting is fractionated into light, heavy petrol, and light petrol carries out facing hydrogen absorption desulfurization, and heavy petrol adds into selective hydrogenation reactor
Hydrogen desulfurization, reaction effluent enter back into hydro-upgrading reactor and carry out hydro-upgrading, reduce olefin(e) centent, the heavy petrol after modification
The clean gasoline of standard requirement is met with light petrol absorption desulfurization product reconciliation.Absorbing desulfurization catalyst is in gasoline
Although sulfide has good removal effect, absorption desulfurization carries out under conditions of hydrogen is faced, can saturation catalytically cracked gasoline
In alkene, especially light petrol carries out absorption desulfurization, and the olefin component octane number in light petrol is higher, can cause the pungent of gasoline
Alkane value is largely lost.
Sulfur-containing compound in absorption method removing fuel oil, is that light oil is carried out using adsorbent to face hydrogen reaction absorption, raw
Into metal sulfide or using sulfide polarity removing sulphur, hydrogen consumption is relatively low, and desulfuration efficiency is high, can produce sulfur content in 10 μ g/g
Following gasoline.Although absorbing process realizes the deep desulfuration of gasoline under the conditions of low hydrogen consumption, gasoline product octane number still omits
There is loss.Especially when handling the gasoline stocks that olefin(e) centent is high and sulfur content is high, still cause octane number loss compared with
Greatly.
For most of catalytic cracking units, for propylene enhancing and butylene yield and the octane number for improving gasoline,
It is effective method using containing the catalyst with MFI structure molecular sieve or auxiliary agent.United States Patent (USP) USP3758403 is invented
The method of ZSM-5 molecular sieve is added in catalytic cracking catalyst can improve the octane number of gasoline and increase C3~C4 alkene
Yield.But as it is known by one skilled in the art, propylene enhancing and butylene yield are to sacrifice gasoline production as cost.
Aromatizing low-carbon paraffin is the effective ways for improving low-carbon alkanes utility value.People are to high silica alumina ratio molecular sieve
Substantial amounts of research is carried out for the aromatization process of catalyst, especially using ZSM-5, ZSM-11, ZSM-21 molecular sieve as catalyst
Process carried out substantial amounts of research, and using the zeolite with MFI structure be used to produce from coking or pyrolysis gasoline low
The aromatisation of carbon hydro carbons.
The content of the invention
The object of the present invention is to provide a kind of vapour oil treatment process, method provided by the invention can be reduced in gasoline
Sulphur and olefin(e) centent, and the octane number of gasoline can be improved at the same time and keep high yield of gasoline.
To achieve these goals, the present invention provides a kind of vapour oil treatment process, which includes：Gasoline is former
Material, which is sent into fluidizing reactor, to be contacted with mixed catalyst and desulfurization and aromatization is carried out under hydro condition, is taken off
Sulphur and aromatization products；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；The alkene
The preparation process of hydrocarbon aromatizing catalyst includes：Fresh aromatized catalyst is subjected to burin-in process.
Preferably, the condition of the burin-in process includes：Temperature is 500-800 DEG C, when the time is 1-360 small, aging gas
Atmosphere contains vapor.
Preferably, the micro-activity of the alkene aromatized catalyst is 20-55, and the micro-activity uses RIPP 92-
The mat activity test method of 90 catalytic cracking industry equilibrium catalysts is measured.
Preferably, volume fraction of olefins is more than 20 body % in the gasoline stocks.
Preferably, in the gasoline stocks sulfur content more than 10 μ g/g.
Preferably, the gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, thermal cracking vapour
At least one of oil and direct steaming gasoline.
Preferably, the cut point of the light gasoline fraction and heavy naphtha is 60-80 DEG C.
Preferably, the fluidizing reactor is riser reactor and/or dense-phase fluidized bed reactor.
Preferably, the absorbing desulfurization catalyst contains silica, aluminium oxide, zinc oxide and desulphurizing activated metal, institute
It is selected from least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium to state desulphurizing activated metal.
Preferably, on the basis of the butt weight of the absorbing desulfurization catalyst and in terms of oxide weight, the absorption
Zinc oxide described in desulphurization catalyst accounts for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for 5-30 weight %；
On the basis of the butt weight of the absorbing desulfurization catalyst and in terms of element wt, taken off described in the absorbing desulfurization catalyst
The content of sulphur active metal is 5-30 weight %.
Preferably, counted and on the basis of the gross weight of the alkene aromatized catalyst by butt, the alkene aromatisation
Catalyst contains the molecular sieve of 10-30 weight %, the aromatization activity metal oxide of 0-20 weight % and 50-90 weight %'s
Carrier；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, and the aromatization activity metal is selected from the
The metallic element of Group IVB, the metallic element of Group VB, the metallic element of group VIB, the metallic element of group VIII, group ib
Metallic element, the metallic element of group iib and at least one of the metallic element of group III A, the carrier includes oxidation
Silicon and/or aluminium oxide.
Preferably, the MFI structure molecular sieve is selected from least one of ZSM-5, ZSM-8 and ZSM-11, the virtue
Structure active metal is selected from least one of Fe, Zn and Ga.
Preferably, by weight, the ratio that the alkene aromatized catalyst accounts for the mixed catalyst is 1-30 weights
Measure %.
Preferably, the condition of the desulfurization and aromatization includes：Reaction temperature is 350-500 DEG C, and weight (hourly) space velocity (WHSV) is
When 2-50 is small-1, reaction pressure 0.5-3.0MPa, hydrogen and gasoline stocks volume ratio are 1-500.
The present invention has following technique effect compared with prior art：
1st, method of the invention is by the gasoline stocks of the high alkene of high-sulfur and absorbing desulfurization catalyst and alkene Aromatizatian catalytic
Agent carries out desulfurization and aromatization, while content of sulfur in gasoline is reduced, the alkene in gasoline can be carried out aromatisation, from
And the content of alkene in gasoline had both been reduced, and also improve the octane number of gasoline and keep the high income of gasoline stocks, Neng Gouzhi
Connect the even VI label gasoline of state of producing country V.
2nd, desulfurization and aromatization of the invention are carried out using two kinds of catalyst in a fluidizing reactor, are both carried
High reaction efficiency, also reduces cost of investment, without increasing or changing reactor.
3rd, method of the invention can also reduce the light component in gasoline, reduce gasoline vapour pressure.
4th, alkene aromatized catalyst of the invention passes through burin-in process, makes the active moderate of alkene aromatized catalyst,
Be conducive to the progress of aromatisation.
5th, of the invention desulfurization and aromatization are carried out using two kinds of catalyst in a fluidizing reactor, can be with
Gasoline step-by-step processing method (desulfurization after aromatisation, or gasoline elder generation aromatisation after the desulfurization of gasoline elder generation) is avoided to need individually increase aromatization
Change reactor and subsystem, can also avoid gasoline desulfurization and aromatisation coupled catalyst is needed to change existing absorption desulfurization and urged
The preparation process flow and catalyst abrasion intensity of agent and aromatized catalyst, both improve reaction efficiency, also reduce
Cost of investment.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of flow diagram of embodiment of the method for the present invention.
Description of reference numerals
1 gasoline stocks, 2 hydrogen, 3 fluidizing reactor
6 tail gas of 4 desulfurization and 5 high-pressure separator of aromatization products
Complete 8 fractionating column of cut, 9 lighter hydrocarbons of 7 gasoline
10 gasoline products
Embodiment
The embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
RIPP test methods for details, reference can be made in the present invention《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, nineteen ninety version.
The present invention also provides a kind of vapour oil treatment process, which includes：It is anti-that gasoline stocks are sent into fluidization
Answer and contacted in device with mixed catalyst and desulfurization and aromatization are carried out under hydro condition, obtain desulfurization and aromatisation production
Thing；Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；The alkene Aromatizatian catalytic
The preparation process of agent includes：Fresh aromatized catalyst is subjected to burin-in process.
According to the present invention, desulfurization and aromatization refer to gasoline stocks under hydro condition in absorbing desulfurization catalyst and
Desulfurization is carried out under the collective effect of alkene aromatized catalyst and alkene is converted into the process of aromatic hydrocarbons, it is during which anti-with cracking
Should, its condition can include：Reaction temperature is 350-500 DEG C, is preferably 380-420 DEG C, when weight (hourly) space velocity (WHSV) is 2-50 small-1, it is excellent
Elect as 5-20 it is small when-1, reaction pressure 0.5-3.0MPa, is preferably 1.5-2.5MPa, hydrogen is with gasoline-volume ratio (in standard shape
Condition (STP) 0 DEG C of (273K), 1.01 × 105Under Pa) it is 1-500, it is preferably 50-200.
According to the present invention, absorbing desulfurization catalyst is well-known to those skilled in the art that can contain silica, oxygen
Change aluminium, zinc oxide and desulphurizing activated metal, the desulphurizing activated metal can be selected from cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver,
At least one of tin and vanadium.
A kind of embodiment, on the basis of the butt weight of the absorbing desulfurization catalyst and with oxide weight
Meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for
5-30 weight %；On the basis of the butt weight of the absorbing desulfurization catalyst and in terms of element wt, the absorption desulfurization is urged
The content of desulphurizing activated metal described in agent is 5-30 weight %.
According to the present invention, the absorbing desulfurization catalyst can also contain 1-10 weight % class coke mass.Industrial practice table
Bright, desulfuration efficiency and octane number loss of the carbon content to absorbing desulfurization catalyst on absorbing desulfurization catalyst has shadow
Ring, with increasing for absorbing desulfurization catalyst carbon content, absorbing desulfurization catalyst desulfuration efficiency progressively declines, octane number damage
Mistake reduces therewith.Similarly, the sulfur content that absorbing desulfurization catalyst keeps certain is very important.Practice have shown that suction to be generated
It is 9 weight %-10 weight % that attached desulphurization catalyst, which carries sulfur content, and regenerative adsorption desulphurization catalyst carries 5 weight %-6 weight % of sulfur content,
The sulphur difference of absorbing desulfurization catalyst to be generated and regenerative adsorption desulphurization catalyst is the most suitable for 4 weight % or so.To reduce gasoline
Loss of octane number, the behaviour that will have been generally acknowledged that rational " small sulphur is poor, big cycle volume " operation adjustment is " partial circulating amount, big sulphur are poor "
Make, reduce regenerative adsorption desulphurization catalyst sulfur content, improve absorbing desulfurization catalyst sulfur content to be generated, reduce octane number damage
Lose, two kinds of operation essence have been to maintain the higher load sulfur content for the absorbing desulfurization catalyst that reaction is participated in reactor, reduce and inhale
The activity of attached desulphurization catalyst, reduces loss of octane number.
According to the present invention, alkene aromatized catalyst is to refer to hydrocarbon conversions such as the alkene in gasoline stocks be aromatic hydrocarbons
Catalyst, generally comprise molecular sieve, preferably include molecular sieve, carrier and metal, for example, in terms of butt and with the alkene virtue
On the basis of the gross weight of structure catalyst, the alkene aromatized catalyst can the molecular sieve containing 10-30 weight %, 0-20
The aromatization activity metal oxide of weight % and the carrier of 50-90 weight %；Wherein, the molecular sieve can include Y molecules
Sieve and/or MFI structure molecular sieve, be preferably five-membered ring high-silica zeolite, the high-silica zeolite can be Hydrogen or
By rare earth and/or P Modification, its silica alumina ratio is preferably greater than 100, and more preferably greater than 150.The MFI structure molecular sieve is can
With selected from least one of ZSM-5, ZSM-8 and ZSM-11.The aromatization activity metal can play partial desulfurization or hydrocarbon
Class transformation function, such as can be the metallic element selected from group ivb, the metallic element of Group VB, the metal member of group VIB
The metallic element of element, the metallic element of group VIII, the metallic element of group ib, the metallic element of group iib and group III A
At least one of；The metallic element preferred Zr or/and Ti of wherein group ivb, the preferred V of metallic element of Group VB, group VIB
Metallic element preferred Mo or/and W, one or both of metallic element preferred Fe, Co, Ni of group VIII above element,
The preferred Cu of metallic element of group ib, the preferred Zn of metallic element of group iib, the preferred Ga of metallic element of group III A, into one
Step ground, the aromatization activity metal are preferably selected from least one of Fe, Zn and Ga, and content is preferably 0.5-5 weight %.
The carrier preferably includes silica and/or aluminium oxide.It is micro- that the particle diameter of the alkene aromatized catalyst is generally 20-120
Rice is suitable with absorbing desulfurization catalyst particle diameter.Absorbing desulfurization catalyst and alkene aromatized catalyst are separately formed by the present invention
It is used in mixed way after (such as spray drying).
A kind of embodiment, the MFI structure molecular sieve, its preparation process can include ammonia exchange, P Modification,
Metal component modification and calcination process step, are in particular by the conventional crystallization obtained sodium form with MFI structure point
Son sieve is according to molecular sieve：Ammonia salt：H2O=1：(0.1-1)：The weight ratio of (5-10) is in room temperature to when exchange 0.3-1 is small at 100 DEG C
After filter, be introduced into phosphorus-containing compound and containing one or more compounds pair in Fe, Co, Ni, Zn, Mn, Ga and Sn
Molecular sieve is modified, when roasting 0.5-8 is small at 400-800 DEG C afterwards, wherein the processing procedure of described roasting can also be
Carried out under steam atmosphere.Further, MFI structure molecular sieve provided by the present invention, to molecular sieve in preparation process
Being modified can be carried out by the way of dipping or ion exchange.Further, the phosphorus-containing compound can be choosing
From one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate or its mixture.Further, the Fe, Co, Ni, Zn,
Mn, Ga and Sn compound can be selected from their water soluble salt, the water soluble salt can be selected from sulfate, nitrate,
One kind in chlorate.Further, MFI structure molecular sieve provided by the present invention, contains phosphorus and metal component, its acid site
Combined with the dehydrogenation close centre of metal, and the presence of phosphorus at the same time can not only improve the structural stability of molecular sieve but also make gold
The ability of dehydrogenation sulfurization of category.
The method that the present invention introduces metal active constituent on molecular sieve or carrier, can use existing various gold-supporteds
Belong to the method for the method of oxide, such as dipping, i.e., using one or more of metal salt solution impregnated zeolites or carrier；It is or heavy
The method in shallow lake, i.e., using on one or more of metal salt solutions or its oxide, hydroxide deposition to molecular sieve or carrier；Or
Person's soild oxide and/or its precursor-metal salt or its hydroxide and molecular sieve or carrier mechanical mixture, grinding or not
The method of grinding；Or colloidal sol facture, gelling process and hydro-thermal method etc..The metal salt is mainly the sulfate of metal, nitre
Hydrochlorate, acetate, halide and metal ammonium salt, metal sodium salt etc..Method for optimizing present invention introduces metal active constituent is heavy
The method in shallow lake or the method for dipping.
According to alkene in gasoline and the difference of sulfur content, absorbing desulfurization catalyst and alkene aromatisation in fluidizing reactor
The ratio of catalyst can be different, for example, by weight, the alkene aromatized catalyst accounts for the ratio of the mixed catalyst
It is preferably 3-15 weight % for 1-30 weight %.
Present inventors discovered unexpectedly that the micro-activity of alkene aromatized catalyst effect in 20-55 is more excellent,
The micro-activity is measured using the mat activity test method of RIPP 92-90 catalytic cracking industry equilibrium catalysts.But
From manufacturer's production or homemade qualified not yet used fresh aromatized catalyst, activity is generally more than 60, activity
Higher, cracking performance is stronger, and therefore, fresh aromatized catalyst needs to be handled, and to reduce acid amount, increases acid strength, has
Beneficial to the generation for reducing hydrogen transfer reaction.
A kind of embodiment, the alkene aromatized catalyst pass through burin-in process.Burin-in process refers to deposit in vapor
Fresh aromatized catalyst is subjected to high-temperature process under the conditions, to reduce its activity.The condition of the burin-in process can be with
Including：Temperature is 500-800 DEG C, and when the time is 1-360 small, aging atmosphere contains vapor, is preferably 100% vapor gas
Atmosphere.
A kind of embodiment of burin-in process, by fresh aromatized catalyst and vapor or steam-laden aging
Media contact, when (temperature be 500 DEG C -800 DEG C) aging 1 is small under certain thermal and hydric environment -360 it is small when after, obtained aging
Aromatized catalyst.Further, the burin-in process refers to fresh aromatized catalyst in 800 DEG C and 100% vapor
Under condition (with reference to RIPP 92-90) aging certain time to reduce activity, if ageing time is 4h or 17h.Further, newly
The ageing method of fresh aromatized catalyst is implemented：Fresh aromatized catalyst is loaded into the preferably close phase of reactor
Fluid bed, contacts with vapor or steam-laden aging medium, under certain thermal and hydric environment (temperature is 500 DEG C -800 DEG C)
When aging 1 is small -360 it is small when after, obtain aging aromatized catalyst.Further, the aging medium include air, dry gas,
Gas or air after regenerated flue gas, air and dry combustion gas and the gas or other gases such as nitrogen after burning oil firing.Institute
The weight ratio for stating the vapor in steam-laden aging medium and aging medium is 0.2-0.9, is preferably 0.40-0.60.Institute
The regenerating unit that regenerated flue gas can come from invention is stated, can be from regenerating unit.
According to the present invention, it can be selected from catalytically cracked gasoline that gasoline stocks, which are well-known to those skilled in the art, urge
Change at least one of drippolene, coker gasoline, pressure gasoline and direct steaming gasoline.The gasoline that the present invention is handled is preferably height
Alkene and high sulfur oil, its volume fraction of olefins are generally higher than 20 body %, preferably greater than 30 body %, more preferably greater than 40 body %,
Further preferably greater than 50 body %；Sulfur content is generally more than 10 μ g/g, preferably greater than 50 μ g/g, more preferably greater than 100 μ g/g,
Further preferably greater than 500 μ g/g, still more preferably more than 1000 μ g/g, the organic sulfur compound in gasoline be generally mercaptan,
Thioether, thiophene, alkylthrophene, benzothiophene and methyl benzothiophene etc..
According to the present invention, fluidizing reactor is well-known to those skilled in the art, for example, can be selected from fluid bed,
It is riser, downstriker pipeline reactor, the compound reactor being made of riser with fluid bed, defeated by riser and downstriker
Line sending form compound reactor, be made of two or more risers compound reactor, by two or two with
On the fluid bed compound reactor, the compound reactor that is made of two or more downstriker pipelines that form, it is excellent
Elect riser reactor and/or fluidized-bed reactor as, above-mentioned every kind of reactor is segmented into two or more reactions
Area.The fluidized-bed reactor can be selected from fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying
One or more in bed and dense-phase fluidized bed；The riser reactor can be selected from equal diameter riser, etc. linear speed carry
One or more in riser and various variable diameters risers.Preferably, it is anti-to be selected from dense-phase fluidized for the fluidizing reactor
Answer device.
The present invention is further illustrated below in conjunction with attached drawing, but it is not thereby limiting the invention.
As shown in Figure 1, enter fluidizing reactor 3 after the gasoline stocks 1 of high alkene high-sulfur are mixed with hydrogen 2, with suction
Attached desulphurization catalyst and the aromatized catalyst contact Jing Guo aging, carry out absorption desulfurization and aromatization, desulfurization and virtue
Structure product 4 enters high-pressure separator 5, obtains the full cut 7 of low-sulphur oil and tail gas 6.The full cut 7 of gasoline enters fractionating column 8, point
Evaporate for lighter hydrocarbons 9 and super-low sulfur high octane gasoline products 10.
The following examples will be further described the present invention, but not thereby limiting the invention.
The full cut of gasoline stocks used in embodiment and comparative example is stable gasoline A, its property is listed in table 1.
Absorbing desulfurization catalyst used in embodiment and comparative example is catalyzed by Sinopec Group
Agent branch company produces, goods number FCAS, and used aromatized catalyst makes catalyst by oneself for laboratory, and the trade mark is
OTAZ-C-3, absorbing desulfurization catalyst and aromatized catalyst property are listed in table 2.
Wherein, the preparation method of aromatized catalyst OTAZ-C-3 is：By 50g (NH4)2SO4It is dissolved in 1000g water, to institute
Obtain and 100g (butt) crystallization product ZSM-5 molecular sieve (Chang Ling catalyst plant produces, non-amine method synthesis) is added in solution, at 95 DEG C
After exchanging 1h, filter cake is filtered to obtain；By 8.6g (NH4)2HPO4It is dissolved in 60g water, is mixed with dipping and dries with filter cake；Add
6.0gGa(NO3)3·9H2O is dissolved in 120g water, is mixed with dipping and is dried with above-mentioned sample；Gained sample is in 580 DEG C of calcination process 3
Hour, obtain molecular sieve product；Gained molecular sieve product is added in 500 grams of sial colloids, the spray-dried microballoon that is made is urged
Agent.
In following embodiment and comparative example, Na in catalyst2O、NiO、ZnO、Ga2O3、Al2O3、SiO2Content X
Ray fluorescence measures, wherein Al2O3、SiO2Content referring specifically to RIPP134-90 measure, remaining composition measuring method phase
Seemingly.
GB/T 5487-1995 and GB/ is respectively adopted in the octane number RON and MON of gasoline in the embodiment of the present invention and comparative example
T 503-1995 standard methods are measured, anti-knock index=(MON+RON)/2, and gasoline PONA is using simulation distillation and gasoline list
Body hydrocarbon analyzes (ASTM D2887 and ASTM D6733-01 (2011) test method is respectively adopted to be tested), content of sulfur in gasoline
It is measured using SH/T0689-2000.
Embodiment 1
The fresh aromatized catalyst that the trade mark is OTAZ-C-3 is loaded into dense-phase fluidized bed reactor, in aging temperature 780
DEG C, when continuous ageing 8 is small under 100% water vapor conditions, obtain the OTAZ-C-3 catalyst of aging, micro-activity 43.
Stable gasoline raw material A is in small-sized continuous fluidized bed reactor with including absorbing desulfurization catalyst FCAS and aging virtue
The mixed catalyst contact of structure catalyst OTAZ-C-3 (OTAZ-C-3 accounts for the 7% of total catalyst weight), carries out absorption desulfurization
And aromatization.Operating condition is：Reaction temperature is 400 DEG C, reactor pressure 2.1MPa, the weight (hourly) space velocity (WHSV) of gasoline stocks
For 6 it is small when-1, the volume ratio of hydrogen and gasoline stocks is 75.The desulfurization that is obtained by reactor head and aromatization products through cooling,
The isolated full cut of tail gas and gasoline.The regeneration temperature of mixed catalyst is 550 DEG C, and the mixed catalyst after regeneration returns anti-
Answer in device and recycle, the full cut of gasoline is listed in table 3 as gasoline products, its property.
Comparative example 1
Essentially identical with the operation of embodiment 1, difference is to replace using not aged aromatized catalyst equal
The aging aromatized catalyst of weight, the full cut of gasoline are listed in table 3 as gasoline products, its property.
Comparative example 2
Essentially identical with the operation of comparative example 1, difference is all to be inhaled using absorbing desulfurization catalyst FCAS
Attached desulphurization reaction, the full cut of gasoline are listed in table 3 as gasoline products, its property.
It can be seen from Table 3 that on the premise of desulfuration efficiency is consistent, relative to comparative example 2, the gasoline of embodiment 1 is received
Rate is suitable, and the yield of gasoline of comparative example 1 reduces about 1.3 percentage points, and the research octane number (RON) of embodiment 1 increases than comparative example 2
Add about 1.2 units, increase about 2.8 units than comparative example 2.
Table 1
Table 2
| Catalyst | FCAS | OTAZ-C-3 |
| Chemical composition, weight % | ||
| Aluminium oxide | 13 | 50.3 |
| Sodium oxide molybdena | / | 0.06 |
| Nickel oxide | 21 | / |
| Zinc oxide | 52 | / |
| Gallium oxide | / | 1.5 |
| Silica | 14 | 48.14 |
| Apparent density, kg/m3 | 1010 | 800 |
| Pore volume, mL/g | / | 0.27 |
| Specific surface area, m2/g | / | 218 |
| Abrasion index, again during %-1 | / | 1.5 |
| Screening composition, weight % | ||
| 0~40 micron | 14.5 | 13.9 |
| 40~80 microns | 51.9 | 49.5 |
| >80 microns | 33.6 | 36.6 |
| Micro-activity | / | 80 |
Table 3
Claims (14)
1. a kind of vapour oil treatment process, the processing method include：
Gasoline stocks are sent into fluidizing reactor desulfurization and aromatization are contacted and carried out under hydro condition with mixed catalyst
Change reaction, obtain desulfurization and aromatization products；
Wherein, the mixed catalyst includes absorbing desulfurization catalyst and alkene aromatized catalyst；
The preparation process of the alkene aromatized catalyst includes：Fresh aromatized catalyst is subjected to burin-in process.
2. according to the method described in claim 1, wherein, the condition of the burin-in process includes：Temperature is 500-800 DEG C, when
Between for 1-360 it is small when, aging atmosphere contains vapor.
3. according to the method described in claim 1, wherein, the micro-activity of the alkene aromatized catalyst is 20-55, described
Micro-activity is measured using the mat activity test method of RIPP 92-90 catalytic cracking industry equilibrium catalysts.
4. according to the method described in claim 1, wherein, volume fraction of olefins is more than 20 body % in the gasoline stocks.
5. according to the method described in claim 1, wherein, sulfur content is more than 10 μ g/g in the gasoline stocks.
6. according to the method described in claim 1, wherein, the gasoline stocks are selected from catalytically cracked gasoline, catalytic pyrolysis vapour
At least one of oil, coker gasoline, pressure gasoline and direct steaming gasoline.
7. according to the method described in claim 1, wherein, the cut point of the light gasoline fraction and heavy naphtha is 60-80
℃。
8. according to the method described in claim 1, wherein, the fluidizing reactor is riser reactor and/or dense-phase flow
Fluidized bed reactor.
9. according to the method described in claim 1, wherein, the absorbing desulfurization catalyst contains silica, aluminium oxide, oxidation
Zinc and desulphurizing activated metal, the desulphurizing activated metal be in cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium at least
It is a kind of.
10. according to the method described in claim 9, wherein, on the basis of the butt weight of the absorbing desulfurization catalyst and with
Oxide weight meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weights
% is measured, aluminium oxide accounts for 5-30 weight %；On the basis of the butt weight of the absorbing desulfurization catalyst and in terms of element wt, institute
The content for stating desulphurizing activated metal described in absorbing desulfurization catalyst is 5-30 weight %.
11. according to the method described in claim 1, wherein, in terms of butt and with the gross weight of the alkene aromatized catalyst
On the basis of, the alkene aromatized catalyst contains the molecular sieve of 10-30 weight %, the aromatization activity metal of 0-20 weight %
The carrier of oxide and 50-90 weight %；Wherein, the molecular sieve includes Y molecular sieve and/or MFI structure molecular sieve, the virtue
Structure active metal is the metallic element selected from group ivb, the metallic element of Group VB, the metallic element of group VIB, Section VIII
The metallic element of race, the metallic element of group ib, the metallic element of group iib and group III A metallic element at least one
Kind, the carrier includes silica and/or aluminium oxide.
12. according to the method for claim 11, wherein, the MFI structure molecular sieve is selected from ZSM-5, ZSM-8 and ZSM-
At least one of 11, the aromatization activity metal is selected from least one of Fe, Zn and Ga.
13. according to the method described in claim 1, wherein, by weight, the alkene aromatized catalyst accounts for the mixing and urges
The ratio of agent is 1-30 weight %.
14. according to the method described in claim 1, wherein, the condition of the desulfurization and aromatization includes：Reaction temperature is
350-500 DEG C, when weight (hourly) space velocity (WHSV) is 2-50 small-1, reaction pressure 0.5-3.0MPa, hydrogen and gasoline stocks volume ratio are 1-
500。
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| CN110857394A (en) * | 2018-08-24 | 2020-03-03 | 中国石油化工股份有限公司 | Method and system for processing coking gasoline and heavy raw oil |
| CN111068767A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for producing clean gasoline and preparation and application thereof |
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| CN110857394A (en) * | 2018-08-24 | 2020-03-03 | 中国石油化工股份有限公司 | Method and system for processing coking gasoline and heavy raw oil |
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| CN111068767B (en) * | 2018-10-18 | 2023-01-10 | 中国石油化工股份有限公司 | Catalyst for producing clean gasoline and preparation and application thereof |
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