CN1259983A - Hydrocarbon cracking with positive reactor temp. gradient - Google Patents

Hydrocarbon cracking with positive reactor temp. gradient Download PDF

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CN1259983A
CN1259983A CN 98805992 CN98805992A CN1259983A CN 1259983 A CN1259983 A CN 1259983A CN 98805992 CN98805992 CN 98805992 CN 98805992 A CN98805992 A CN 98805992A CN 1259983 A CN1259983 A CN 1259983A
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陈诞仁
J·T·罗
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ExxonMobil Chemical Patents Inc
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06Catalytic processes
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/50Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the eroionite or offretite type, e.g. zeolite T
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/60Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/65Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2529/86Borosilicates; Aluminoborosilicates
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/88Ferrosilicates; Ferroaluminosilicates
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/89Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins

Abstract

The invention provides an improvement in processes for cracking hydrocarbons to prime olefins, ethylene and propylene, which comprises applying a positive temperature gradient across a catalyst contact zone. The temperature gradient may be uniform or stepwise, may be one reactor or a series of reactors so long as at least one down stream cracking zone is operated at a higher temperature than an upstream zone.

Description

The hydrocarbon pyrolysis of positive reactor temperature gradient method
The present invention has provided a kind of technology, by adopting the positive reactor temperature gradient method, has improved the productive rate of ethene in the Deep Catalytic Cracking process and/or propylene.
Realize it being an important production process with heat and catalysis from the hydro carbons to the conversion of olefines, the annual alkene that all utilizes it to produce thousands of tons.Because turnout is huge, so the slight improvement on the operation efficiency all can bring significant benefit.Have in the conversion process that adds in the selection from the hydro carbons to alkene, catalyzer plays an important role.
The catalyzer of particularly important can be sought in natural and synthetic zeolite.Zeolite is a class compound crystalline aluminosilicate, AlO 4And SiO 4Tetrahedron is connected with shared Sauerstoffatom and constitutes network.Tetrahedral negative charge obtains balance because of the participation of proton or positively charged ion such as basic metal or alkaline-earth metal ions.The space or the pipeline that form because of the crystalline state network make zeolite to use as molecular sieve in separating technology.The ability of zeolite adsorption material also makes them to be applied in the catalysis.No matter be natural or the synthetic zeolite, the number of its structure is huge.Its letter lid the wide of scope can know something about from monograph, " Atlas of ZeoliteStructure Types " (4th ed., Butterworths/Intl.Zeolite Assoc.[1996]), the author is W.M.Meier, D.H.Olson and C.H.Baerlocher.Find that the catalyzer that contains zeolite has the ability the lightweight raw gasline to be cracked into ethene and propylene, the elementary alkene of a class.
Noticeable especially is the acidifying attitude of zeolite, and it can change into elementary alkene with light hydrocarbons such as lower boiling raw gasline effectively.Typical catalyzer comprises the ZSM-5 zeolite, at U.S.Pat.No.3, has in 702,886 and describes and be required, and ZSM-11, sees U.S.Pat.No.3,709,979, and the various variants of these catalyzer, and describe to some extent in some patents afterwards and be required.
Use and realized preparing ethane and propane with hydrocracking or hydrogenolysis method the early stage of multistage temperature section in the elementary olefin production process, and obtained a spot of elementary alkene in elementary section.Franck etc. are at U.S.Pat.No.4, have adopted a kind of multistage hydrogenolysis section in 137,147, and each section operates under than high 5~25 ℃ temperature of last section.Separating C 4 +Product and will be that its part is delivered to further hydrogenolysis step with after extra production ethane and the propane at least, with in the hydrogenolysis section effluent≤C 3The light hydrocarbons steam cracking becomes elementary alkene.Substantially the cut of being made up of ethane and propane is fed in the steam cracking equipment to change into ethene.Lionetti etc. are at U.S.Pat.No.4, have provided a kind of two section systems that prepare aromatic hydrocarbons from heavy oil in 388,175.The working temperature of second section is than the first section height, with production lightweight raw gasline, gasoline and needle-like coke.Do not mention any application about elementary olefin production.Tabak is at U.S.Pat.No.4, and 487,985 and division U.S.Pat.No.4,560, introduced the oligomerization of elementary alkene in the multi-region section serial reaction device in 536, wherein before catalyst regeneration, what the second higher section of temperature adopted is the catalyzer of part inactivation in elementary section.In european patent application 0 023 802, a kind of step of hydrocracking has prepared C 2~C 5Paraffinic hydrocarbons then is prepared into elementary alkene by the higher thermal cracking processes of downstream temperature with it.GB 2,105, and 362 have introduced two section thermal cracking process of a kind of catalyst-free system, and wherein the primary reaction section is heated to 1000 ℃ with steam/raw material from 800 ℃, then raw material is transferred in the secondary catalyst-free section, is heated to 1150 ℃ from 850 ℃.Mauleon etc. are at U.S.Pat.No.5,506,365 and 5,264, introduced a kind of multistage section technology in 115, in a technology, in slight steam heat cleavage step, adopted hot catalyzer, and under lower temperature, at downstream section further reaction has taken place with the catalyzer of adding at gasoline production.
European patent application 0 262 049 has been introduced a kind of hydro carbons (propane is example) steam cracking process, then contacts with the polycomponent zeolite that contains catalyzer, and it has added the metal oxide of tool hydrogenation/dehydrogenation function.This thermal cracker is worked under the temperature higher than cat cracker.Adams is at U.S.Pat.No.3, and also having introduced steam cracking step back in 360,587 then is cat cracker, and this cat cracker still temperature than upstream heat cracker is low.In european patent application 0 023 802, a kind of catalysis (hydrocracking) reactions steps has prepared C 2~C 5Be main catenanes, be fed to subsequently in the optional high temperature pyrolysis device to change into elementary alkene.Disclosed PCT application WO 95/13255 has described a kind of association system, from being to isolate light ends the effluent of degree of depth cat cracker of raw material than heavy oil fraction, and it is circulated in the thermal cracker to prepare elementary alkene.Disclosed PCT application WO86/02376 has described the cracking of heavy oil, isolates overhead fraction after being included in pre-pyrolytic cleavage step, with its thermo-cracking to prepare elementary alkene.Burich is at U.S.Pat.No.3, described a kind of associating refining unit in 702,292, wherein different streams separated and is fed in two devices of hydrogenolysis and thermo-cracking.The Derwent WPI Accession No.88-053890/08 of Japanese Patent 60235890 has described in the system of one two section hydrocarbon pyrolysis.The Detwent WPI AccessionNo.86-011144/02 of Japanese Patent 63010693 has described the by product lightweight oil that will contain alkene and has been fed to the thermo-cracking process furnace from cat-cracker, reclaims elementary alkene with high purity.
Up to now, existing technology is not also recognized, crosses over the thermograde or the temperature sectionization of a plurality of reactors, cooperates with suitable catalyzer, just can realize significantly improving of elementary olefin yield, and remove each component of pre-separation from or remove C from feedstream 4 +The step of material, and saved the trouble of in downstream or circulation loop, settling steam cracking equipment.
The present invention has provided the technology that improves from hydrocarbon raw material to the light olefin transformation efficiency, is included in one by the step that in the reactor of forward thermograde running hydrocarbon raw material is contacted with catalyst for cracking.In an optional embodiment of the present invention, provided a kind of technology for preparing ethene and propylene in the catalytic pyrolysis mode, wherein hydrocarbon raw material contacts with catalyst for cracking, improvements comprise that the elementary catalyzer that an elementary temperature is provided contacts section and is positioned at the secondary catalyzer contact section that this elementary catalyzer contacts a secondary temperature in section downstream, and this secondary catalyzer contact section remains on than under the high temperature of elementary catalyzer contact section, and the hydrocarbon raw material of cracking is transferred to secondary catalyzer contact section from elementary catalyzer contact section.In another embodiment, for preparing required product mixture, the catalyzer in downstream can be identical or different.Second embodiment can comprise a plurality of reaction vessels, and prerequisite is that the downstream reservoir of at least one is to turn round under the temperature higher than upstream reactor, and the catalytic pyrolysis section can both be provided.Explanation of nouns
" lightweight raw gasline " refers to C 5~C 7Hydro carbons is main hydrocarbon-fraction.
" virgin naphta " refer to come from crude oil or Sweet natural gas, without the hydrocarbon-fraction of additional conversion processing.
" catalysis raw gasline " refers to from than the catalytic pyrolysis of heavy hydrocarbon fraction and the hydrocarbon-fraction that comes.
" BTX " refers to the mixture that contains benzene, toluene and dimethylbenzene.
" light olefin " or " elementary alkene " refers to ethene, propylene or its mixture.
" raising transformation efficiency " refers to and reached raising on output, promptly in the accuracy rating of detection system, can realize higher light olefin productive rate than the situation with the identical raw material of identical cracking catalyst under the steady temperature.
" hydrocarbon raw material " refers to the hydrocarbon material that comprises one or more hydrocarbon, and because of heat, chemistry or catalytic active function are broken into fragment, these fragments form light olefin.
" forward thermograde " refers to the comparatively high temps of temperature from the low temperature change of primary position to secondary location, and secondary location is in the downstream of primary position.Reaction conditions and catalyzer
At catalyzer, particularly contain the cracking of carrying out hydrocarbon raw material such as lightweight catalysis raw gasline (LCN) or lightweight virgin naphta (LVN) on the zeolite that ZSM-5 becomes divided catalyst, prepare a large amount of propylene and ethene.The present invention has provided a kind of method that improves ethene and productivity of propylene, and it is included on the reactor beds by the running of the thermograde of forward feedstream is contacted with catalyzer.Preferred feedstream is LCN or LVN, but but the hydrocarbon material stream of any catalytic pyrolysis can both adopt.
By the employing of temperature of reactor gradient method, any catalyst for cracking that can be used to optionally to prepare elementary alkene can both be improved.Suitable to any typically natural existence of zeolite of catalyst for cracking or the acidifying attitude, particularly silica alumina ratio about 2.0: 1~2,000 of synthetic crystalline zeolite: a kind.Usually, hydrocarbon cracking can be become light olefin, and realize any catalyzer that transformation efficiency improves, all be applicable to this technology by the use temperature gradient.Use following simple small-scale test, be familiar with to judge this in the forces of this area, the sectionization whether a kind of catalyzer can Yin Wendu and realize the raising of transformation efficiency.
Zeolite example useful in described technology comprises, silicic acid gallium zeolite, and its example is seen U.S.Pat.No.5,096,686, zeolite-β, zeolite-ρ, ZK5, titanosilicate, ferrosilicate; Borosilicate zeolites; By the Linde Division of Union Carbide with the zeolite of alphabetical X, Y, A, L name (this type of zeolite is respectively at U.S.Pat.No.2,882,244; 3,130,007; State in 3,882,243 and 3,216,789); Naturally occurring crystalline zeolite, such as phillipsite, ferrierite, mazzite, heulandite, faujusite, chabazite, erionite, mordenite, offretite, sarcolite, euthalite etc., ZSM-5, U.S.Pat.No.3 is seen in its description, 702,886.
Shi Yi catalyzer can be sought in the zeolite of medium and small-bore especially.The constraint factor that it is believed that these intermediate pore size zeolite is about 1~about 12.The measuring method of constraint factor sees U.S.Pat.No.4 for details, and 016,218.Meet the zeolite of intermediate pore size zeolite particular constraints coefficient value, comprise ZSM-5, ZSM-11, the ZSM-5/ZSM-11 intermediate, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, MCM-22 and zeolite-β, it is described example and sees U.S.Pat.No.3,702,886, and Re.No.29,949,3,709,979,3,832,449,4,046,859,4,556,447,4,076,842,4,016,245,4,229,424,4,397,827,4,954,325,3,308,069, Re.28,341 and EP 127,399, the inside has the details of these catalyzer can be for reference.Can prepare with 12: 1 is this type of zeolite of different sial (silica/alumina) mol ratio of starting point.In fact obtained preparation from the reaction mixture of oxygen-free aluminium specially, with the high material of preparation silica alumina ratio, silica alumina ratio can be extended to infinity theoretically at least.Preferred intermediate pore size zeolite comprises ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-35 and MCM-22.Particularly preferably be ZSM-5.The zeolite of small-bore comprises crystalline aluminosilicate zeolite such as erionite, chabazite, phillipsite, and corresponding synthetics such as zeolite A and ZK5, respectively at U.S.Pat.No.2, states in 882,243 and 3,247,195.
Preferred zeolite catalyst is selected from following thing group, comprise faujusite, chabazite, erionite, mordenite, offretite, sarcolite, euthalite, phillipsite, ZSM-5, ZSM-11, ZSM-5/ZSM-11 intermediate, ZSM-12, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, MCM-22, silicic acid gallium zeolite, zeolite-β, zeolite-ρ, ZK5 and titanium silicate zeolite, and the ferrosilicate zeolite of silica alumina ratio scope about 2.0: 1~2,000: 1; As the described borosilicate zeolites of Belgian Pat.No.859656 (4584091) and by the zeolite of the Linde Division of Union Carbide with alphabetical X, Y, A, L name.A suitable especially zeolite is ZSM-5.The preferred zeolite that contains catalyzer can be prepared by the described method of previous reference, perhaps buys in the businessman's hand known to the people who is familiar with this area.
Cracking process can adopt typical hydrocarbon raw material stream and implement by any equipment commonly used, can be fixed bed, moving-bed, fluidized-bed, such as being overflow type or tight type fluidised bed system, or fixed fluidized bed system.Preferably under the temperature of 500~750 ℃ of scopes, contact with catalyzer; More preferably scope 550-725 ℃; 600~700 ℃ of most preferred range.The temperature of reactor gradient is preferably in 10~150 ℃ scope; More preferably scope is 50~100 ℃; About 60~80 ℃ of most preferred range.Gradient may be a certain section homogeneous in catalytic bed, and wherein each downstream section is higher slightly than the temperature of adjacent upstream section.Gradient is also optional to be inhomogenous, and wherein the temperature of downstream section is than the temperature height of upstream zone.This optimal process is about 0.1 Hr in weight hourly space velocity (WHSV) -1WHSV~about 100 Hr -1Carry out in the scope of WHSV, more preferably about 1.0 Hr of scope -1WHSV~about 50 Hr -1WHSV, about 1.0 Hr of most preferred range -1WHSV~about 30 Hr -1WHSV.
The example that can be used for preparing the hydrocarbon material of high producing light olefins comprises ethane, propane, butane, raw gasline, gas oil, fischer-tropsch liquid, and the material such as butylene, divinyl, steam cracking raw gasline, catalytic pyrolysis raw gasline, coker naphtha and the kerosene that contain alkene or diolefine.A preferred raw material is lightweight catalysis raw gasline (LCN) or lightweight virgin naphta (LVN).
For the forward thermograde of single reaction container scale, an optional embodiment is the coupling in turn of a plurality of reactors, and the downstream reactor of at least one keeps the temperature higher than upstream reactor.In this optional embodiment, can adopt a plurality of reactors with gradient, or between a plurality of olefin production reactors, big temperature ladder is set near homogeneous.The difference of the preferred product mixture that obtains according to hope, the catalyzer in each reactor can be identical or different.Selection by catalyzer and thermograde size can improve the selectivity between ethene and the propylene.Embodiment 1
In mini-reactor, implement a series of test with lightweight catalysis raw gasline.Controlled trial is in 650 ℃ and 1.9 Hr -1Under the condition of WHSV, at 2.4 gram ZCAT40, a kind of from Inercat, inc.of Sea Girt carries out on the fixed bed of the ZSM-5 class zeolite catalyst that New Jersey buys.Before breaking test, ZCAT40 is with 100% steamed of 704 ℃ and one barometric points 16 hours, so that aging this catalyzer.In the process that test is implemented, the weight ratio of vapour hydrocarbon elect as 0.85 and the pressure-controlling of reactor at 6psig.Effusive material is analyzed with online gas-chromatography.Analyzing selected is 60 meters chromatographic columns that the fused silica of the dual flame ionization detector gas chromatograph of Hewlett-Packard's 5880A type is filled.With identical raw material, and with 1.9 Hr -1WHSV and 2.5 Hr -1WHSV tests on two fixed beds, and first section is 610 ℃ and second section is 680 ℃.
The data of principal product productive rate are shown in table 1.With 650 ℃ of homogenization temperatures down the mean number of about 26.9wt% compare, 65 ℃ forward thermograde makes the gain in yield of ethene to 32.0wt%.Productivity of propylene in this test is low slightly, is about 21.7wt%, compares the 23.2wt% under the homogenization temperature.At 2.5 Hr -1WHSV and the test that subtracts slightly under the catalyzer condition show, is the function (other parameter remains unchanged) of the temperature and the residence time to the selectivity of propylene.At 2.5Hr -1In the test of WHSV, the productive rate of ethene drops to 28.3% and propylene has been raised to 30.9%, and the small loss on the transformation efficiency reflects that the residence time is shorter.These data declarations, the present invention has superiority than the reactive mode of homogenization temperature in the prior art.
Table 1 thermograde is to the influence of principal product productive rate
WHSV?Hr -1 ????1.9 ????1.9 ????2.5
Temperature distribution ??650-650 ??608-680 ??615-680
Transformation efficiency, wt% ????95.9 ????98.4 ????91.4
Principal product, wt%
Ethene ????26.9 ????32.0 ????28.3
Propylene ????23.2 ????21.7 ????30.9
The butylene class ????7.0 ????4.7 ????8.8
Arene ????21.1 ????21.8 ????11.9
The lightweight saturated hydrocarbons ????17.8 ????18.2 ????11.5
Methane ????6.9 ????6.8 ????4.0
Ethene+propylene ????50.1 ????53.7 ????59.2
Embodiment 2
With the hexane is that model compound carries out a series of test of adding in as embodiment 1 described mini-reactor.Condition is with embodiment 1, and just weight hourly space velocity is 12 Hr -1The pressure of reactor is 6psig, and maintenance vapour hydrocarbon ratio is 0.33.
It is as shown in the table, has benefited from the sectionization of catalytic bed temperature of reaction, and the productive rate of light olefin has remarkable change.When catalytic bed preceding half section at 610 ℃ and the second half section 680 ℃ of whens operation, the productive rate of ethene is 28.9wt%, the productive rate of propylene is 31.9wt%.This productive rate not less than under the isothermal condition when operation catalytic bed productive rate that can reach, it is in scope 15.6~26.4wt% to ethene, and is 21.1~23.5wt% to propylene.
Table 2
Temperature, ℃ ????610 ????650 ????680 Sectionization 610 → 680
Transformation efficiency, wt% ???93.1 ???96.9 ???97.8 ????96.8
The principal product productive rate, wt%
Ethene ???15.6 ????27.7 ????26.4 ????28.9
Propylene ???21.1 ????27.4 ????23.5 ????31.9
The butylene class ???10.3 ????8.6 ????6.8 ????9.6
Arene ???22.6 ????19.8 ????23.1 ????14.9
The lightweight saturated hydrocarbons ???23.5 ????13.4 ????18.0 ????11.5
Methane ???2.0 ????4.5 ????8.2 ????2.8
Ethene+propylene ???36.7 ????45.1 ????49.9 ????60.8
Previous embodiment is of the present invention in order to illustrate, rather than is used for limiting its.The people who is familiar with this area obviously can make many accommodations to the present invention.The present invention is placing claims after this to define and limit.

Claims (18)

1. improve a kind of technology, comprising: in a reactor that turns round by forward thermograde mode, realize contacting of hydrocarbon raw material and catalyst for cracking from hydro carbons to the light olefin transformation efficiency.
2. technology for preparing ethene and propylene in the catalytic pyrolysis mode, wherein hydrocarbon raw material contacts with catalyst for cracking, improvements comprise that the elementary catalyzer that an elementary temperature is provided contacts section and is positioned at the secondary catalyzer contact section that this elementary catalyzer contacts a secondary temperature in section downstream, and this secondary catalyzer contact section remains on than under the high temperature of elementary catalyzer contact section, and the hydrocarbon raw material of cracking is transferred to secondary catalyzer contact section from elementary catalyzer contact section.
3. technology for preparing ethene and propylene in the catalytic pyrolysis mode, wherein hydrocarbon raw material contacts with catalyst for cracking, improvements comprise that the elementary catalyzer that an elementary temperature is provided contacts section and is positioned at the secondary catalyzer contact section that this elementary catalyzer contacts a secondary temperature in section downstream, and this secondary catalyzer contact section remains on than under the high temperature of elementary catalyzer contact section, and the hydrocarbon raw material of cracking transferred to secondary catalyzer contact section from elementary catalyzer contact section, the temperature range of wherein elementary catalyzer contact section is at about 500~about 750 ℃, and secondary catalyzer contacts temperature high 10~150 ℃ scope of the temperature of section than elementary catalyzer contact section, and raw material is with about 0.1 Hr of scope -1WHSV~about 100 Hr -1The weight hourly space velocity of WHSV flows.
4. claim 2 or 3 technology, the temperature range of wherein elementary catalyzer contact section is about 500~about 750 ℃, the temperature of secondary catalyzer contact section is than high 10~150 ℃ scope of temperature of elementary catalyzer contact section, and raw material is with about 0.1 Hr of scope -1WHSV~about 100 Hr -1The weight hourly space velocity of WHSV flows.
5. claim 2 or 3 technology wherein contact with catalyzer when elementary catalyzer contact section temperature range is 600~700 ℃, and raw material are 1.0 Hr with scope -1WHSV~30 Hr -1The weight hourly space velocity of WHSV flows.
6. claim 2 or 3 technology, wherein elementary catalyzer contact section contacts the gradient of the temperature increase formation homogeneous between the section with secondary catalyzer.
7. claim 2 or 3 technology, wherein elementary catalyzer contact section contacts the gradient of the temperature increase formation homogeneous between the section with secondary catalyzer.
8. the technology of aforementioned any claim, wherein catalyst for cracking comprises that the silica alumina ratio scope is about 2.0: 1~2,000: 1 zeolite.
9. the technology of aforementioned any claim, its mesolite is selected from following thing group, comprises phillipsite, heulandite, mazzite, ferrierite, faujusite, chabazite, erionite, mordenite, offretite, sarcolite, euthalite, ZSM-5, ZSM-11, the ZSM-5/ZSM-11 intermediate, ZSM-12, ZSM-18, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, MCM-22, silicic acid gallium zeolite, zeolite-β, zeolite-ρ, ZK5, titanium silicate zeolite, ferrous silicate zeolite, borosilicate zeolites; By the zeolite of the Linde Division of Union Carbide with alphabetical X, Y, A, L name.
10. the technology of claim 1~7, wherein catalyzer comprises ZSM-5.
11. the technology of claim 1~7, wherein catalyzer comprises ZCAT40.
12. the technology of aforementioned any claim, wherein raw material is selected from following thing group, comprises ethane, propane, butane, raw gasline, gas oil, fischer-tropsch liquid, butylene, divinyl, steam cracking raw gasline, catalytic pyrolysis raw gasline, coker naphtha and kerosene.
13. the technology of aforementioned any claim, wherein in a reactor that is equipped with catalyzer contact entrance zone, threshold zone to contact exit zone with catalyzer, contact with catalyzer, the temperature range of this catalyzer contact entrance zone, threshold zone is 500~750 ℃, and catalyzer contact exit zone remains on high 10~150 ℃ scope of temperature than catalyzer contact entrance zone, threshold zone, and raw material is with about 0.1 Hr of scope -1WHSV~about 100 Hr -1The weight hourly space velocity of WHSV flows.
14. the technology of aforementioned any claim wherein contacts with catalyzer under scope is 550~725 ℃ temperature in.
15. the technology of aforementioned any claim, wherein raw material is 1.0 Hr with scope -1WHSV~50 Hr -1The weight hourly space velocity of WHSV flows.
16. the technology of aforementioned any claim wherein contacts with catalyzer under scope is 600~700 ℃ temperature in.
17. the technology of aforementioned any claim, wherein raw material is 1.0 Hr with scope -1WHSV~30 Hr -1The weight hourly space velocity of WHSV flows.
18. the technology of aforementioned any claim, wherein temperature increase forms the gradient of homogeneous.
CN 98805992 1997-06-10 1998-06-08 Hydrocarbon cracking with positive reactor temp. gradient Pending CN1259983A (en)

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