CN102215958A - Catalytic cracking for enhanced propylene yield and reduced benzene naphtha fractions - Google Patents
Catalytic cracking for enhanced propylene yield and reduced benzene naphtha fractions Download PDFInfo
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- CN102215958A CN102215958A CN2009801453330A CN200980145333A CN102215958A CN 102215958 A CN102215958 A CN 102215958A CN 2009801453330 A CN2009801453330 A CN 2009801453330A CN 200980145333 A CN200980145333 A CN 200980145333A CN 102215958 A CN102215958 A CN 102215958A
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- Prior art keywords
- benzene
- catalyst
- naphtha
- cut
- weight
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Classifications
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- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
- C07C4/18—Catalytic processes
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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
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
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- 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
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- C10G2300/20—Characteristics of the feedstock or the products
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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
- C10G2300/80—Additives
- C10G2300/805—Water
- C10G2300/807—Steam
-
- 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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- 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
- C10G2400/20—C2-C4 olefins
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A process in which a catalytic cracking unit is operated to crack a hydrocarbon feedstock in a manner to enhance light olefin yields. The accompanying benzene-containing naphtha product stream is further processed through a benzene selective membrane to provide a low content benzene stream Refiners frequently operate their cracking units to optimize light olefin yields, e g, propylene, in response to needs in the petrochemical industry, and it has been discovered that units operated in this manner frequently produce naphtha containing increased amounts of benzene. The method of this invention therefore allows one to operate the unit when it is desired to optimize light olefin yields, yet at the same time produce a naphtha yield having a low benzene content. The invention is particularly useful when the cracking unit utilizes pentasil zeolites at increased concentrations to enhance light olefins yield.
Description
Background of invention
The present invention relates to be intended to produce the catalyst cracking method of light olefin.The invention further relates to the method for benzene in the naphtha cut that reduction in this way produces.
Benzene is a kind of known carcinogenic substance, and it appears in the gasoline production.Benzene in European Union, the U.S. and other the regional laws and regulations requirement gasoline is lower than 1%.At oil plant, produce gasoline by concocting each component materials flow, described component materials flow comprises butane, isopentane, alkylates, isomers, straight-run naphtha, isocrackate, catalytic naphtha, steam cracking naphtha, coking naphtha, drippolene, catalytic reformate, vacuum gas oil (VGO) and oxide (oxygenate).The naphtha that is formed by catalytic cracking such as fluid catalytic cracking (FCC) can further be fractionated into light catalytic naphtha, middle catalytic naphtha and heavy catalytic naphtha.
Product distribution from current FCC technology also comprises many components except the gasoline naphtha.Yet for most of refiners, gasoline is its main interest, and light olefin and LPG also find in the FCC product, and becomes refiner's interest day by day, and is more valuable because those products become.The light olefin that produces can be used for many purposes, upgrades to high-quality alkylates as them by sulphur or HF alkylation.LPG is used for the cooking and/or heating purposes.Therefore, the operator of FCC apparatus can change the content of its product, this depend on market that they serve with the FCC product in the relevant value of every kind of component found.
Propylene is a kind of light olefin of special, high demand.It is used for the synthetic material and the thermoplastic of many in the world maximums and the fastest growth.The FCC apparatus that the refiner more and more depends on them to be satisfying the propylene growth of requirement the profit maximization because the operator seeks chance, therefore, with the focus of traditional F CC device from the transport fuel call away to and more shift to petrochemical material production.In fact, FCC apparatus provides 1/3rd propylene in the world, and when the propylene price was high, it was valuable increasing propone output from this device.
If oil plant can not enlarge its existing FCC apparatus, Zhuan Zhi operator has quite limited selection and is used to increase light olefin output so.The selection of report comprises:
(a) in FCC apparatus, use additive ZSM-5 catalyst and/or additive; With
(b) harshness such as the temperature of condition in the increase device are for example produced cracked gas by gas oil under pentasil zeolite such as ZSM-5 effect.
Yet people notice that the product that many methods such as above-mentioned method are produced usually has with device operation under the condition of maximization yield of gasoline compares higher benzene concentration when being fractionated into the materials flow of gasoline naphtha.May contain benzene from the naphtha cut of the FCC apparatus of operating in the mode that improves yield of light olefin more than 2%.The refiner is not easy to discern the source of the benzene of increase.
Therefore, be unwilling to rely on FCC apparatus to satisfy the alkene demand basically, the pentasil catalyst for additives is used in the maximization of perhaps being unwilling.Consider that when the refiner uses the pentasil additive with the raising olefin yields usually can sacrifice the yield of gasoline, this is unwilling further to strengthen.In other words, except this method requires to handle product with the benzene of removing recruitment, the other problem that the refiner faces is that the yield of valuable product reduces.
Reported that polymeric membrane separated aromatic hydrocarbon.
United States Patent (USP) 2,930,754 (Stuckey), United States Patent (USP) 2,958,656 (Stuckey), United States Patent (USP) 3,370,102 (people such as Carpenter), United States Patent (USP) 4,115,465 (people such as Elfert), United States Patent (USP) 4,944,880 (people such as Ho), United States Patent (USP) 5,028,685 (people such as Ho), United States Patent (USP) 5,063,186 (Schucker) and United States Patent (USP) 5,635,055 people such as () Sweet relate to the film that is used to separate aromatic hydrocarbon/non-aromatic hydrocarbon, but nobody discusses remove benzene from hydrocarbon flow.
United States Patent (USP) 6,180,008 (White) and United States Patent (USP) 6,187,987 people such as () Chin are mentioned polyimide film and are used ultrafiltration to reclaim the method for aromatic solvent.Yet do not discuss and from hydrocarbon flow, remove benzene.
US5,914,435 (Streicher and Prevost) have described a kind of method, wherein will handle to reduce the content of benzene in the processed hydrocarbon flow with the film infiltration area from the side run-off that is rich in benzene of destilling tower.Benzene is had selectivity to this film and the low retentate (retentate) of near small part benzene content is divided into two bursts of materials flows and is circulated to two varying levels of this destilling tower.It is believed that destilling tower is to be designed to separation of C
5-C
10The naphtha prefractionator of hydrocarbon, its mid-boiling point are that those hydrocarbon of 150-200 ℃ are collected in the bottom of tower and boiling point is that about 50 ℃ hydrocarbon is collected at the top of tower.
Title is " Reduce Your Tier 2Gasoline Compliance Costs with GraceDavison S-Brane
TMTechnology " and described by using S-by the publication that J.Balko proposes in Spring 2002NPRA meeting (AM-02-21)
Film reduces the sulfur content in the gasoline.Also referring to United States Patent (USP) 6,896,796 (White, Wormsbecher and Lesemann).Balko mentions delay aromatic hydrocarbon concentration (particularly benzene) usually and reduces by the method for using the S-Brane film basically, but does not mention about the gasoline stream that relates to alkene production and so doing, and the main purpose of use S-Brane film is to reduce sulphur.In fact, Balko does not provide the support data of removing about benzene.
Following list of references has also been described the use film and removed sulphur from the hydrocarbon charging.' 761, these lists of references are not mentioned removal benzene except Balko's.United States Patent (USP) 6,649,061 (people such as Minhas), US7,048,846 (people such as White) and US7,267,761 (Balko).
Jonqueres, R.Cl é ment, P.Lochon, J.N é el, M.Dresch and B.Chr é tien; " Industrial state-of-the-art of pervaporation and vapour permeation in the western countries ",
J.Membrane Sci.206 (2002) 87-117 have stated " petrochemical industry is considering that now the good alternative approach of these new separation methods conducts is to accept challenge of removing the global range of aromatic hydrocarbon from gasoline on the horizon; it remains one of at present great problem of public health ", but do not provide extra reference or information.Also referring to A.Jonquieres, R.Cl é ment and P.Lochon, " Permeability of block copolymers to vapors and liquids ",
Prog.Polym.Sci.27 (2002) 1803-1877.
United States Patent (USP) 6,232,518 (Ou) relate to the use cyclodextrin and remove benzene from hydrocarbon flows.
J.Garci Villaluenga and A.Tabe-Mohammadi, " A review of the separation of benzene/cyclohexane mixtures by pervaporation processes "; J.Membrane Sci.169 (2000) 159-174 has summarized the prior art that reclaims benzene.Yet, do not discuss and remove benzene to low concentration.
New legislation requires the concentration of benzene in the gasoline low.Because FCC apparatus is produced gasoline blending component, keeping benzene concentration low is vital for the refiner.Therefore, wish to have a kind of method that propone output is reduced in the benzene concentration in the FCC gasoline of producing in this production process simultaneously that allows to increase.Prove also there is not openly or advises the actual solution of this difficult problem by top discussion.
Brief Description Of Drawings
Fig. 1 wherein handles light catalytic naphtha to reduce the schematic diagram of one embodiment of the invention of the amount of benzene in this materials flow with film for showing.
Fig. 2 is for setting forth the curve map that reduces the performance of the present invention of benzene concentration with film M1 that describes among the embodiment 3 and M2.
Brief summary of the invention
We find, thereby film method can be used to be devoted to when the condition of using pentasil zeolite catalyst or other known raising yield of light olefin with the raw material cracking during as light olefin such as propylene unfavorable benzene accumulation problem be convenient to improve process conditions from the yield of light olefin of FCC apparatus, a kind of naphtha materials flow that can mix the more environmental protection in the gasoline pool is provided simultaneously.This paper light olefin is meant ethene, propylene and butylene, promptly contains 2-4 carbon atom (C
2-C
4) alkene.
The present invention includes hydrocarbon feed is introduced in the reaction zone of catalytic cracking unit, this raw material is characterised in that to have about 120 ℃ initial boiling point and up to about 850 ℃ final boiling point.By raw material contact and cracking with Cracking catalyst under the condition of temperature, catalyst/oil ratio, pressure, steam dilution and air speed, operate the yield of light olefin of comparing from this device in condition more commonly used under as those conditions of hereinafter listing and improved by feasible and same apparatus in the reaction zone of device for raw material.。
Thereby the product that this device is produced comprises light olefin, naphtha and benzene, and wherein this product comprises based on the propylene of the hydrocarbon feed weight in the above-mentioned cracking step of introducing for about 6%-about 20%.This product is fractionated into cut that contains light olefin and the naphtha cut that contains benzene then at least.This materials flow can comprise gamut catalytic naphtha (benzene of 220 ℃ of 50 ℃ of boiling points-Yue and the about 3 weight % of 0.6 weight %-) or light catalytic naphtha (benzene of 105 ℃ of 50 ℃ of boiling points-Yue and the about 6 weight % of 1.2 weight %-).
Recovery contains the cut of light olefin, and the naphtha cut that contains benzene is contacted with film.The film of selecting to use has selectivity to benzene, therefore should have enough flux and selectivity to separate rich benzene penetrant cut (permeate fraction) and poor benzene naphtha retentate cut from naphtha, described rich benzene penetrant cut is compared with retentate and is rich in benzene.Reclaim poor benzene naphtha retentate cut then and rich benzene penetrant cut is sent to further processing.
When operating such method, when the type of the condition of selecting device such as catalyst and composition, temperature, catalyst/oil ratio, pressure, steam dilution and/or air speed when improving the yield of light olefin in the catalytic cracking unit, can use the method for the naphtha that production light olefin and benzene content are low in catalytic cracking unit.
Can remove benzene in this way, the permission refiner maximizes the yield of light olefin in the materials flow of FCC product.When this device used the pentasil zeolite to produce alkene, the weight that materials flow can contain based on raw material in the FCC apparatus was the propylene of the about 20 weight % of 6 weight %-.
Therefore, the aromatic hydrocarbon selective film is preferentially removed benzene from gasoline stocks, provides simultaneously from the light olefin of the raising of FCC apparatus such as the yield of propylene, still produces a large amount of benzene concentrations simultaneously and is lower than 1%, preferably is lower than 0.6% gasoline fraction.With the pervaporation of aromatic hydrocarbon selective film is the method for optimizing of removing benzene.
Can adjust catalyst in the FCC apparatus and process conditions in addition to improve C from the light oil stripper
3And C
4The yield of light olefin is extremely greater than 20 weight %.Even this method makes naphtha cut may contain benzene more than 1%, film step of the present invention is split as main fractions with gasoline fraction, has the retentate that is lower than 1% benzene, and minor fraction, contains the penetrant greater than 1% benzene.Main retentate cut can directly use in gasoline pool, simultaneously less important penetrant cut is sent to further processing in the oil plant.
Detailed Description Of The Invention
Catalytic cracking process
The preferred FCC technology of catalytic cracking process of the present invention.The catalyst that uses in the FCC technology is particle form, has the particle mean size of 20-200 micron usually, and circulates between cracker and catalyst regenerator.In reactor, hydrocarbon charging contact catalyst heat, regeneration, its evaporation and cracked charge.FCC apparatus can be operated under a series of conditions, and wherein reaction temperature is about 400-700 ℃, and regeneration is carried out under about 500-900 ℃ temperature.The condition that the product materials flow that actual conditions depends on pending petroleum, want and other refiners know.For example, lighter raw material cracking at a lower temperature.Catalyst (being reserve) is circulation between catalytic cracking reaction and regeneration in a continuous manner in device, keeps the catalyst balance in the reactor simultaneously.The present invention can use in FCC apparatus under conventional cracking conditions.Below representative condition in FCC apparatus is listed in.
Some embodiment of the present invention can use a little more exacting terms.These harsher technologies comprise those that are called DCC (DCC), Deep Catalytic Cracking process (CPP) and ultracat cracking (UCC).The exemplary condition of harsher technology is listed in the following table.
Those skilled in the art are familiar with when such technology and can use with the present invention.When the present invention uses such technology, in order to optimize the validity of carbon monoxide-olefin polymeric in those technologies, may need the present invention is carried out some adjustment, may need to change catalyst as active and abrasion.Such adjustment is known to those skilled in the art.For example, when pentasil zeolite that uses recruitment such as ZSM5, operation is to improve yield of light olefin under the conventional FCC condition that FCC apparatus can be listed in last table the first row.
The hydrocarbon or the coke of cracking reaction deposited carbon-containing on catalyst, thus make catalysqt deactivation.Catalyst separation crackate from close-burning.The catalyst of close-burning is gone out volatile matter with the steam elution usually in catalyst elution device, then regeneration.The catalyst regenerator oxygen-containing gas, normally air burning to recover catalyst activity and heatable catalyst to as 500-900 ℃, is generally 600-750 ℃ from the coke of catalyst.This hot regenerated catalyst is circulated in the cracker with the more raw feed of cracking.Can handle from the flue gas of regenerator to remove particle or to transform CO, be disposed in the atmosphere then.Fluid Catalytic Cracking Report, Amos.A.Avidan, Michael Edwards and Hartley Owen are at Oil ﹠amp; In the version in the January 8 nineteen ninety of Gas Journal FCC technology and its development have been described.
Various hydrocarbon feeds can be in FCC apparatus cracking to produce light olefin and gasoline.It is typical that raw material is all or part of comprises initial boiling point more than about 120 ℃ [250 °F], mid-boiling point at least about 315 ℃ [600] and final boiling point up to the gas oil of about 850 ℃ [1562] (light, in or heavy gas oil).Raw material also can comprise deep drawing gas oil, vacuum gas oil (VGO), coker gas oil, deep fat, residual oil, recycle oil, all tops crude oil, tar sand oils, shale oil, synthetic fuel, heavy hydrocarbon fraction, tar, pitch, pitch derived from the destruction hydrogenation of coal, derived from the hydrotreated feed of any above-mentioned raw materials etc.Be familiar with as meeting, must under vacuum, be carried out to avoid thermal cracking in the distillation of about higher petroleum distillate more than 400 ℃.Express for convenience, boiling temperature used herein is the boiling point that is accurate to atmospheric pressure.Even final boiling point also may cracking up to the residual oil of about 850 ℃ more deep drawing gas oil or high tenor.
Y-type zeolite is generally used in the FCC technology to produce gasoline.These zeolites comprise y-type zeolite (United States Patent (USP) 3,130,007); Ultrastable (USY) (United States Patent (USP) 3,449,070), the USY (REUSY) of the y-type zeolite (REY) (United States Patent (USP) 4,415,438) of rare earth exchanged, rare earth exchanged, dealuminium Y type beta stone (DeAlY) (United States Patent (USP) 3,442,792, United States Patent (USP) 4,331, and 694) and super-hydrophobic Y type zeolite (UHPY) (United States Patent (USP) 4,401,556).These zeolites are the large pore molecular sieve of aperture greater than about 7 dusts.In present business practice, most of Cracking catalyst contains these zeolites.
Also can use the zeolite of metal cation exchange, as MgUSY, ZnUSY and MnUSY zeolite, its exchange solution that contains the slaine of Mg, Zn or Mn or its mixture by use forms in the mode identical with forming REUSY, except the salt that uses magnesium, zinc or manganese replaces forming the used rare earth metal salt of REUSY.The content of these catalyst and preparation are known in the art.
The amount that is used for carbon monoxide-olefin polymeric y-type zeolite of the present invention should enough be produced the molecule of naphtha range in the gasoline.Generally speaking, y-type zeolite exists with the amount of the 1-99 weight % of catalyst.The catalyst that comprises the about 60 weight %Y type zeolites of about 12 weight %-more commonly used, concrete amount depends on the amount of required activity.The amount of y-type zeolite make usually the total amount of y-type zeolite and pentasil described below account for total catalyst composition weight at least about 35%.
As mentioned above, adding the pentasil zeolite in the catalysis reserve is to operate FCC apparatus according to the present invention to improve a kind of method of yield of light olefin.These catalyst are well-known and are commonly referred to as catalyst for additives.Being suitable for pentasil zeolite of the present invention, to comprise that those have pentacyclic zeolite structured.In preferred embodiments, carbon monoxide-olefin polymeric of the present invention comprises one or more pentasil, and it has the X-ray diffractogram of ZSM-5 or ZSM-11.Suitable pentasil is included in US5, those that describe in 380,690, and its content is incorporated this paper by reference into.It is commercially available that synthetic to select the shape zeolite also suitable.
Preferred pentasil zeolite generally has the restricted index of 1-12.At J.Catalysis, 67, the details that provide restricted index to test in 218-222 (1981) and the United States Patent (USP) 4,711,710, both all incorporate this paper by reference into.This pentasil illustrates with the interstitial hole zeolite, and for example those apertures are the zeolite of about 7 dusts of about 4-.Preferred ZSM-5 (United States Patent (USP) 3,702,886 and Re.29,948) and ZSM-11 (United States Patent (USP) 3,709,979).The preparation method of these synthetic pentasil is well-known in the art.The preferred embodiment of pentasil has low relatively silicon/aluminum ratio, for example less than 100: 1, preferably less than 50: 1.The preferred embodiments of the invention have the silicon/aluminum ratio less than 30: 1.Pentasil also can exchange with metal cation.Suitable metal comprises the metal dopant that those are described in US2004/011029, its content is incorporated this paper by reference into.Briefly, these metals can be alkaline-earth metal, transition metal, rare earth metal, phosphorus, boron, noble metal and combination thereof.The catalyst that comprises ZSM-5pentasil is by W.R.Grace; Co.-Conn. commercially available and with Olefins
Olefins
And Olefins
The trade mark catalyst is sold.Olefins
The HZ additive is particularly suitable among the present invention.
It is known with the yield that improves light olefin that these catalyst for additives and macropore y-type zeolite catalyst are united use, and can be used for the present invention according to technology known in the art and condition.For example, the refiner can in their FCC apparatus, add contain pentasil catalyst as catalyst for additives, 10-80 weight % wherein, 12-35 weight % usually, more generally the pentasil zeolite of 25-50 weight % is in amorphous carrier.In this example, pentasil adds as particle, itself and the particle separation that contains traditional macro-porous zeolite catalyst.Prepare these additives and make it to have the physical property that allows them between reaction zone and renewing zone, to circulate with the large pore zeolite Cracking catalyst.In the additive that separates, use pentasil to allow the refiner to keep the ability of the commercially available large pore zeolite Cracking catalyst of using present obtainable numerous types, and allow the refiner between centralized production gasoline and production light olefin, to change.
No matter the content of pentasil zeolite in the additive granules, in the whole catalyst inventory amount of pentasil zeolite crystal with when not having or only existing this catalyst of low concentration (as 1 weight % or still less), compare the olefin yields that be enough to improve FCC apparatus, as improving octane." pentasil zeolite crystal " meaning is meant the crystallization pentasil zeolite of pure form.Selected pentasil zeolite crystal, preferred ZSM-5, content be preferably the about 20 weight % of 2 weight %-of catalyst system therefor of the present invention.The amount of pentasil crystal can use x x ray diffraction technology well known by persons skilled in the art to be calculated by the catalyst granules that contains carrier and/or matrix.
In order to obtain the crystal amount of above-mentioned scope, the catalyst granules of the preferred high pentasil zeolite content of the present invention.Use the high-load particle should avoid diluting the gasoline cracking activity of y-type zeolite.The catalyst of this high pentasil zeolite content is known and at United States Patent (USP) 6,916, describes in 757, and its content is incorporated this paper by reference into.
These catalyst additives can use under the condition in FCC apparatus widely, and yield of light olefin depends on used condition.The harshness of temperature, i.e. higher temperature is used in combination pentasil zeolite such as ZSM5 and can causes the yield of light olefin that improves usually, but means also that usually yield of gasoline reduces, and follows benzene content to increase.
Be used for FCC apparatus and describe in WO 2006/050487 and US 2008/0093263 from the specially suitable pentasil zeolite catalyst of the olefin yields of FCC apparatus with raising, its content is incorporated this paper by reference into.Briefly, this catalyst makes it to contain the pentasil zeolite of 10%-about 50% of having an appointment with y-type zeolite preparation, and the ratio of pentasil zeolite and y-type zeolite is at least 0.25.For this catalyst, the pentasil zeolite generally should be not more than about 3.0 with the ratio of y-type zeolite.Typical embodiments of the present invention comprises the about 30 weight % of about 10 weight %-, more generally the pentasil zeolite of the about 20 weight % of 10 weight %-.The amount of pentasil zeolite is generally and makes that the amount of above-mentioned pentasil zeolite and y-type zeolite is at least 35 weight % of total catalyst composition in this catalyst.
The another kind of suitable pentasil zeolite catalyst that is used for the present invention is to contain based on the pentasil zeolite catalyst of the weight that contains the pentasil zeolite granular at least 1 weight % ferriferous oxide.Described this catalyst in WO 2007/005075, its content is incorporated this paper by reference into.The pentasil zeolite of these oxides-containing irons generally comprises the ferriferous oxide of 1-10 weight %, and the iron of this quantity is positioned at outside the skeleton of pentasil skeleton, for example iron is present in the matrix of pentasil particle, be present in pentasil sial skeleton in relative.WO 2007/005075 has described the method for preparing these types pentasil catalyst, and how this catalyst can be incorporated in the catalyst inventory of FCC apparatus.Special these catalyst of design to be improving the olefin yields of FCC apparatus, and contain the FCC apparatus of this catalyst for catalyst inventory, and the present invention can have special effectiveness.
The present invention also is particularly suitable for its catalyst inventory and comprises the ferrum-based catalyst FCC apparatus of (as describing among the U.S. Patent application 2006-0011513), wherein the pentasil catalyst comprises the metal phosphate binding agent, especially comprises those catalyst of iron phosphate binders.
As mentioned above, listed DCC, UCC and CPP also improved the yield of light olefin in the FCC apparatus during the harsher operation of utilization was as above shown.These methods use with FCC in the identical catalyst of normally used catalyst, but adjustment amount and ratio make suitable selected specified conditions.Each a series of conditions in these operations are provided in the last table.These methods and wherein used catalyst are known in the art.Referring to people such as Chapin, " Deep Catalytic Cracking, Maximize Olefin Production ", Presented at 1994NPRA Annual Meeting, San Antonio, Texas, 20-22 day in March, 1994 (DCC); People such as Meng, " Production of Light Olefins by Catalytic Pyrolysis of Heavy Oil ", Petroleum Science and Technology, the 24th volume, 413-422 page or leaf, 2006 (CPP) and United States Patent (USP) 5,846,402 (UCC).
Also envision the present invention and can use the method for carrying out the known and approval of Kellogg Brown and Root device as the Superflex method.In this embodiment, when direct processing light naphthar charging, press design operation Superflex method, then according to the instruction processing of this paper product from this device to improve yield of light olefin.
Hydrocarbon effluent or product from FCC apparatus are not only relevant with raw material, and be also relevant with the condition in the device.The hydrocarbon flow of under typical FCC condition, handling, and handle according to the present invention those, cause having the hereinafter product of specification described in the embodiment.
To deliver to fractionating column and further handle from the product of FCC apparatus then according to the present invention.When the operation FCC apparatus when improving the yield of light olefin in the FCC product, the weight that light olefin comprises based on the charging of FCC apparatus is the propylene of the about 20 weight % of 6-.Above-mentioned be the exemplary elaboration of FCC apparatus product specification about the DCC method with the table 2 in the NPRA report of maximization propene yield, for example to maximize C
3About 8% propene yield of the FCC apparatus of olefin yields operation.The exemplary FCC product that obtains under the normal condition more 7% the propene yield according to appointment of having set forth in the table 3 of " Reformulated Gasoline ": The Role of Current and Future FCC Catalysts, people such as Young, presented at the 1991NPRA Annual Meeting, 17-19 day in March, 1991, San Antonio, Texas.
Fractionation
End product target according to oil plant is separated into various cuts with the FCC product.For the present invention, fractionating column for example is also referred to as FCC king-tower (FCC Main Column), the FCC product is separated at least cut and the naphtha cut that contains light olefin.The cut that contains light olefin generally comprises C
4Or lower saturated and/or unsaturated cut.Described tower or fractionator can be known in the art those.Referring to Fluid Catalytic Cracking Handbook-Design, Operation, and Troubleshooting of FCC Facility, Sadeghbiegi, 18-21 page or leaf, (1995).The service condition of these towers changes according to required fractionation number of times.The refiner moves FCC apparatus, generally the FCC product is fractionated into light olefin cut, gasoline naphtha cut, light cycle oil (LCO) cut and recirculates or bottom fraction.
Contain C
4Or the lower general conduct of light olefin cut " moisture " saturated and/or unsaturated cut is distilled.It is generally acknowledged that the moisture cut is for having 50 ℃ or more lower boiling those cuts.These cuts generally reclaim in compressor plant and processed/be distilled into independent light olefin, from the fractionating column flash distillation.
The gasoline naphtha cut generally comprises C
5-C
12Hydrocarbon.For the present invention, the term of the commutative use of this paper " naphtha " and " gasoline naphtha " refer to the hydrocarbon flow of finding with about 50 ℃-Yue 220 ℃ of boiling ranges in refinery operations.Naphtha cut contains alkene, aromatic hydrocarbon and non-aromatic hydrocarbon such as the aliphatic hydrocarbon compounds of various amounts, and mainly by following boiling range difference.Light olefin has 50 ℃-Yue 105 ℃ boiling point.Middle (in) naphtha has 105 ℃-Yue 160 ℃ boiling point.Heavy catalytic naphtha has about 160 ℃-Yue 220 ℃ boiling point.
Benzene has 80 ℃ boiling point and most of benzene meeting and the naphtha cut in the FCC product distills together.Can comprise the benzene of the about 3 weight % of 0.6-, the benzene that common 1 weight % is above from the naphtha products cut of the FCC apparatus of operating in the mode of the olefin yields that produce to improve.
If with the FCC product be separated into gently, middle and heavy catalytic naphtha cut, the benzene of significant quantity can with light catalytic naphtha, i.e. 50-105 ℃ cut, flash distillation together.Can comprise the benzene of the about 6 weight % of 1.2-, common benzene more than 2% from the light catalytic naphtha of the FCC apparatus of operating in the mode of the olefin yields that produce to improve.Such benzene concentration pentasil zeolite such as ZSM5 crystal therein comprises in the light catalytic naphtha of producing in the device of 2-20 weight % catalyst inventory and finds.
Do not follow particular theory, believe when utilizing harsher method to produce more light olefins in FCC apparatus, dealkylation, cyclisation and the dehydrogenation reaction of carrying out the aromatic hydrocarbon side chain are to produce the benzene of higher concentration.Depend on the technology of pentasil zeolite, on the other hand, from naphtha cut, remove the cracking molecule, thereby cause having the materials flow of higher benzene concentration to olefin hydrocarbon molecules with the production light olefin.In other words, the pentasil catalyst is removed from the naphtha materials flow and can be diluted the molecule of the existence of benzene.
From tower, collect and contain benzene naphtha cut such as gamut or light fraction and deliver to film then and further handle according to the present invention.Referring to Fig. 1.Remaining cut leaves this tower, and for example LCO and HCO represent C respectively
12-C
22And C
22The hydrocarbon-fraction of higher scope.Can expect that these cuts generally do not require according to the present invention and further handle.The materials flow of these back of general collection is also sent to separating treatment, perhaps recycles by FCC apparatus.
Film separates
The film that is used for the present invention be have enough flux and selectivity with the hydrocarbon that contains multiple arene compound as contain the benzoline naphtha in the presence of permeate those films of benzene at least.Can use any aromatic hydrocarbon selective film.Based in conjunction with the high yield of high flux and good aromatic hydrocarbon selective with stand the ability of common 80-120 ℃ hot operating temperature, select favourable film.Benzene height infiltrate aromatic hydrocarbon selective film.When benzene relatively passes C in the transfer rate of benzene selective film and the raw material
5When reaching the transfer rate of above compound, the relative speed that removes benzene is the fastest, thereby makes the present invention quite effective, keeps valuable gasoline fraction in the retentate simultaneously.In addition, the film system can be designed to handle extensive incoming flow, 34000 barrels/day the order of magnitude for example, thus for utilizing, the refiner the invention provides the potential economical efficiency of scale.
Film generally has the rich benzene factor greater than 1.5, is preferably greater than 2, even more preferably about 2-is about 20, most preferably from about 2.5-15.Preferred film has unsymmetric structure, and it can be defined as by the ultra-thin top of densification " skin " layer integral body of forming on the thicker loose structure of identical or different material.Usually, anisotropic membrane loads on suitable the porous backing or support material.
In one embodiment of the invention, film is served as reasons
5218 or as at United States Patent (USP) 6,180, the polyimide film of the Lenzing polyimide polymer preparation of describing in 008, its content is incorporated this paper by reference into.
In another embodiment of the invention, film is to have silica alkyl polymer for example to be coated in film on micropore or the ultrafiltration supporting layer as the active separating layer of part.In conjunction with the example of the membrane structure of polysiloxanes functional group at United States Patent (USP) 4,781,733, United States Patent (USP) 4,243,701, United States Patent (USP) 4,230,463, United States Patent (USP) 4,493, and 714, United States Patent (USP) 5,265,734, United States Patent (USP) 5,286,280 and United States Patent (USP) 5, find in 733,663, described document is incorporated this paper by reference into.
In yet another embodiment of the present invention, film is as at United States Patent (USP) 4,962, and disclosed aromatics polyureas/carbamate film in 271 is incorporated this paper by reference into.This polyureas/carbamate film is characterised in that and has at least 20% but be lower than 100% urea index, and the aromatic carbon content of at least 15 moles of % is at least about the functional group densities of 10/1000g polymer be lower than about 8 C=O/NH ratio.
During Separation of Benzene, above-mentioned film based on polyimides, polyureas-carbamate and polysiloxanes is particularly useful in the gasoline of producing the device of pentasil zeolite crystal that comprises the about 20 weight % of 2-from its catalyst such as ZSM-5 (as light catalytic naphtha).The benzene that can comprise as previously described, 1.2-6.0 weight % by the light catalytic naphtha of this Catalyst Production.
Film can use with any conventionally form such as plate, pipe or doughnut.Plate can be used to make the spiral winding element that those skilled in the art are familiar with.Perhaps, plate can be used to make the slab reactor permeability apparatus, and it comprises a plurality of being fed-retentate spacer and the penetrant spacer replaces the rete of separating.At United States Patent (USP) 5,104, this device has been described in 532, incorporate this paper by reference into.
Pipe can use with the form of leafy assembly, wherein each Guan Jun by graduation and with the parallel placement of other graduation pipes.Spacer is all contained in the inside of each pipe.The graduation pipe of phase adjacency pair is separated by spacer material layer.The graduation pipe of configuration isolation material is put into the pressure-proof outer cover that is equipped with fluid intake and outlet device.The end of clamping pipe is to make the inside and outside zone that separates with respect to the pipe in the shell.At United States Patent (USP) 4,761, describe in 229 and claimed such device, incorporate this paper by reference into.
Thereby doughnut can be with the inside of separator tube and the outside of pipe in the spread pattern of arbitrary end tinning bunchy is used with the formation tube sheet and the pressure vessel of packing into.Such device is known in the art.The improvement of standard design comprises hollow fiber bundle become separated region by using barrier partitions, and it redirects fluid in the pipe side of this bundle and flows and stop fluid in pipe side fluting and polarization.At United States Patent (USP) 5,169, this improvement is disclosed in 530, incorporate this paper by reference into.
A plurality of resolution elements, no matter they are spiral winding, plate and frame, pipe or hollow fiber elements, can use by serial or parallel connection.United States Patent (USP) 5,238,563 is incorporated this paper by reference into, discloses the multicomponent shell, and wherein each element is in parallel organizes into groups, and has the charging/retentate zone of the definition space that is surrounded by two tube sheets that are arranged in the same end of element.
No matter will contain benzoline under the condition of pervaporation or infiltration extraction (perstraction), be gamut gasoline or light catalytic naphtha for example, carries out selective membrane and be separated into penetrant and retentate.Preferably under the pervaporation condition, carry out this technology.
Pervaporation technology depends on that generally permeate side removes penetrant and keep the concentration gradient driving force that drives this separating technology to the vacuum of evaporant side or from the surface to film.Charging is liquid phase and/or gaseous state.When being gaseous state, this technology can be described as evaporating-osmosis.The maximum temperature of using in the pervaporation still is lower than film by the temperature of physical damage simultaneously for must evaporate the component of wishing selectivity infiltrate film in the charging.Pervaporation can be carried out under about 25-200 ℃ or higher temperature, and maximum temperature is that film is by the temperature of physical damage.The feed pressure that enters film device is generally 1-20 atmospheric pressure and device is operated under the vacuum of 0.1-300 millimetres of mercury.Preferred pervaporation technology is operated to reduce fund cost as the single phase operation.As another selection of vacuum, can use sweep gas to remove product in permeate side.Under this pattern, permeate side under atmospheric pressure.
In the infiltration extraction process, the penetrant molecular diffusion in the charging enters in the film, and migration reappears in permeate side by film and under the influence of concentration gradient.Use purging liquid stream to keep the concentration gradient driving force in the permeate side of film.At United States Patent (USP) 4,962, the infiltration extraction process has been described in 271, incorporate this paper by reference into.
No matter be pervaporation or infiltration extraction, can easily regulate selected membrane process to adapt to the various products of FCC apparatus by changing charging flow velocity or operating temperature.Therefore the present invention provides the method for control variables to increase yield to help oil plant in addition, and still has the method that contains the materials flow of benzene naphtha of handling.
According to the present invention, realized reducing very significantly benzene in the naphtha by selective membrane.Generally, retentate, this paper also are poor benzene retentate, have to be lower than 1% benzo and to be low to moderate 100ppm, depend on benzene concentration in the naphtha, film separation condition etc.The present invention preferably reduces gasoline benzene makes retentate contain to be lower than the benzene of 0.6 weight %.Generally, realize that easily benzene enough in the retentate reduces, and keeps the level of gasoline naphtha molecule in the retentate simultaneously in fact or significantly.Refiner's gasoline pool is delivered in the retentate materials flow then, wherein combines with other refinery stream to form gasoline product.
The BTX device (benzene, toluene and dimethylbenzene) of rich benzene penetrant being delivered to oil plant is to collect and suitably to process, to use and/or to handle.Usually the benzene (and toluene) that has 1-10 weight % from penetrant of the present invention.Depend on oil plant, the penetrant that is rich in high benzene can be sent to processing, and further concentrate feed flow to the purified petroleum benzin basically that uses in chemical operation, and perhaps penetrant can further be handled to become the raw material in reformation or the alkylation process.
Can be by fractionation contains the efficient that benzene naphtha (gamut or light) obtains the present invention's increase the depentanize destilling tower being used for before the film device of naphtha cut Separation of Benzene.Depend on selected film, the C in the gasoline stream
5Alkene usually remains in the retentate, but these alkene also can concentrate in penetrant.Handle the naphtha materials flow and from penetrant, remove C
5Therefore alkene, concentrate the benzene in the raw material of delivering to film.Generally speaking this should reduce the requirement of segmentation cut.C
5Cut is removed, and with when having low concentration benzene faster absolute speed remove higher benzene concentration.Condensation does not have C
5The expense of the penetrant of cut also can reduce.Can be with the C that from depentanizer, reclaims
5Alkene is further handled then to satisfy another oil plant needs, perhaps is back in the retentate materials flow handling to gasoline pool.The depentanize destilling tower is known in the art.The tower that uses in this embodiment of the present invention can be distilled into flash distillation cut and the bottom fraction under 150-200 ℃ temperature at the top of tower under 50 ℃.
In order to further specify the present invention and its advantage, provide following specific embodiment.Embodiment only provides purposes for illustrative purposes only and does not mean that restriction to claims.Should be appreciated that and the invention is not restricted to detail described in the embodiment.
Embodiment and specification remainder relate to all parts and the percentage of solid composition or concentration, except as otherwise noted all by weight.Yet all parts and percentage that embodiment and specification remainder relate to gas composition are mole or by volume except as otherwise noted.
In addition, any number range of quoting in specification or the claim, as represent the specific collection of performance, measurement unit, condition, physical state or percentage, on literal, incorporate this paper clearly into by reference, perhaps any numerical value that falls into this scope comprises any numerical value subclass in any scope of being quoted.
Embodiment 1
Make benzene selective polyureas/carbamate film (M1) with two step coating processes.Preparation is the polyethylene glycol adipate and 4 of the toluene di-isocyanate(TDI) end-blocking of 1.05-1 by mol ratio, 4 '-di-2-ethylhexylphosphine oxide (2, the 6-diethylaniline) form two
Solution in the alkane, solid content are 4%.This makes and reacts 16 hours nights to generate polyureas/carbamate solution.With gained solution dip-coating polyacrylonitrile ultrafiltration matrix.The ventilated drying oven that the matrix that applies is transferred under 100 ℃ carries out drying and curing then.In second step, preparation toluene di-isocyanate(TDI) end-blocking polyethylene glycol adipate and 4, another solution of 4 '-di-2-ethylhexylphosphine oxide (2, the 6-diethylaniline), but specifically two
Solid content in the alkane is 2.65%.This makes and reacts 16 hours nights to generate polyureas/carbamate solution.Then with this solution dip-coating to previous coating substrate, they aging 7 days.The matrix of this new coating is transferred in the ventilated drying oven under 100 ℃ again.The film of finishing is dry and durable.
Use the performance of people's such as Feimer method (US4,879,044) calculating M1 polymer separating layer.Aromatic hydrocarbon index=17.56 of calculating, urea index=50, (C=O+NH)/1000g's and=12.64, and C=O/NH value=5.34.
Embodiment 2
To make the second benzene selective film (M2) to embodiment 1 described two similar step coating processes.Preparation is the polyethylene glycol adipate and 4 of the toluene di-isocyanate(TDI) end-blocking of 1.05-1 by mol ratio, 4 '-di-2-ethylhexylphosphine oxide (2, the 6-diethylaniline) form two
Solution in the alkane, solid content are 2.65%.This makes and reacts 16 hours nights to generate polyureas/carbamate solution.The identical above-mentioned polyacrylonitrile ultrafiltration matrix of dip-coating is transferred to ventilated drying oven under 100 ℃ then with dry and solidify.Behind aging 7 days of applying for the first time, use with top identical coating and apply coated matrix for the second time.The film of finishing is dry and durable.
M2 is another polyureas/carbamate film with more aromatic hydrocarbon contents and Geng Gao functional group densities.Calculate aromatic hydrocarbon index=29.63, urea index=50, (C=O+NH)/1000g's and=12.97, and C=O/NH value=2.33.
Embodiment 3
In Davison Circulating Riser, under the regenerator temperature of the reactor pressure of 1010 temperature of reactor, 25psig and 1300, use the mixed catalyst of 80%Ultima and 20%Ultra to handle to have the FCC raw material of the nitrogen of 25.5 api gravity, 11.94 the K factor, 0.68% Kang Laxun carbon residue and 0.12 weight %.Propene yield is 8.37 weight % based on raw feed.Light C
3And C
4Compound separates from naphtha by the destilling tower of operating under 90 bottom temp and 12 head temperature.The naphtha that reclaims contains the benzene of 1.1 weight %.
By charging pond, circulating pump, flowmeter, be arranged in the pervaporation system that the test chamber that contains membrane sample, permeate collection vessels and the vavuum pump of oven interior form and use benzene selective film M1 and M2 further to handle this naphtha.Cooled permeate in liquid nitrogen (195 ℃).Incoming flow is for removing the FCC naphtha of C3 and C4 compound.In the pervaporation device, under 120 ℃ and vacuum, carry out film test to reduce the benzene level in this naphtha for each film M1 and M2.Pressure regulator makes naphtha be forced into 80psi and keep liquid phase when hot.Vavuum pump produces the vacuum that is lower than 10 holders in the permeate side of film.
Each penetrant sample was collected 1-2 hour.Collect multiple penetrant sample and produce big segmentation cut.Retentate returns the charging pond continuously with in the film cocycle.Each penetrant fraction collection begin to collect the retentate sample, when this end of run, collect a final sample.
Use standard GC method is measured the hydrocarbon concentration (weight %) of retentate and penetrant.
The result is presented among the figure (Fig. 2), and wherein the segmentation cut refers to the charging cut of removing as penetrant.M1 is created in has the retentate that is lower than 0.6% benzene under the 25% segmentation cut.M2 has more optionally film, and the segmentation cut by 21% produces and is lower than 0.6% benzene.
Claims (32)
1. a catalyst cracking method comprises
A. hydrocarbon feed is introduced in the reaction zone of catalytic cracking unit, its feature of raw material is to have: about 120 ℃ initial boiling point and up to about 850 ℃ final boiling point;
B. Cracking catalyst, temperature, catalyst/oil ratio, pressure, steam dilution and the air speed that use to make olefin yields from described device improve in described reaction zone comes the described raw material of catalytic cracking to comprise the product of alkene, naphtha and benzene with production, and it is the propylene of about 6%-about 20% that wherein said product comprises based on the weight of introducing the hydrocarbon feed among the above-mentioned steps a;
C. described product is fractionated at least cut that contains light olefin and the naphtha cut that contains benzene;
D. reclaim the cut that contains light olefin;
E. make the naphtha cut that contains benzene and have enough flux and optionally the film contact is to separate rich benzene penetrant cut and poor benzene naphtha retentate cut, described rich benzene penetrant cut is compared with retentate and is rich in benzene;
F. reclaim poor benzene naphtha retentate cut; With
G. rich benzene penetrant cut is sent to further processing.
2. according to the catalyst cracking method of claim 1, wherein the Cracking catalyst among the step b comprises the pentasil zeolite crystal content of the about 20 weight % of 2-of catalyst.
3. according to the catalyst cracking method of claim 1, wherein the Cracking catalyst among the step b comprises catalyst additive, and described catalyst additive contains the ZSM5 of the about 80 weight % of 10-of catalyst additive.
4. according to the catalyst cracking method of claim 1, wherein contain the benzene that the benzene naphtha cut comprises the about 3 weight % of 0.6-among the step c.
5. according to the catalyst cracking method of claim 1, wherein the benzene naphtha cut that contains among the step c is the light catalytic naphtha with boiling point of 50-105 ℃, and comprises the benzene of the about 6 weight % of 1.2-.
6. according to the catalyst cracking method of claim 2, wherein the benzene naphtha cut that contains among the step c is the light catalytic naphtha with boiling point of 50-105 ℃, and comprises the benzene of the about 6 weight % of 1.2-.
7. according to the catalyst cracking method of claim 1, wherein said method is the DCC method, and the condition in the reaction zone of step a is as follows:
8. according to the catalyst cracking method of claim 1, wherein the film among the step e comprises the film that is selected from polyimides, polyureas-carbamate, polysiloxanes and combination thereof.
9. according to the catalyst cracking method of claim 2, wherein the film among the step e comprises the film that is selected from polyimides, polyureas-carbamate, polysiloxanes and combination thereof.
10. according to the catalyst cracking method of claim 5, wherein the film among the step e comprises the film that is selected from polyimides, polyureas-carbamate, polysiloxanes and combination thereof.
11., wherein contain the benzene naphtha cut and under the pervaporation condition, contact with film according to the catalyst cracking method of claim 1.
12. according to the catalyst cracking method of claim 1, wherein poor benzene naphtha retentate comprises the benzene that is lower than the about 100ppm of 1 weight %-.
13. according to the catalyst cracking method of claim 1, wherein poor benzene naphtha retentate comprises the benzene that is lower than the about 100ppm of 0.6 weight %-.
14. according to the catalyst cracking method of claim 1, wherein rich benzene penetrant comprises the benzene of the about 10 weight % of 1-.
15. according to the catalyst cracking method of claim 1, further be included in according to step e make contain the benzene naphtha cut and film contact before, fractionation contains the benzene naphtha cut to remove C from step c's
5Cut.
16. produce light olefin and the low method that contains the benzene naphtha by hydrocarbon feed for one kind in catalytic cracking unit, described method comprises:
A. selecting catalyst, temperature, catalyst/oil ratio, pressure, steam dilution and/or air speed are to improve the olefin yields in described catalytic cracking unit;
Raw material is contacted in device with Cracking catalyst, thereby produce the product that comprises alkene, naphtha and benzene;
C. product is fractionated at least cut that contains light olefin and the naphtha cut that contains benzene;
D. reclaim the cut that contains light olefin;
E. make to contain the benzene naphtha cut and have enough flux and optionally film contact is to separate rich benzene penetrant cut and poor benzene naphtha retentate cut, described rich benzene penetrant cut is compared with retentate and is rich in benzene;
F. reclaim poor benzene naphtha retentate cut; With
G. rich benzene penetrant cut is sent to further processing.
17. according to the method for claim 16, wherein the benzene naphtha cut that contains among the step c has the about 220 ℃ boiling point of 50-, and described cut comprises the benzene of the about 3 weight % of 0.6-.
18. according to the method for claim 16, wherein the benzene naphtha cut that contains among the step c has the about 105 ℃ boiling point of 50-, and described cut comprises the benzene of the about 6 weight % of 1.2-.
19. according to the method for claim 16, wherein to comprise based on the raw material weight among the step a be the propylene of the about 20 weight % of 6-to the product of step b.
20. according to the method for claim 16, wherein the film among the step e comprises the film that is selected from polyimides, polyureas-carbamate, polysiloxanes and combination thereof.
21., wherein contain the benzene naphtha cut and under the pervaporation condition, contact with film according to the method for claim 16.
22. according to the method for claim 16, wherein poor benzene naphtha retentate comprises the benzene that is lower than the about 100ppm of 1 weight %-.
23. according to the method for claim 16, wherein poor benzene naphtha retentate comprises the benzene that is lower than the about 100ppm of 0.6 weight %-.
24. according to the method for claim 18, wherein poor benzene naphtha retentate comprises the benzene that is lower than the about 100ppm of 1 weight %-.
25. according to the method for claim 19, wherein poor benzene naphtha retentate comprises the benzene that is lower than the about 100ppm of 1 weight %-.
26. according to the method for claim 16, wherein raw material contacts with the catalyst that comprises ZSM5.
27. according to the method for claim 16, wherein the raw material among the step b contacts with the catalyst that comprises the about 20 weight %pentasil crystal of 2-.
28. according to the method for claim 19, wherein the raw material among the step a contacts with the catalyst that comprises the about 20 weight %pentasil crystal of 2-.
29. according to the method for claim 27, wherein pentasil is ZSM-5.
30. according to the method for claim 28, wherein pentasil is ZSM-5.
31. according to the method for claim 16, wherein the Cracking catalyst among the step b comprises catalyst additive, described catalyst additive contains the ZSM5 of the about 80 weight % of 10-of catalyst additive.
32. according to the method for claim 19, wherein the Cracking catalyst among the step b comprises catalyst additive, described catalyst additive contains the ZSM5 of the about 80 weight % of 10-of catalyst additive.
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| US61/192,074 | 2008-09-15 | ||
| PCT/US2009/005095 WO2010030369A1 (en) | 2008-09-15 | 2009-09-11 | Catalytic cracking for enhanced propylene yield and reduced benzene naphtha fractions |
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| US (1) | US20110163002A1 (en) |
| JP (1) | JP2012503038A (en) |
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- 2009-09-11 CN CN2009801453330A patent/CN102215958A/en active Pending
- 2009-09-11 JP JP2011526859A patent/JP2012503038A/en active Pending
- 2009-09-11 US US13/063,254 patent/US20110163002A1/en not_active Abandoned
- 2009-09-11 WO PCT/US2009/005095 patent/WO2010030369A1/en active Application Filing
- 2009-09-11 KR KR1020117008557A patent/KR20110059879A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106554811A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | The Application way of benzene-enriched cut in de-pentane oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012503038A (en) | 2012-02-02 |
| WO2010030369A1 (en) | 2010-03-18 |
| US20110163002A1 (en) | 2011-07-07 |
| KR20110059879A (en) | 2011-06-07 |
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