CN101379166A - Fluid catalytic cracking process - Google Patents

Fluid catalytic cracking process Download PDF

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Publication number
CN101379166A
CN101379166A CNA2007800044474A CN200780004447A CN101379166A CN 101379166 A CN101379166 A CN 101379166A CN A2007800044474 A CNA2007800044474 A CN A2007800044474A CN 200780004447 A CN200780004447 A CN 200780004447A CN 101379166 A CN101379166 A CN 101379166A
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oil
feed
paraffinic
hydrocarbon
catalyzer
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CN101379166B (en
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J·L·M·德里克斯
G·A·海德吉乔治
C·J·斯查沃里恩
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • 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
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/1022—Fischer-Tropsch products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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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

A fluid catalytic cracking process for the preparation of cracked products by contacting in a reactor a hydrocarbon feedstock with a cracking catalyst, wherein the hydrocarbon feedstock comprises a paraffinic feedstock and triglycerides.

Description

Fluidized catalytic cracking method
Technical field
The present invention relates to fluidized catalytic cracking method.
Background technology
In fluidized catalytic cracking method, the hydrocarbon feed of the high boiling point scope of preheating is contacted with the cracking catalyst of heat in catalyst cracker (normally riser tube).This raw material is lower boiling product by cracking, for example dry gas, LPG, gasoline and turning oil.In addition, coke and nonvolatile product formation of deposits spent catalyst on catalyzer.This reactor effluent enters separator, therein spent catalyst and reaction product is separated.In subsequent step, spent catalyst is carried out stripping to remove nonvolatile hydrocarbon product from catalyzer with steam.Enter revivifier through steam stripped catalyzer, combustion of coke and remaining hydrocarbon material therein, and therein catalyzer is heated to the required temperature of cracking reaction.Turning back in the reactor heat then through the regenerated catalyzer.
As hydrocarbon feed, can cracking comprise the hydrocarbon feed of most of paraffinic hydrocarbons.But this hydrocarbon feed (for example fischer-tropsch product) that is rich in paraffinic hydrocarbons of cracking is not direct.
US-A-4684756 has described the method that the fischer-tropsch wax that obtains by fluid catalytic cracking prepares gasoline fraction in the catalytic Fischer-Tropsch process of iron.Yield of gasoline is 57.2wt%.The shortcoming of disclosed method is that yield of gasoline is lower among the US-A-4684756.
EP-A-454256 described by the fischer-tropsch product by under 580-700 ℃ temperature in moving-burden bed reactor with the ratio of the catalyzer of 65-86kg/kg and oil with this product and the method that comprises the catalyzer contact preparation light alkene of ZSM-5.
WO-A-2004/106462 has described wherein the method that the catalyst system contact preparation of will heavier fischer-tropsch product and comprising the catalyzer that contains acidic matrices and large pore molecular sieve has the gasoline product that goes far towards high-octane isoparaffin and alkene of high level.
The shortcoming of handling this paraffinic feed in the FCC unit is that coke output is too low.In so-called FCC revivifier, remove coke on the catalyzer by oxidation.In such processing step, the temperature of catalyzer makes it be applicable to the temperature of actual catalytic cracking step because thermopositive reaction raises and reaches.If the coke content of catalyzer is low excessively, need in revivifier, add additional fuel, this situation obviously is not needed.
NL-A-8700587 has described anhydrous butter oil, and catalytic cracking is hydrocarbon product, for example C on the RE-USY type catalyzer of active crystal alumina substrate further comprising 4Gas and light gas, gasoline (C 5-216 ℃), light cycle oil and coke.
The objective of the invention is to obtain thermal equilibrium better method than art methods.
Summary of the invention
Have been found that now and can realize above-mentioned purpose by in the presence of triglyceride level, paraffinic feed being carried out fluid catalytic cracking.
Therefore, the invention provides by in reactor with the fluidized catalytic cracking method of hydrocarbon feed and cracking catalyst contact preparation crackate, wherein said hydrocarbon feed comprises paraffinic feed and triglyceride level.
Have been found that mixture, can on cracking catalyst, generate more coke by cracking paraffinic feed and triglyceride level.Another advantage of this mixture of cracking has been to obtain to have the gasoline of higher octane.The applicant further finds can obtain sulphur content and be higher than 87 gasoline product less than 10ppm, aromaticity content less than 35 volume % (preferably less than 25 volume %) and octane value by selecting paraffinic feed and the proper equilibrium between the triglyceride level on the one hand on the other hand.The triglyceride level that exists in the hydrocarbon feed is carried out cracking, and the product of formation causes the RON octane value of gross product to improve.
Embodiment
Triglyceride level is the glyceryl ester that wherein makes glycerine esterification with three lipid acid.Preferably, be used for that the fatty acid part scope is a 4-30 carbon atom in the lipid acid that the triglyceride level of the inventive method comprises, this lipid acid the most saturated or comprise 1,2 or 3 two key.Triglyceride level is the main component in vegetables oil, fish oil and the animal tallow.
Preferably, described hydrocarbon feed comprises vegetables oil, animal tallow or fish oil so that triglyceride level to be provided.This vegetables oil, animal tallow or fish oil need not be anhydrous or pure state or through hydrogenation in advance.This oil or fat can comprise the free fatty acid and/or the ester of different amounts, and the both can be converted into hydrocarbon in procedure of the present invention.This oil or fat can further comprise carotenoid, hydrocarbon, phosphatide, simple fatty acids and ester thereof, terpenes, sterols, Fatty Alcohol(C12-C14 and C12-C18), tocopherol, polyisoprene, carbohydrate and protein.
The vegetables oil that is fit to comprises rapeseed oil, plam oil, cocounut oil, Semen Maydis oil, soya-bean oil, Thistle oil, sunflower oil, linseed oil, sweet oil and peanut oil.The animal tallow that is fit to comprises lard, tallow, suet and chicken fat.Can use the raw material of the oily or fatty mixture of different sources as this catalytic conversion step.Therefore, can use the mixture of vegetables oil, animal tallow, fish oil and comprise the mixture of vegetables oil, animal oil and/or fish oil.Preferred oil is rapeseed oil and plam oil, particularly plam oil.Have been found that and use plam oil to cause the higher conversion of crackate and the higher yields of gasoline.
Described hydrocarbon feed can further comprise the ester of natural acid and non-triglyceride level, for example is derived from the fatty acid methyl ester of the transesterification effect of above-mentioned vegetables oil and animal oil.
Do not wish to be retrained by any theory, the catalytic cracking that we find triglyceride level is stepwise process seemingly, wherein in the first step, has formed fatty acid molecule and glycerol backbone.This fatty acid molecule cracking is lighter component then.We find that it almost is moment that triglyceride level is converted into lipid acid in the presence of cracking catalyst, and in next step, for example catalyzer and the ratio of oil, type, temperature and the residence time of catalyzer are depended in the conversion of lipid acid.
Usually, we wish that the oxygen that exists in the triglyceride level is converted into CO in the catalytic cracking step 2But we find that most oxygen is converted into water as by product.This water is as stripping gas, and separates with useful product in the stripping step of this fluidized catalytic cracking method.
The example of the paraffinic feed that is fit to is Fisher-Tropsch derived hydrocarbon stream or wax oil.
Wax oil is the tower bottom distillate of hydroeracking unit.Hydroeracking unit in the context of the present invention is meant wherein the normally hydrocracking process of petroleum naphtha, kerosene and gas oil of primary product.Be higher than 370 ℃ cut with the raw material mid-boiling point that enters hydroeracking unit and be lower than 370 ℃ the transformation efficiency of weight percent meter of hydrocarbon with respect to boiling point usually above 50wt%.The example that can produce the hydrocracking process of the tower bottom distillate that can be used for the inventive method has been described in EP-A-699225, EP-A-649896, WO-A-97/18278, EP-A-705321, EP-A-994173 and US-A-4851109.
" Fisher-Tropsch derived hydrocarbon stream " is meant that this hydrocarbon stream is to obtain by hydrotreating step (being hydrocracking, hydroisomerization and/or hydrogenation) from the product of fischer-tropsch hydrocarbon synthesis process or by this product.
Fischer-Tropsch reaction is at the catalyzer that is fit to usually under high temperature (for example 125-300 ℃, preferred 175-250 ℃) and high pressure (for example 5-100 crust, preferably 12-80 clings to), and carbon monoxide and hydrogen are converted into long chain hydrocarbon (being generally paraffinic hydrocarbons):
N (CO+2H 2)=(-CH 2-) n+ nH 2The O+ heat,
If desired, can use the hydrogen that is not 2:1: the ratio of carbon monoxide.
Carbon monoxide and hydrogen are usually from the partial oxidation of hydrocarbonaceous raw material.The hydrocarbonaceous raw material that is fit to comprises hydrocarbon gas, for example the residual fraction of Sweet natural gas or methane, coal, biomass or crude distillation.
This Fisher-Tropsch derived hydrocarbon stream can suitably be the so-called synthetic crude described in GB-A-2386607, GB-A-2371807 or the EP-A-0321305 for example.Other fischer-tropsch hydrocarbon stream that is fit to can be the hydrocarbon-fraction of boiling point in petroleum naphtha, kerosene, gas oil or wax scope that is obtained by the fischer-tropsch hydrocarbon synthesis process that carries out hydrotreating step after optional.
Preferably, this fischer-tropsch hydrocarbon stream product is to be obtained by the hydrocarbon hydroisomerization that directly obtains in the fischer-tropsch hydrocarbon synthesis reaction.It is favourable using the hydrocarbon-fraction of hydroisomerization, because make it help to obtain the gasoline of high yield owing to have high-load isoparaffin in described cut.Can compatibly use the hydro-isomerised fraction of boiling point in kerosene or gas oil range as Fisher-Tropsch derived hydrocarbon stream.But preferably, use more high boiling hydro-isomerised fraction as raw material.
Particularly suitable hydroisomerization hydrocarbon-fraction is that the T10wt% boiling point is that 350-450 ℃, T90wt% boiling point are that 450-600 ℃ and wax content are the cut of 5-60wt%.The so-called waxy raffinate of this cut.Preferably, wax content is 5-30wt%.This wax content is to measure by carrying out solvent dewaxing at-27 ℃ in the methyl ethyl ketone of 50/50 volume ratio and toluene mixture.The example of this hydrocarbon stream is the waxy raffinate product of selling at commercial available Shell MDS (Malaysia) Sdn Bhdsnf, and this waxy raffinate product obtains by the method described in WO-A-02/070630 or the EP-B-0668342.
This paraffinic feed preferably comprises the paraffinic hydrocarbons of 50wt%, more preferably the paraffinic hydrocarbons of 70wt% at least.This paraffinic hydrocarbons is make a comment or criticism structure and isomerization alkanes.The paraffinicity of paraffinic feed is to measure by the comprehensive multidimensional gas chromatographic (GCxGC) described in the following document in the context of the present invention: P.J.Schoenmakers, J.L.M.M.Oomen, J.Blomberg, W.Genuit, G.van Velzen, J.Chromatogr.A, p.29 892 (2000) reach other.
Hydrocarbon feed of the present invention comprises paraffinic feed and triglyceride level.Preferably, the weight ratio between the amount of the paraffinic feed that exists in described hydrocarbon feed and the amount of triglyceride level is 20:1 to 1:5, preferred 5:1 to 1:2.
Described hydrocarbon feed can also randomly comprise the component that is not triglyceride level or paraffinic feed.The component that is fit to is so-called conventional FCC raw material, and it is derived from crude oil refining usually, and its paraffinicity than above-mentioned paraffinic feed is lower.The conventional FCC raw material that can be used for the inventive method comprises the non-irreducible oil cut of high boiling point, for example vacuum gas oil, straight run (normal pressure) gas oil, coker gas oil and the normal pressure of crude oil or the Residual oil of vacuum distilling.The boiling point of these raw materials preferably 220 ℃-650 ℃, more preferably in 300 ℃ of-600 ℃ of scopes.
This routine FCC raw material can change according to available raw material and desired product quality with respect to the amount of paraffinic feed and triglyceride level.In the methods of the invention, described hydrocarbon feed can comprise the conventional FCC raw material of 90wt% at the most, the preferred conventional FCC raw material of 70wt% at the most, the more preferably conventional FCC raw material of 50wt% at the most, even the more preferably conventional FCC raw material of 40wt% at the most.The advantage of handling the mixture of conventional FCC raw material, paraffinic feed and triglyceride level for example is the gasoline that produces the aromaticity content with reduction.Another advantage is that the light alkene yield improves when adding triglyceride level and paraffinic feed in the conventional FCC raw material of heavy.When comprising the conventional FCC raw material of lower aq in raw material, advantage of the present invention becomes more obvious.
Therefore, by selecting the proper equilibrium between the paraffinic feed and triglyceride level and conventional on the other hand FCC raw material on the one hand, can obtain having for example acceptable octane value of required character, the gasoline product of low sulphur content and required aromaticity content.The character of this crackate can be regulated.
In the methods of the invention, cracking catalyst comprises large pore zeolite.For large pore zeolite, be meant the zeolite that comprises porous crystalline aluminosilicate structure, this aluminosilicate structure have porous internal crystal framework structure and at the main shaft in hole on this crystalline network in the 0.62-0.8 nanometer range.At " Atlas of Zeolite Structure Types ", W.M.Meier, D.H.Olson and Ch.Baerlocher, Fourth Revised Edition 1996, Elsevier has described the axle of zeolite among the ISBN0-444-10015-6.The example of this large pore zeolite is FAU or faujusite, preferred synthetic faujasites, for example zeolite Y, USY, Rare Earth Y (=REY) or rare earth USY (REUSY).According to the present invention, preferably use USY as this large pore zeolite.
High if desired propene yield, this cracking catalyst preferably further comprise mesopore zeolite.Can be used for mesopore zeolite of the present invention and be interpreted as the zeolite that comprises porous crystalline aluminosilicate structure, this aluminosilicate structure have porous internal crystal framework structure and at the main shaft in hole on this crystalline network in the 0.45-0.62 nanometer range.The example of this mesopore zeolite has MFI structure type, for example ZSM-5; MTW type, for example ZSM-12; The TON structure type, for example θ 1; With FER structure type, for example ferrierite.According to the present invention, preferably use ZSM-5 as this mesopore zeolite.
In cracking catalyst, the weight ratio of large pore zeolite and mesopore zeolite is preferably in 99:1 to 70:30 scope, more preferably in 98:2 to 85:15 scope.
The large pore zeolite that in cracking catalyst, exists and/or the total amount of mesopore zeolite with respect to the catalyzer total mass preferably in the 5-40wt% scope, more preferably in the 10-30wt% scope, even more preferably in the 10-25wt% scope.
Except this macropore or mesopore zeolite, this catalyzer can comprise one or more porous inorganic refractory metal oxide binder materials or carrier and/or active matrix materials.These binder materials or carrier can be contributed or not contribution to some extent to this cracking reaction.The example of this binder material is silicon-dioxide, aluminum oxide, titanium oxide, zirconium white and magnesium oxide or two or more combination in them.Also can use organic binder bond.
The temperature that contacts of hydrocarbon feed and cracking catalyst is preferably 450-650 ℃.More preferably, this temperature is higher than 475 ℃, even more preferably is higher than 500 ℃.Discovery is being higher than the yield of gasoline that obtains under 600 ℃ the temperature.But the temperature that is higher than 600 ℃ also can produce heat cracking reaction and form unwanted gaseous product, for example methane and ethane.This temperature preferably is lower than 600 ℃ for this reason.
This method can be carried out in various types of reactors.For simplifying the regeneration of catalyzer, preferred fast fluidized bed reactor or riser reactor.If this method is carried out in riser reactor, be 1-10 second preferred duration of contact, more preferably 2-7 second.Catalyzer is preferably 2-20kg/kg with the ratio of oil (hydrocarbon feed).Have been found that the result that can access when ratio at catalyzer and oil is greater than 6kg/kg, this is because the ratio of higher catalyzer and oil can cause forming the coke of high level on catalyzer.
Embodiment
The present invention is further described by the following examples.The most important character of wax oil is shown in Table 1.
Table 1
Feedstock property Wax oil
Density (D70/4) 0.807
Nitrogen concentration (ppmw) 2
Viscosity (100 ℃) (cSt) 6.73
Sulphur (wt%) 0.5
Total aromatic substance (wt%) 6.07
Carbon (wt%) 85.7
Hydrogen (wt%) 14.3
Initial boiling point (℃) 196
Full boiling point (℃) 608
Embodiment 1
Be to carry out the catalytic cracking experiment in little riser reactor of operation of isothermal plug-flow area.This little riser reactor is once-through laboratory scale fluid catalytic cracking reactor, and it simulates the hydrokinetics of industrial FCC reactor.Temperature of reactor is set at 525 ℃.The length of reactor is 21.2 meters in these experiments.Used catalyzer is a commercial silica sol based FCC equilibrium catalyst (e-cat), comprises the USY zeolite crystal of 11wt%.Before each experiment, regenerated catalyst in fluidized-bed reactor, therein under 600 ℃ in air combustion of coke 3 hours.By catalyst charge device charging catalyzer in reactor.Use nitrogen so that catalyzer flows.Oily raw material is imported in the preheating oven, therein with its partial gasification by the no pulse syringe pump.Final section before injection point is gasified totally oil and adopts this temperature of reaction and catalyzer.In the vertical injecting catalyst stream of raw material.This raw material is by pure wax oil or be mixed with 20wt% or the wax oil of the rapeseed oil that slightly comes unstuck of 40wt% constitutes.
When reaching steady state operation, this system begins to collect sample.By cyclonic separator separating catalyst and gaseous product.In this steady state operation process, storage catalyst under reaction conditions is used the nitrogen stripping then.Eluting gas is guided three placed in-line condensers operating by respectively continuously under 25 ,-60 and-60 ℃.Any uncooled product all is captured in the airbag.Use the C in the gas Chromatographic Determination airbag 1-C 4The hydrocarbon component.Detect the C that carries secretly as two different sets by this analytical procedure 5And C 6Hydrocarbon, and it is added in the gasoline fraction.With simulation distil analyzing liquid product.Provided amount like this: gasoline (C based on the product of following boiling spread set 5-215 ℃), light cycle oil (LCO, 215-325 ℃) and heavy cycle oil and slurry oil (HCO+SO, 325+ ℃).With the coke on the LECO C-400 carbon analyzer mensuration catalyzer.The results are shown in the table 2.
Compare with 100% wax oil, add rapeseed oil (RSO) and cause the amount of coke and LCO to increase.In addition, compare,, observe the RON calculated value and obviously improve for the wax oil of catalytic cracking and the mixture of 40wt% rapeseed oil with 100% wax oil.
Table 2
Experiment 100％HWX HWX+20wt％RSO HWX+40wt％RSO
CTO (g catalyzer/g oil) 3.8 4.5 4.6
Duration of contact (s) 4.4 4.4 4.5
Yield (wt%)
Coke 2.0 2.1 3.3
Gas 11.7 9.2 7.9
Gasoline (C 5-215℃) 60.2 59.4 55.7
LCO(215-325℃) 15.7 18.1 20.7
HCO+SO(325+) 11 12
RON 85.7 89.2
Embodiment 2
In the small-sized fluidized bed reactor, use equilibrium catalyst e-cat2 to carry out the catalytic cracking of the mixture of wax oil and rapeseed oil and plam oil (5,10,25wt%).Therein with nitrogen to experimentizing in the constant fluidizing reactor of the commercial e-catalyzer of 10g.According to the ratio of catalyst/oil, the oil of 1.25-3.33 gram amount is injected this reactor.In stripping process, product liquid is collected in temperature in the Glass Containers (receptor) in-15 ℃ the bath.Gas with gas-chromatography on-line analysis preparation.After stripping 660 seconds, by in regeneration step from the catalyzer combustion of coke measure the amount of the coke that catalyzer forms.In 40 minutes processes, the temperature of reactor is 650 ℃ in air ambient.Coke is converted into CO 2, and on-line determination.After regeneration, reactor cooling is arrived temperature of reaction and begins new injection.The results are shown in table 3 and 4.
Table 3. uses the products distribution of e-cat2 mixture of wax oil (HWX) and wax oil and rapeseed oil (RSO) when 500 ℃ (ratio of catalyst/oil is 6.3)
100％HWX HWX+5％RSO HWX+10％RSO HWX+25％RSO
CTO (g catalyzer/g oil) 6.3 6.3 6.3 6.3
Transformation efficiency 87.1 87.9 86.5 82.4
CO 0.0 0.0 0.0 0.1
CO 2 0.0 0.1 0.1 0.2
H 2O Inapplicable 0.6 1.2 2.8
Coke 2.0 2.2 2.5 3.1
Dry gas 1.0 1.0 1.1 1.2
LPG 24.2 25.2 24.7 21.6
Gasoline (C 5-215℃) 59.9 59.5 58.2 56.5
LCO(215-325℃) 7.3 7.3 8.0 10.0
HCO+SO(325+) 5.6 4.2 4.2 4.5
GC-RON 86.3 86.7 87.3 87.7
GC-MON 77.4 77.8 78.4 78.5
Table 4. uses the products distribution of e-cat2 wax oil (HWX) and wax oil and palmitic mixture when 500 ℃ (ratio of catalyst/oil is 6)
The HWX+5% plam oil The HWX+10% plam oil The HWX+25% plam oil
CTO (g catalyzer/g oil) 5.8 5.7 5.5
Transformation efficiency 88.2 89.9 83.7
CO 0.1 0.1 0.3
CO 2 0.1 0.1 0.3
H 2O 0.6 1.1 2.7
Coke 1.8 2.0 2.4
Dry gas 0.9 1.0 1.0
LPG 23.6 23.4 21.3
Gasoline (C 5-215℃) 61.8 63.5 58.9
LCO(215-325℃) 7.5 6.3 8.4
HCO+SO(325+) 3.7 2.5 4.6
GC-RON 88.0 87.8 88.3
GC-MON 79.4 79.4 79.7

Claims (11)

  1. By in reactor with the fluidized catalytic cracking method of hydrocarbon feed and cracking catalyst contact preparation crackate, wherein said hydrocarbon feed comprises paraffinic feed and triglyceride level.
  2. 2. the method for claim 2, wherein said paraffinic feed comprises the paraffinic hydrocarbons of 50wt% at least, the preferred paraffinic hydrocarbons of 70wt% at least.
  3. 3. claim 1 or 2 method, wherein the weight ratio scope of paraffinic feed that exists in described hydrocarbon feed and triglyceride level is 20:1 to 1:5, more preferably 5:1 to 1:2.
  4. 4. each method of claim 1-3, wherein said hydrocarbon feed comprises the conventional FCC raw material of 90wt% at the most, more preferably 70wt% at the most.
  5. 5. each method of claim 1-4, wherein said hydrocarbon feed comprises vegetables oil, preferred plam oil or rapeseed oil.
  6. 6. each method of claim 1-5, wherein said paraffinic feed is a wax oil.
  7. 7. each method of claim 1-5, wherein said paraffinic feed is Fisher-Tropsch derived hydrocarbon stream.
  8. 8. each method of claim 1-7, wherein said cracking catalyst comprises large pore zeolite.
  9. 9. the method for claim 8, wherein said large pore zeolite is USY.
  10. 10. each method of claim 1-9, wherein said cracking catalyst further comprises mesopore zeolite.
  11. 11. the method for claim 10, wherein said mesopore zeolite is ZSM-5.
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