CN101279285A - Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene - Google Patents
Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene Download PDFInfo
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Abstract
The present invention relates to a catalyst used for manufacturing ethylene and propylene by naphtha catalytic pyrolysis which mainly solves the problems of high reaction temperature and low ethylene and propylene yield of the existing catalyst to manufacture ethylene and propylene by catalytic pyrolysis. The present invention better solves the problems by adopting the technical proposal of loading at least one element or the oxide thereof of the IVB group, or the VB group in the periodic table of elements on the symbiosis molecular sieves of ZSM-5 and mordenite zeolites, ZSM-5 and Beta zeolites or ZSM-5 and Y zeolites to compose the catalyst. The present invention can be used for the industrial production of ethylene and propylene by naphtha catalytic pyrolysis.
Description
Technical field
The present invention relates to a kind of catalyst that is used for naphtha catalytic pyrolysis preparing ethylene propylene.
Background technology
Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half.Whole world ethene is raw material with naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of total output.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard cracking reactions, and therefore than common steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; CO2 emission also can reduce, and can adjust the product mix flexibly, can increase the total recovery of ethene and propylene, and production cost of ethylene reduces significantly.
U.S. Pat P6211104 and domestic patent CN1504540A adopt a kind of 10～70 weight % clays that contain, 5～85 weight % inorganic oxides, 1～50 weight % molecular sieve is formed catalyst, various raw materials to traditional steam heat cracking, the activity, the especially ethene that well are converted into light olefin have been demonstrated.With molecular sieve be by 0～25 weight %Y zeolite of high silica alumina ratio or have the ZSM molecular sieve of MFI structure, form by phosphorus/Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyst and yield are not high.
Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the molecular sieve of aperture between 0.5～0.65 nanometer are catalyst, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower.
Exxon Mobil (00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550～600 ℃, and conversion of raw material is lower.
Mobil Oil Corporation (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyst and elementary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the serviceability temperature of catalyst, conversion of raw material and product yield are all lower.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst activity that uses in the existing naphtha catalytic pyrolysis preparing ethylene propylene reaction is lower, the problem that the yield of ethylene, propylene is low, reaction temperature is high provides a kind of new catalyst that is used for naphtha catalytic pyrolysis preparing ethylene propylene.This catalyst has the catalytic activity height, ethylene propylene yield height, the advantage that reaction temperature is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for preparing ethylene propylene from catalytic pyrolysis comprises following active component by weight percentage:
A) at least a in the coexisting molecular sieve of the coexisting molecular sieve of 80～99.5% the coexisting molecular sieve that is selected from ZSM-5 and modenite, ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry thereon
B) surplus is selected from least a element or its oxide in periodic table of elements IVB family's element or the VB family element.
In the technique scheme, coexisting molecular sieve is at least a in ZSM-5/ mercerization zeolite symbiosis molecular screen, ZSM-5/ beta zeolite coexisting molecular sieve and the ZSM-5/Y zeolite coexisting molecular sieve; The weight percentage preferable range of ZSM-5 is 60～99.5% in the used coexisting molecular sieve, and more preferably scope 80～99%; The silica alumina ratio preferable range of used coexisting molecular sieve is 10～300, and more preferably scope is 12～50; The quality consumption preferable range of coexisting molecular sieve is 85～99% by weight percentage.IVB family element preferred version is to be selected from least a among Ti, Zr or the Hf; VB family element preferred version is to be selected from least a among V, Nb or the Ta; Be selected from the consumption preferable range 0.01～2% of at least a or its oxide in periodic table of elements IVB family's element or the VB family element by weight percentage, more preferably scope is 0.1～1%.
The raw material that the preparation coexisting molecular sieve uses: the silicon source is metasilicate, silicate sodium or Ludox, the aluminium source is aluminium salt or aluminate, the template agent is at least a in 4-propyl bromide, TPAOH, triethylamine, n-butylamine, tetraethyl ammonium hydroxide, ethylenediamine or the ethamine, and the pH value of regulating colloidal sol with diluted acid is 10～13.The coexisting molecular sieve modification is with the acid solution and the salting liquid of corresponding active component element.
The synthetic method of coexisting molecular sieve is, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds one or more template agent of aequum then, stirs after a period of time with rare acid for adjusting pH value in 10～13 scopes, supply distilled water again, add the corresponding crystal seed of aequum.Colloidal sol is put into autoclave, control temperature crystallization a period of time of 150～170 ℃ after, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours, can obtain corresponding coexisting molecular sieve.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make the Hydrogen coexisting molecular sieve.
The present invention since adopted acid strong, have multi-stage artery structure, ethylene, propylene selectivity good coexisting molecular sieve be carrier, select for use transition metal that coexisting molecular sieve is carried out modification with the easy transition of the big electronics of charge density, strengthen the hydrothermal stability and the acidity of coexisting molecular sieve, make the catalyst acid density that makes big, the acid strength height, acid stable is difficult for running off, and is suitable for alkane cracking and becomes ethylene, propylene.
In order to check and rate activity of such catalysts, the related catalyst compressing tablet of invention, break into pieces, sieve after, get 20～40 purpose particles with standby.The C that adopts Shanghai Gaoqiao petro-chemical corporation to produce
4～C
10The naphtha of hydrocarbon is a raw material, naphtha physical index such as table 1.With internal diameter is 12 millimeters down examination of fixed bed reactors normal pressure, is 600～700 ℃ in reaction temperature, and reaction pressure is 0.001MPa～0.5MPa, and weight space velocity is 0.25～4 hour
-1, under the condition of water/feedstock oil weight ratio 1～4: 1, naphtha being carried out catalytic pyrolysis, the ethylene, propylene yield can reach 54%, has obtained better technical effect.
Table 1 feed naphtha index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.18 |
| N-alkane % (weight %) in the alkane | ＞32.5 |
| Cycloalkane % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, stir after 30 minutes, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, add the crystal seed that contains ZSM-5 and modenite presoma, stir and after 30 minutes mixed solution is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the coexisting molecular sieve of ZSM-5 and modenite, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 and modenite weight content be respectively 95% and 5%.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5 and mercerization zeolite symbiosis molecular screen, be designated as FH-1.
[embodiment 2]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 16.7 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram ethylenediamines and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring a period of time, regulate the pH value 11 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.05: 0.4: 40, add 2.8 gram β zeolite seed crystals, mixed solution is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ beta zeolite coexisting molecular sieve, the XRD diffracting spectrum is shown in curve among Fig. 11, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 weight percentage be 94.6%, the β zeolite is 5.4%.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve, be designated as FH-2.
[embodiment 3]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, stir after 20 minutes, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, add 2.8 gram Y zeolite seed crystals, mixed solution is put into autoclave, 130 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/Y zeolite coexisting molecular sieve.Quantitatively contain 94.5% ZSM-5 and 5.5% Y zeolite as can be known in the coexisting molecular sieve by weight percentage with the XRD diffraction.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5/Y zeolite coexisting molecular sieve, be designated as FH-3.
[embodiment 4～7]
The Hydrogen ZSM-5/Y zeolite coexisting molecular sieve that the Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen that embodiment 1 is made, the Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve that embodiment 2 makes and embodiment 3 make mixes according to a certain percentage, make mechanical impurity, as shown in table 2.
Table 2
| Embodiment | The coexisting molecular sieve kind | Ratio (weight ratio) | Sample number into spectrum |
| Embodiment 4 | ZSM-5/ modenite+ZSM-5/ β zeolite | 1∶1 | FH-4 |
| Embodiment 5 | ZSM-5/ modenite+ZSM-5/Y zeolite | 1∶1 | FH-5 |
| Embodiment 6 | ZSM-5/ β zeolite+ZSM-5/Y zeolite | 1∶1 | FH-6 |
| Embodiment 7 | ZSM-5/ modenite+ZSM-5/ β zeolite+ZSM-5/Y zeolite | 1∶1∶1 | FH-7 |
[embodiment 8～25]
According to the method for embodiment 1, embodiment 2 and embodiment 3,, make a collection of Hydrogen coexisting molecular sieve respectively by changing the amount of feed molar proportioning, pH value and adding crystal seed, as shown in table 3.
Table 3
| Embodiment | The coexisting molecular sieve type | SiO 2/Al 2O 3Mol ratio | ZSM-5 content (weight %) | Sample number into spectrum |
| Embodiment 8 | The ZSM-5/ modenite | 12 | 61.5 | FH-8 |
| Embodiment 9 | The ZSM-5/ modenite | 16 | 73.6 | FH-9 |
| Embodiment 10 | The ZSM-5/ modenite | 40 | 85.4 | FH-10 |
| Embodiment 11 | The ZSM-5/ modenite | 100 | 96.8 | FH-11 |
| Embodiment 12 | The ZSM-5/ modenite | 300 | 99.2 | FH-12 |
| Embodiment 13 | The ZSM-5/ modenite | 20 | 90.1 | FH-13 |
| Embodiment 14 | ZSM-5/ β zeolite | 12 | 98.0 | FH-14 |
| Embodiment 15 | ZSM-5/ β zeolite | 20 | 90.4 | FH-15 |
| Embodiment 16 | ZSM-5/ β zeolite | 60 | 60.5 | FH-16 |
| Embodiment 17 | ZSM-5/ β zeolite | 100 | 74.6 | FH-17 |
| Embodiment 18 | ZSM-5/ β zeolite | 300 | 85.3 | FH-18 |
| Embodiment 19 | ZSM-5/ β zeolite | 40 | 99.0 | FH-19 |
| Embodiment 20 | The ZSM-5/Y zeolite | 12 | 60.2 | FH-20 |
| Embodiment 21 | The ZSM-5/Y zeolite | 16 | 71.8 | FH-21 |
| Embodiment 22 | The ZSM-5/Y zeolite | 50 | 85.3 | FH-22 |
| Embodiment 23 | The ZSM-5/Y zeolite | 100 | 97.3 | FH-23 |
| Embodiment 24 | The ZSM-5/Y zeolite | 300 | 99.5 | FH-24 |
| Embodiment 25 | The ZSM-5/Y zeolite | 20 | 91.0 | FH-25 |
[embodiment 26]
Get ZSM-5/ mercerization zeolite symbiosis molecular screen 20 grams that embodiment 1 makes, 83.5 milliliters of Titanium Nitrates that add 0.05 mol stir evaporates to dryness at 70 ℃ then, 120 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours make the ZSM-5/ mercerization zeolite symbiosis molecular screen catalyst of titanium modification.The catalyst compressing tablet, break into pieces, sieve after, get 20～40 purpose particles and put into fixed bed reactors, be 0.02MPa, weight space velocity 1 hour in 650 ℃ of reaction temperatures, reaction pressure
-1, check and rate under water/condition of 3: 1 of feedstock oil weight ratio, the results are shown in Table 4.
[embodiment 27～31]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 26.
[embodiment 32]
Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 2 makes, 8.8 milliliters of zirconium nitrates that add 0.05 mol, stir evaporate to dryness at 70 ℃ then, behind the drying and roasting, 50.1 milliliters of Titanium Nitrates that add 0.05 mol again, stir evaporate to dryness at 70 ℃, behind the drying and roasting, make the ZSM-5/Y zeolite coexisting molecular sieve catalyst of modification zirconium and titanium modification.Method examination according to embodiment 26 the results are shown in Table 4.
[embodiment 33～37]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 32.
[embodiment 38]
Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 3 makes, 51.8 milliliters of Titanium Nitrates that add 0.05 mol, 21.5 milliliters of nitric acid niobiums that add 0.05 mol again, stir evaporate to dryness at 70 ℃ then, behind the drying and roasting, make the ZSM-5/Y zeolite coexisting molecular sieve catalyst of titanium and titanium modification.Method examination according to embodiment 26 the results are shown in Table 4.
[embodiment 39～45]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 38.
[embodiment 46～53]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 38.
Table 4
| Embodiment | The numbering of specimen in use | The type of modifying element and content (weight %) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 26 | FH-1 | 1％Ti | 21.65 | 28.21 | 49.86 |
| Embodiment 27 | FH-4 | 0.5％Zr | 22.62 | 28.89 | 51.51 |
| Embodiment 28 | FH-6 | 0.2％Hf | 23.20 | 23.77 | 46.97 |
| Embodiment 29 | FH-7 | 0.5％V | 18.64 | 28.55 | 47.19 |
| Embodiment 30 | FH-14 | 0.2％Nb | 23.24 | 25.62 | 48.86 |
| Embodiment 31 | FH-20 | 1％Ta | 23.55 | 24.68 | 48.23 |
| Embodiment 32 | FH-2 | 0.2％Zr+0.6％Ti | 28.88 | 23.56 | 52.44 |
| Embodiment 33 | FH-5 | 0.5％Hf+0.5％Zr | 22.05 | 26.46 | 48.51 |
| Embodiment 34 | FH-8 | 0.2％V+0.2％Nb | 29.87 | 23.66 | 53.53 |
| Embodiment 35 | FH-15 | 0.2％V+0.2％Ta | 25.54 | 26.42 | 51.96 |
| Embodiment 36 | FH-21 | 0.2％Ta+0.2％Nb | 23.42 | 25.85 | 49.27 |
| Embodiment 37 | FH-25 | 0.5％Ti+0.5％V | 24.44 | 26.32 | 50.76 |
| Embodiment 38 | FH-3 | 0.5％Ti+0.5％Nb | 28.62 | 24.31 | 52.93 |
| Embodiment 39 | FH-9 | 0.5％Ti+0.5％Ta | 28.33 | 25.16 | 53.49 |
| Embodiment 40 | FH-11 | 0.2％Zr+0.2％V | 25.79 | 26.64 | 52.43 |
| Embodiment 41 | FH-13 | 0.2％Zr+0.2％Nb | 23.47 | 26.56 | 50.03 |
| Embodiment 42 | FH-16 | 0.2％Zr+0.2％Ta | 23.90 | 27.49 | 51.39 |
| Embodiment 43 | FH-18 | 0.5％Hf+0.5％V | 23.04 | 26.88 | 49.92 |
| Embodiment 44 | FH-22 | 0.5％Hf+0.5％Nb | 23.24 | 27.46 | 50.70 |
| Embodiment 45 | FH-24 | 0.5％Hf+0.5％Ta | 23.22 | 26.93 | 50.15 |
| Embodiment 46 | FH-10 | 0.2％Ti+0.2％Zr+0.2％Hf | 28.75 | 23.27 | 52.02 |
| Embodiment 47 | FH-12 | 0.5％V+0.5％Nb+0.5％Ta | 27.75 | 23.64 | 51.39 |
| Embodiment 48 | FH-17 | 0.5％Ti+0.5％V+0.5％Zr | 23.29 | 27.66 | 50.95 |
| Embodiment 49 | FH-19 | 0.5％Ti+0.5％V+0.5％Nb | 23.33 | 28.25 | 51.58 |
| Embodiment 50 | FH-23 | 0.2％Ti+0.2％Zr+0.2％V +0.2％Nb | 24.61 | 26.90 | 51.51 |
| Embodiment 51 | FH-3 | 0.2％Ti+0.2％Zr+0.2％V +0.2％Ta | 28.67 | 25.62 | 54.29 |
| Embodiment 52 | FH-5 | 0.2％Ti+0.2％Zr+0.2％V +0.2％Nb+0.2％Ta | 27.60 | 26.28 | 53.88 |
| Embodiment 53 | FH-7 | 0.2％Ti+0.2％Hf+0.2％Zr+ 0.2％V+0.2％Nb+0.2％Ta | 28.15 | 25.20 | 53.35 |
[comparative example 1]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 40 ZSM-5 molecular sieve, according to the method modification of embodiment 46, makes the catalyst of cerium and modified zirconia, checks and rates result such as table 5 according to the mode of embodiment 46.
[comparative example 2]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 20 modenite, according to the method modification of embodiment 41, makes the catalyst of neodymium, zirconium and titanium modification, checks and rates result such as table 5 according to the mode of embodiment 41.
[comparative example 3]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 40 β zeolite, according to the method modification of embodiment 49, makes the catalyst of lanthanum, cerium, zirconium and niobium modification, checks and rates result such as table 5 according to the mode of embodiment 49.
[comparative example 4]
Get the SiO that Shanghai petrochemical industry research institute produces
2/ Al
2O
3Mol ratio is 20 Y zeolite, according to the method modification of embodiment 37, makes the catalyst of cerium, neodymium, vanadium and niobium modification, checks and rates result such as table 5 according to the mode of embodiment 37.
Table 5
| Comparative example | Used molecular sieve type | The type of modifying element and content (weight %) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Comparative example 1 | ZSM-5 | 0.2％Ti+0.2％Zr+0.2％Hf | 23.23 | 24.34 | 47.57 |
| Comparative example 2 | Modenite | 0.2％Zr+0.2％Nb | 22.60 | 22.55 | 45.15 |
| Comparative example 3 | The β zeolite | 0.5％Ti+0.5％V+0.5％Nb | 22.24 | 22.30 | 44.54 |
| Comparative example 4 | The Y zeolite | 0.5％Ti+0.5％V | 21.29 | 22.37 | 43.66 |
Claims (6)
1. catalyst that is used for naphtha catalytic pyrolysis preparing ethylene propylene comprises following component by weight percentage:
A) at least a in the coexisting molecular sieve of the coexisting molecular sieve of 80～99.5% the coexisting molecular sieve that is selected from ZSM-5 and modenite, ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry thereon
B) surplus is selected from least a element or its oxide in periodic table of elements IVB family's element or the VB family element.
2. according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that the weight percentage of ZSM-5 molecular sieve is 60～99.5% in ZSM-5/ mercerization zeolite symbiosis molecular screen, ZSM-5/ beta zeolite coexisting molecular sieve or the ZSM-5/Y zeolite coexisting molecular sieve; The SiO of coexisting molecular sieve
2/ Al
2O
3Mol ratio is 10～300; The coexisting molecular sieve consumption is 85～99% by weight percentage.
3. according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 2, it is characterized in that the SiO of coexisting molecular sieve
2/ Al
2O
3Mol ratio is 12～50; The weight percentage of ZSM-5 molecular sieve is 80～99%.
4. according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that IVB family element is selected from least a among Ti, Zr or the Hf; VB family element is selected from least a among V, Nb or the Ta.
5. according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, its feature in being selected from periodic table of elements periodic table IVB family's element or VB family element by weight percentage at least a element or the consumption of its oxide be 0.01～2%.
6. according to the catalyst of the described naphtha catalytic pyrolysis preparing ethylene propylene of claim 5, its feature in being selected from periodic table of elements periodic table IVB family's element or VB family element by weight percentage at least a element or the consumption of its oxide be 0.1～1%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863308A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing olefin by catalyzing and cracking naphtha |
| CN106552673A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of catalyst for preparing olefin by catalytic cracking and preparation method thereof |
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| DE69907935T2 (en) * | 1998-09-22 | 2004-03-11 | Exxonmobil Chemical Patents Inc., Baytown | METHOD FOR THE PRODUCTION OF ZEOLITHS WITH A HIGH SIO2 CONTENT BONDED BY ZEOLITH AND THEIR USE |
| CN1194891C (en) * | 2002-02-01 | 2005-03-30 | 中国石油天然气股份有限公司 | Composite molecular sieve and preparing process thereof |
| CN1296276C (en) * | 2003-06-30 | 2007-01-24 | 中国石油化工股份有限公司 | Synthetic method for ZSM-5/mordenite mixed crystal material |
| CN1332759C (en) * | 2004-01-19 | 2007-08-22 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 and beta zeolite mixed crystal material |
| CN100443168C (en) * | 2005-08-15 | 2008-12-17 | 中国石油化工股份有限公司 | Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102863308A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing olefin by catalyzing and cracking naphtha |
| CN102863308B (en) * | 2011-07-07 | 2014-05-28 | 中国石油化工股份有限公司 | Method for preparing olefin by catalyzing and cracking naphtha |
| CN106552673A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of catalyst for preparing olefin by catalytic cracking and preparation method thereof |
| CN106552673B (en) * | 2015-09-30 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of catalyst for preparing olefin by catalytic cracking and preparation method thereof |
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