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CN101314126B - Steam cracking catalyst, preparation and application thereof - Google Patents

Steam cracking catalyst, preparation and application thereof Download PDF

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Publication number
CN101314126B
CN101314126B CN2007100998446A CN200710099844A CN101314126B CN 101314126 B CN101314126 B CN 101314126B CN 2007100998446 A CN2007100998446 A CN 2007100998446A CN 200710099844 A CN200710099844 A CN 200710099844A CN 101314126 B CN101314126 B CN 101314126B
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catalyst
calcium aluminate
aluminum
carrier
calcium
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CN101314126A (en
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张书红
王子军
崔德春
李萍
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

一种蒸汽裂解制低碳烯烃催化剂及其制备方法和应用，该催化剂含有1～10重量％的铝酸钙，90～99重量％的除铝酸钙之外的其他含铝化合物载体，比表面积为80～300m2/g。该催化剂具有孔结构适宜、催化活性高、反应温度低、机械强度高等优点。以及应用该催化剂制取低碳烯烃的方法，该方法具有空速高、转化率高、低碳烯烃产率高的优点。A catalyst for producing low-carbon olefins by steam cracking and its preparation method and application. The catalyst contains 1-10% by weight of calcium aluminate, 90-99% by weight of other aluminum-containing compound supports except calcium aluminate, and the specific surface area 80-300m 2 /g. The catalyst has the advantages of suitable pore structure, high catalytic activity, low reaction temperature, high mechanical strength and the like. And a method for preparing low-carbon olefins by using the catalyst, the method has the advantages of high space velocity, high conversion rate and high yield of low-carbon olefins.

Description

A kind of steam cracking catalyst and its production and application
Technical field
The invention relates to cracking petroleum hydrocarbon vapor and produce the catalyst and the application thereof of low-carbon alkene, in particular, the present invention is to be catalyst and the application thereof that raw material is produced ethene and propylene with the petroleum hydrocarbon.
Background technology
The tube furnace steam cracking technology dominates in petroleum hydrocarbon cracking ethylene preparation and production of propylene all the time, its technology is gradually improved, but the problem that exists mainly contains at present: the energy consumption height, and the steam cracking process consumed energy accounts for 40% of whole petrochemical enterprise at present; Ethene, propene yield are difficult to improve again, in recent years, because reaction condition harsh more (is that 900 ℃, the time of staying are 0.1 second as the millisecond furnace cracking temperature) is subjected to the restriction of furnace tube material, is difficult to improve ethene, propene yield by the severity that improves cracking reaction again; Harsh reaction condition makes the easier coking of boiler tube and has shortened the cycle of burning, and damages easily owing to carburizing makes boiler tube.Various countries researcher research thinks that the method for catalytic pyrolysis can effectively address the above problem.Catalytic pyrolysis is meant the hydrocarbon cracking reaction of carrying out in the presence of catalyst, can reduce reaction temperature, improves selectivity and product yield.
CN1317545A discloses a kind of catalyst for steam cracking reaction, by CaO/Al 2O 3Crystallization calcium aluminate and the oxide of molybdenum and/or vanadium of mol ratio in 1/6 to 3 scope form, described two kinds of oxide content sums are 0.5～10 weight %, its preparation method is at first to prepare the calcium aluminate presoma with the homogeneous phase preparation method, the calcium aluminate presoma makes the crystallization calcium aluminate 1300～1400 ℃ of roastings then, with the granular crystal calcium aluminate in the salting liquid that contains molybdenum and vanadium, flood, dry, roasting forms, this catalyst shows higher activity in steam cracking.
US2003070963A1 discloses a kind of hydrocarbon vapours cleavage method and consersion unit, and inside reactor has the coating that the coating of catalytic activity is calcium aluminate and alkali metal vanadate or pyrovanadic acid potassium in this method.
Calcium aluminate is because of the difference of CaO content, and CaO.6Al is arranged 2O 3, CaO.2Al 2O 3, 3CaO.5Al 2O 3, CaO.Al 2O 3, 5CaO.3Al 2O 3, 12CaO.7Al 2O 3, 2CaO.Al 2O 3And 3CaO.Al 2O 3Multiple thing phase, research think catalytic activity best be 12CaO.7Al 2O 3The calcium aluminate catalyst.But seldom about the report of calcium aluminate Preparation of Catalyst, generally all adopt corresponding calcium salt and aluminium salt mechanical mixture, through the method preparation of high-temperature roasting, owing to mix the influence of degree, can cause to have several calcium aluminate thing phases in the catalyst, influence its catalytic activity.
US20030109376A1 discloses a kind of preparation 12CaO.7Al 2O 3Method, the salting liquid of calcic and aluminium is mixed with multicomponent organic acid, be prepared into 12CaO.7Al through spray-drying and high-temperature roasting 2O 3Catalyst, but in preparation catalyst process, need 1300～1400 ℃ high-temperature roasting in this way, its energy consumption is very high, and the specific area of catalyst is very little simultaneously, makes activity of such catalysts center decreased number, and activity of such catalysts and conversion ratio are low.
Summary of the invention
One of purpose of the present invention provides a kind of moulding, mechanical strength height, steam cracking catalyst that catalytic activity is high of being easy to.
Two of purpose of the present invention provides a kind of preparation method of steam cracking catalyst.
Three of purpose of the present invention provides the method that a kind of steam cracking is produced low-carbon alkene.
Steam cracking catalyst provided by the invention, this catalyst contains the calcium aluminate of 1～10 weight %, other aluminum contained compound carriers except that calcium aluminate of 90～99 weight %, the specific area of this catalyst is 80～300m 2/ g.
Preferred this catalyst also contains and is not more than 3 weight %, preferredly consist of the calcium aluminate that this catalyst contains 1～9.9 weight %, other aluminum contained compound carriers except that calcium aluminate of 90～98.9 weight %, the rare earth oxide of 0.1～3 weight % and/or transition metal oxide.
In the catalyst provided by the invention, described catalyst is by the method for flooding calcium aluminate to be loaded on the aluminum contained compound carrier to obtain, or the method by step impregnation is calcium aluminate, and rare earth oxide and/or transition metal oxide load on and obtain on the aluminum contained compound carrier.
In the catalyst provided by the invention, CaO/Al in the described calcium aluminate 2O 3Mol ratio be 1/6～3, preferred CaO/Al 2O 3Mol ratio is 12/7 calcium aluminate.Described aluminum contained compound carrier is aluminium oxide or magnesium aluminate spinel compound, wherein preferred α-Al 2O 3
In the catalyst provided by the invention, described rare earth oxide and/or transition metal oxide are selected from cerium oxide, iron oxide, perovskite oxide and the manganese oxide one or more mixture, wherein preferred cerium oxide.
The calcium aluminate preparation method who reports in patent and the document generally has three kinds: (1) aluminium salt and calcium salt are through fully mixed, and roasting makes calcium aluminate under high temperature (more than 1300 ℃) then; (2) adopt the homogeneous phase preparation method that aluminium salt and calcium salt soln mixing back is spray-dried, ((more than 1300 ℃) roasting down make calcium aluminate at high temperature then; (3) on reactor, adopt the method for coating to make the calcium aluminate Catalytic Layer.All there is a problem in all these methods, and the specific area of the calcium aluminate catalyst that makes exactly is very little, so its active sites quantity is few.The method of employing step impregnation provided by the invention with the catalyst of active constituent loading on porous carrier have with prior art in the different microstructure of catalyst for preparing, active component is distributed in the top layer, duct of catalyst surface and porous carrier, improve specific surface area of catalyst, increased the active sites quantity that contacts with reactant.
Simultaneously, the inventor discovers that formed smooth surface became coarse when high temperature sintering originally after enclosing skim calcium aluminate active component on the carrier surface, so the specific area of carrier has increased about 20% after the load.
In calcium aluminate compound, add a small amount of rare earth oxide and/or transition metal oxide, can improve its activity in the steam cracking reaction process, obviously reduce reaction temperature.
The specific area of catalyst provided by the invention improves greatly than conventional calcium aluminate catalyst, by 0.25m 2/ g brings up to 86～185m 2/ g, average pore size is reduced to 86.4～175 dusts by 775 dusts, and pore structure is preferably; Pure calcium aluminate (12CaO.7Al with routine 2O 3) compare, the catalytic activity of catalyst provided by the invention (calcium aluminate content is 2.91%～8.97%) is higher, and conversion ratio improves 7.99～16.95 percentage points, and the productive rate of ethene+propylene+butadiene improves about 3.49～10.36 percentage points; Have also that reaction temperature is low, the mechanical strength advantages of higher.
The preparation method of steam cracking catalyst provided by the invention is respectively according to the contained component difference of catalyst:
The concrete steps that preparation only contains the catalyst of calcium aluminate, the aluminum contained compound carrier except that calcium aluminate are:
(1) salting liquid that will contain aluminium and calcium floods carrier;
(2) soaked carrier being placed temperature is to carry out drying in 100～150 ℃ the environment;
(3) the above-mentioned soaked carrier of roasting obtained catalyst at least in 2 hours in 800～1200 ℃ temperature range.
The concrete steps that preparation contains the catalyst of calcium aluminate, aluminum contained compound carrier, rare earth oxide and/or transition metal oxide except that calcium aluminate are:
(1) salting liquid that will contain aluminium and calcium floods carrier;
(2) soaked carrier being placed temperature is to carry out drying in 100～150 ℃ the environment;
(3) the above-mentioned soaked carrier of roasting at least 2 hours in 800～1200 ℃ temperature range;
(4) solution that will contain rare earth metal salt and/or transition metal salt floods the carrier of above-mentioned load crystalline phase calcium aluminate;
(5) soaked carrier being placed temperature is to carry out drying in 100～150 ℃ the environment;
(6) in 500～650 ℃ of temperature ranges, above-mentioned dried carrier roasting was obtained catalyst at least in 4 hours.
In the Preparation of catalysts method provided by the invention, the salt of described calcic is calcium acetate and/or calcium nitrate, and the described salt that contains aluminium is aluminum nitrate, describedly contains rare earth metal salt and/or transition metal salt is a nitrate.
The preparation method of steam cracking catalyst provided by the invention, sintering temperature is low, the saving energy consumption, and the requirement of active component is still less.
Steam cracking provided by the invention is produced the method for low-carbon alkene, is hydrocarbon oil crude material and steam are introduced in the reactor, and be that 720～800 ℃, water-oil factor are 0.5～2.0, air speed is 1～100h in temperature -1Condition under, contact with catalyst arbitrary in the claim 1～9 and to react, the separating reaction afterproduct obtains low-carbon alkene.
In the method provided by the invention, described hydrocarbon oil crude material is selected from one or more the mixture in C1～C8 lighter hydrocarbons, naphtha, kerosene, light diesel fuel and the heavy oil.
In the method provided by the invention, described reactor can be fixed bed reactors, also can be fluidized-bed reactor, moving-burden bed reactor or riser reactor.
The method that steam cracking provided by the invention is produced low-carbon alkene has the air speed height, conversion ratio height, the advantage that productivity of low carbon olefin hydrocarbon is high.As in embodiment and Comparative Examples as seen, method conversion ratio provided by the invention improves 7.99～16.95 percentage points, the productive rate of ethene+propylene+butadiene improves about 3.49～10.36 percentage points.
The specific embodiment
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Among Comparative Examples and the embodiment, the specific area of catalyst and average pore size adopt RIPP145-90 standard method (seeing volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publication) to measure by nitrogen adsorption capacity method;
Reagent among Comparative Examples and the embodiment is chemical pure.
Comparative Examples 1
The 12CaO.7Al of pure phase in the Comparative Examples 1 explanation prior art 2O 3The preparation method.
With 151 gram calcium nitrate (CaC 2H 6O 4H 2O) and 375.13 gram aluminum nitrate (Al (NO 3) 39H 2O) be dissolved in and make solution in the distilled water, add 393.1 gram citric acids.The spray-dried machine spray thing of the homogeneous phase solution of gained is also dry, 1350 ℃ of roastings 4 hours, makes crystalline phase calcium aluminate catalyst D, and structure is 12CaO.7Al 2O 3Measure the specific area and the average pore size of catalyst, and the crushing strength of catalyst, the results are shown in Table 1.
Embodiment 1～4 explanation Preparation of catalysts method provided by the invention.
Embodiment 1
With 500 gram α-Al 2O 3In the solution that contains 18.98 gram calcium acetates and 323.39 gram aluminum nitrates, carry out saturated dipping, then in 120 ℃ of dryings 4 hours, 850 ℃ of roastings 4 hours; Catalyst after the roasting is being contained 18.92 gram cerous nitrate (Ce (NO 3) 36H 2O) saturated dipping in the solution, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 5 hours, the catalyst A 1 that makes contains α-Al of 89.68% 2O 3Carrier, 8.97% calcium aluminate, CaO/Al 2O 3Mol ratio be 1/4, contain 1.35% cerium oxide.Measure the specific area and the average pore size of catalyst, and the crushing strength of catalyst, the results are shown in Table 1.
Embodiment 2
With 500 gram α-Al 2O 3In the solution that contains 27.87 gram calcium acetates and 118.71 gram aluminum nitrates, carry out saturated dipping, then in 120 ℃ of dryings 4 hours, 900 ℃ of roastings 4 hours; With the saturated dipping in the solution that contains 31.53 gram cerous nitrates of the catalyst after the roasting, flooded back 110 ℃ of dryings 4 hours, 500 ℃ of roastings 5 hours, the catalyst A 2 that makes contains α-Al of 93.02% 2O 3Carrier, 4.65% calcium aluminate, CaO/Al 2O 3Mol ratio be 1/1, contain 2.33% cerium oxide.Measure the specific area and the average pore size of catalyst, and the crushing strength of catalyst, the results are shown in Table 1.
Embodiment 3
With 500 gram α-Al 2O 3Containing 71.56 gram calcium nitrate (Ca (NO 3) 24H 2O) and in the solution of 132.62 gram aluminum nitrates carry out saturated dipping, then in 120 ℃ of dryings 4 hours, 1000 ℃ of roastings 4 hours; Catalyst after the roasting is being contained 20.2 gram ferric nitrate (Fe (NO 3) 39H 2O) saturated dipping in the solution, 110 ℃ of dryings 4 hours, 600 ℃ of roastings 4 hours, the catalyst A 3 that makes contains α-Al of 92.76% 2O 3Carrier, 6.49% calcium aluminate, CaO/Al 2O 3Mol ratio be 12/7, contain 0.75% iron oxide.Measure the specific area and the average pore size of catalyst, and the crushing strength of catalyst, the results are shown in Table 1.
Embodiment 4
500 gram magnesium aluminate spinels are carried out saturated dipping in the solution that contains 27.3 gram calcium acetates and 46.5 gram aluminum nitrates, then in 120 ℃ of dryings 4 hours, 1100 ℃ of roastings 4 hours, the catalyst A 4 that makes contains 97.09% magnesium aluminate spinel, 2.91% calcium aluminate, CaO/Al 2O 3Mol ratio be 5/2.Measure the specific area and the average pore size of catalyst, and the crushing strength of catalyst, the results are shown in Table 1.
Comparative Examples 2
The effect that the catalytic pyrolysis hydrocarbon ils of the pure crystalline phase calcium aluminate catalyst of this Comparative Examples explanation Comparative Examples 1 preparation is produced low-carbon alkene.
On the small fixed catalyst test apparatus, reactor capacity is 10ml, the catalyst D that Comparative Examples is made packs in the reactor, in reactor, feed normal octane and water vapour, carry out steam cracking reaction, separating obtained gaseous products is analyzed with gas-chromatography, and feedstock property sees Table 2, reaction condition and the results are shown in Table 3.
The effect that embodiment 5～8 explanations catalyst cracking hydrocarbon ils provided by the invention is produced low-carbon alkene.
Embodiment 5
The catalyst A 1 that embodiment 1 is made is packed in the fixed bed reactors, in reactor, feed normal octane and water vapour, carry out steam cracking reaction, separating obtained gaseous products is analyzed with gas-chromatography, feedstock property sees Table 2, reaction condition and the results are shown in Table 3.
Embodiment 6
The catalyst A 2 that embodiment 2 is made is packed in the fixed bed reactors, in reactor, feed naphtha and water vapour, carry out steam cracking reaction, separating obtained gaseous products is analyzed with gas-chromatography, feedstock property sees Table 2, reaction condition and the results are shown in Table 3.
Embodiment 7
The catalyst A 3 that embodiment 3 is made is packed in the fixed bed reactors, in reactor, feed light diesel fuel and water vapour, carry out steam cracking reaction, separating obtained gaseous products is analyzed with gas-chromatography, feedstock property sees Table 2, reaction condition and the results are shown in Table 3.
Embodiment 8
The catalyst A 4 that embodiment 3 is made is packed in the fixed bed reactors, feeds heavy oil and water vapour in reactor, carries out steam cracking reaction, and separating obtained gaseous products is analyzed with gas-chromatography, and feedstock property sees Table 2, reaction condition and the results are shown in Table 3.
Table 1
Comparative Examples 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Catalyst D A1 A2 A3 A4
Form Calcium aluminate 100% α-Al 2O 389.68% calcium aluminate, 8.97% cerium oxide 1.35% α-Al 2O 393.02% calcium aluminate, 4.65% cerium oxide 2.33% α-Al 2O 392.76% calcium aluminate, 6.49% iron oxide 0.75% Magnesium aluminate spinel 97.09% calcium aluminate 2.91%
CaO/Al 2O 3 12/7 1/4 1/1 12/7 5/2
Specific area, m 2/g 0.25 136 185 154 86
Average pore size, dust 775 175 86.4 126 157
Crushing strength, kg/cm 2 2.3 19.7 19.7 19.7 19.7
By data in the table 1 as seen, compare with conventional calcium aluminate catalyst, specific surface area of catalyst provided by the invention improves, by 0.25m 2/ g brings up to 86～185m 2/ g, average pore size is reduced to 86.4～175 dusts by 775 dusts, and pore size distribution is more reasonable.Because crushing strength has directly reflected the mechanical strength of catalyst, the mechanical strength of visible catalyst has improved 7.5 times.
Table 2
Normal octane Naphtha Light diesel fuel Heavy oil
Density (20 ℃), g/cm 3 0.703 0.7374 0.8090 0.8425
The BMCI value -0.03 19.48 17.58 22.54
Refractive power, n d 20 1.3976 1.4163 1.4528
Elementary analysis Cm%Hm%SppmNppm 84.2115.7900 85.2014.731101.1 85.9314.0046754.47 86.1113.771234292
Boiling range, ℃ IBP10%～30%50%～70%90%～95%FBP 125.7125.7125.7125.7125.7 4277～103119～135152～159169 167205～242276～304339～356>360 227298～332355～376396～405420
Table 3
By table 3 data as seen, with the pure calcium aluminate (12CaO.7Al of routine 2O 3) compare, the activity of catalyst provided by the invention (calcium aluminate content is 2.91%～8.97%) is higher, and conversion ratio improves 7.99～16.95 percentage points, and the productive rate of ethene+propylene+butadiene improves about 3.49～10.36 percentage points.

Claims (11)

1.一种蒸汽裂解制低碳烯烃催化剂，其特征在于该催化剂含有1～10重量％的铝酸钙，90～99重量％的除铝酸钙之外的其他含铝化合物载体，还含有不大于3重量％的稀土氧化物和/或过渡金属氧化物，该催化剂的比表面积为80～300m2/g；所述的稀土氧化物和/或过渡金属氧化物选自氧化铈、氧化铁、钙钛矿氧化物和氧化锰中一种或几种的混合物。1. A catalyst for producing low-carbon olefins by steam cracking, characterized in that the catalyst contains 1 to 10% by weight of calcium aluminate, 90 to 99% by weight of other aluminum-containing compound carriers except calcium aluminate, and also contains not More than 3% by weight of rare earth oxides and/or transition metal oxides, the specific surface area of the catalyst is 80-300m 2 /g; the rare earth oxides and/or transition metal oxides are selected from cerium oxide, iron oxide, One or more mixtures of perovskite oxide and manganese oxide. 2.按照权利要求1的催化剂，其特征在于所述的催化剂含有1～9.9重量％的铝酸钙，90～98.9重量％的除铝酸钙之外的其他含铝化合物载体，0.1～3重量％的稀土氧化物和/或过渡金属氧化物。2. according to the catalyst of claim 1, it is characterized in that described catalyst contains the calcium aluminate of 1～9.9 weight %, 90～98.9 weight % except calcium aluminate other aluminum-containing compound supports, 0.1～3 weight % % rare earth oxides and/or transition metal oxides. 3.按照权利要求1或2的催化剂，其特征在于该催化剂是通过浸渍的方法将铝酸钙负载在含铝化合物载体上得到的，或者是通过分步浸渍的方法将铝酸钙，稀土氧化物和/或过渡金属氧化物负载在含铝化合物载体上得到的。3. The catalyst according to claim 1 or 2, characterized in that the catalyst is obtained by impregnating calcium aluminate on an aluminum-containing compound carrier, or by stepwise impregnating calcium aluminate, rare earth oxidation compounds and/or transition metal oxides supported on aluminum-containing compound supports. 4.按照权利要求1或2的催化剂，其特征在于所述的含铝化合物载体为氧化铝或镁铝尖晶石化合物。4. The catalyst according to claim 1 or 2, characterized in that said aluminum-containing compound carrier is alumina or magnesium aluminum spinel compound. 5.按照权利要求4的催化剂，其特征在于所述的含铝化合物载体为α-Al2O3。5. The catalyst according to claim 4, characterized in that said aluminum-containing compound support is α-Al 2 O 3 . 6.按照权利要求1的催化剂，其特征在于所述的铝酸钙中CaO/Al2O3摩尔比为1/6～3。6. The catalyst according to claim 1, characterized in that the molar ratio of CaO/Al 2 O 3 in said calcium aluminate is 1/6-3. 7.按照权利要求1的催化剂，所述的稀土氧化物为氧化铈。7. The catalyst according to claim 1, wherein said rare earth oxide is cerium oxide. 8.权利要求1或2的催化剂的制备方法，其特征在于该方法的具体步骤为：8. the preparation method of the catalyst of claim 1 or 2 is characterized in that the concrete steps of the method are: (1)将含有铝和钙的盐溶液对载体进行浸渍；(1) impregnating the carrier with a salt solution containing aluminum and calcium; (2)将浸渍后的载体置于温度为100～150℃的环境内进行干燥；(2) drying the impregnated carrier in an environment with a temperature of 100-150°C; (3)在800～1200℃的温度范围内焙烧上述浸渍后的载体至少2小时；(3) calcining the impregnated carrier at a temperature of 800-1200° C. for at least 2 hours; (4)将含有稀土金属盐和/或过渡金属盐的溶液对上述负载晶相铝酸钙的载体进行浸渍；(4) impregnating the above-mentioned carrier loaded with crystal phase calcium aluminate with a solution containing rare earth metal salt and/or transition metal salt; (5)将浸渍后的载体置于温度为100～150℃的环境内进行干燥；(5) drying the impregnated carrier in an environment with a temperature of 100-150°C; (6)在500～650℃温度范围内对上述干燥后的载体焙烧至少4小时得到催化剂。(6) Calcining the above-mentioned dried carrier at a temperature range of 500-650° C. for at least 4 hours to obtain a catalyst. 9.按照权利要求8的制备方法，其特征在于所述的含钙的盐为醋酸钙和/或硝酸钙，所述的含铝的盐为硝酸铝，所述的稀土金属盐和/或过渡金属盐为硝酸盐。9. according to the preparation method of claim 8, it is characterized in that described calcium-containing salt is calcium acetate and/or calcium nitrate, and described aluminum-containing salt is aluminum nitrate, and described rare earth metal salt and/or transition Metal salts are nitrates. 10.一种蒸汽裂解生产低碳烯烃的方法，其特征在于将烃油原料和水蒸气引入反应器中，在温度为720～800℃、水油比为0.5～2.0、空速为1～100h-1的条件下，与权利要求1～7中任一的催化剂接触进行反应，分离反应后产物得到低碳烯烃。10. A method for steam cracking to produce light olefins, characterized in that hydrocarbon oil feedstock and water vapor are introduced into a reactor at a temperature of 720-800°C, a water-to-oil ratio of 0.5-2.0, and a space velocity of 1-100h Under the condition of -1 , contact with any catalyst in claims 1 to 7 to react, separate the reaction product to obtain low carbon olefins. 11.按照权利要求10的方法，其特征在于所述的烃油原料选自C1～C8轻烃、石脑油、煤油、轻柴油和重油中的一种或几种的混合物。11. according to the method for claim 10, it is characterized in that described hydrocarbon oil raw material is selected from the mixture of one or more in C1～C8 light hydrocarbon, naphtha, kerosene, light diesel oil and heavy oil.
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