CN101306972A - Process for preparing ethylene and propylene by catalytic scission reaction - Google Patents
Process for preparing ethylene and propylene by catalytic scission reaction Download PDFInfo
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- CN101306972A CN101306972A CNA2007100407018A CN200710040701A CN101306972A CN 101306972 A CN101306972 A CN 101306972A CN A2007100407018 A CNA2007100407018 A CN A2007100407018A CN 200710040701 A CN200710040701 A CN 200710040701A CN 101306972 A CN101306972 A CN 101306972A
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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
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- 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
Abstract
The invention relates to a method for making ethylene and propylene through catalytic cracking, mainly solving the problems of the prior method for making ethylene and propylene through catalytic cracking including high use temperature of catalyst, low activity and poor selectivity of ethylene and propylene. The method solves the problems better through adopting the following technical proposal that: the method takes the solid super acid consisting of the VIB group elements or the VIB group elements and the IVB group elements in the periodic table of elements and loaded on a symbiosis molecular sieve as catalyst, and naphtha with the component being C4-C10 as a raw material so as to carry out catalytic cracking reaction at a temperature of between 550 and 700 DEG C, under a pressure of between 0.01 and 0.5 MPa, at a reaction weight space velocity of between 0.1 and 4 hours<-1> and with the weight ratio between water and naphtha of between 0.5:1 and 4:1, thereby generating ethylene and propylene. Moreover, the method can be used in the industrial production of ethylene and propylene through adopting catalytic cracking.
Description
Technical field
The present invention relates to a kind of method of preparing ethylene propylene from catalytic pyrolysis, can be used in the industrial production of naphtha catalytic pyrolysis preparing ethylene propylene.
Background technology
Ethylene, propylene industry has critical role as the tap of petrochemical industry in the national economic development.Along with the development of society, the market requirement of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and derived product thereof increases year by year, and the home products share of market is less than half.More than 100,000,000 ton of ethene is produced in the whole world per year at present, is raw material with petroleum naphtha (or ethane) mainly, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of ultimate production.But steam cracking needs high temperature of reaction, and energy consumption is big, needs expensive high temperature alloy steel, and the operational cycle is short, and the boiler tube life-span is low, discharge great amount of carbon dioxide, and the ethylene, propylene yield is lower, has restricted further developing of ethylene industry.
Catalytic pyrolysis also is one of important method of producing ethylene, propylene.It is under the condition that catalyzer exists, and petroleum hydrocarbon is carried out the process that catalytic pyrolysis is produced low-carbon alkene.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of equivalent steam scission reactions, and therefore than steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; Carbon emission also can reduce, and can adjust the product mix flexibly.Compare with steam cracking technology, this new technology can also increase the total recovery of ethene and propylene, produces the used feed naphtha of equal amts ethene and can reduce, and production cost of ethylene reduces significantly.Therefore, the preparing ethylene propylene from catalytic pyrolysis technology is as realizing industrialization, is that the petrochemical industry of raw material brings huge economic benefit with giving ethylene, propylene.
The ZSM-5 molecular sieve is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability preferably.
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 catalyzer, to the various raw materials of traditional steam heat cracked, 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 catalyzer 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 catalyzer, 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 petroleum 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 Corp. (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyzer and primary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the use temperature of catalyzer, conversion of raw material and product yield are all lower.
Be in the catalytic cracking reaction of raw material with the petroleum naphtha, for make in the petroleum naphtha contained just, the isoparaffin cracking generates alkene, and higher energy need be provided.Therefore to select strength of acid and the bigger catalytic material of sour density for use.
Solid super-strong acid is because acidity is stronger, and preparation is simple, pollutes lessly, and the selectivity height can use in higher scope, has been subjected to learning this extensive concern both at home and abroad.
Patent WO13869 has reported with two-step approach and has prepared Cs
2.5H
0.5PW
12O
40/ SiO
2Catalyzer is earlier with carrier impregnation CsCO
3, after roasting, flood H again
3PW
12O
40, the catalyst activity component of Zhi Deing becomes elliposoidal to distribute at carrier surface like this, has good catalytic activity.But the carrier specific surface area is less, and the granules of catalyst diameter is less, and bed resistance is too big in fixed-bed reactor, is difficult to operation.
(" Journal of Molecular Catalysis ", 2001,15 (3): such as Ji Shan 228～230) with porousness, compound with regular structure and high-specific surface area and the SO of molecular sieve
4 2-/ ZrO
2Strongly-acid combine, made and had SO
4 2-/ Zr-ZSM-11, SO
4 2-The solid super acid catalyst of/Zr-MCM-41 molecular sieve structure feature, catalyst surface contain more B acid and L acid site, but the easy inactivation of catalyzer, easily run off in the acid site.
Patent USP5345026 and USP5510309 announced with the tungstate modified zirconium white and made solid acid catalyst, is used for hydrogenation/dehydrogenation catalysis to make hydro carbons open loop and the C that contains ring structure
4～C
8Hydrocarbon isomerization, but the report specific surface area of catalyst little, acidity a little less than, use temperature is also lower.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst activity that uses in the existing catalytic pyrolysis is lower, problems such as the selectivity of ethylene, propylene is relatively poor, use temperature height, a kind of method of new preparing ethylene propylene from catalytic pyrolysis is provided, this method has active high, the ethylene, propylene yield height of catalyst, the advantage that use 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 method of preparing ethylene propylene from catalytic pyrolysis, and with C
4～C
10Petroleum naphtha be raw material, be 550～700 ℃ in temperature of reaction, reaction pressure is 0.01～0.5MPa, the reaction weight space velocity be 0.1～4 hour
-1, water/petroleum naphtha weight ratio is under 0.5～4: 1 the condition, and raw material is by beds, and wherein catalyzer comprises following active ingredient 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 mordenite, ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry thereon
B) surplus is selected from the period of element Table VI
BFamily's element or VI
BFamily's element and IV
BAt least a or its oxide compound in family's 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 is 80～99%; The SiO of used coexisting molecular sieve
2/ Al
2O
3The mol ratio preferable range is 10～300, and more preferably scope is 12～50; The consumption preferable range of coexisting molecular sieve is 85～99% by weight percentage.The period of element Table VI
BFamily's element preferred version is to be selected from least a among Cr, Mo, the W, and more preferably scheme is to be selected from least a among Mo or the W; The consumption preferable range 0.01～20% of group vib element or its oxide compound by weight percentage, more preferably scope is 0.1～10%.IV
BFamily's element preferred version is to be selected from least a among Ti, Zr, the Hf, and more preferably scheme is to be selected from least a among Ti and the Zr; IV by weight percentage
BThe consumption preferable range of family's element or its oxide compound is 0.01～20%, and more preferably scope is 0.1～10%.The temperature of reaction preferable range is 550～700 ℃, and more preferably scope is 600～650 ℃; The reaction pressure preferable range is 0.01～0.5MPa, and more preferably scope is 0.02～0.2MPa; Reaction weight space velocity preferable range is 0.1～4 hour
-1, more preferably scope is 0.5-2 hour
-1Water/petroleum naphtha weight ratio preferable range is 0.5～4: 1, and more preferably scope is 1～3: 1.
The raw material that the preparation coexisting molecular sieve uses: the silicon source is metasilicate, silicate sodium or silicon sol, the aluminium source is aluminium salt or aluminate, template is at least a in 4-propyl bromide, TPAOH, triethylamine, n-Butyl Amine 99, tetraethyl ammonium hydroxide, quadrol or the ethamine, and the pH value of regulating colloidal sol with diluted acid is 10～13.Prepare acid solution or salts solution and ammonium solution or the alkaline solution of solid super-strong acid with corresponding active ingredient element.
The synthetic method concrete operations of coexisting molecular sieve are, 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 of aequum then, stirs after 30 minutes with rare acid for adjusting pH value in 10～14 scopes, supply distilled water again, add the corresponding crystal seed of aequum.Colloidal sol is put into autoclave, control temperature crystallization for some time of 120～180 ℃ 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 and have the strength of acid height, catalytic capability is strong, the selectivity height, and use temperature is wide, the acid solid super-strong acid that is difficult for running off carries out loaded modified to coexisting molecular sieve, strengthen the hydrothermal stability and the acidity of coexisting molecular sieve, make the catalyst acid density that makes big, the strength of acid 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 catalyzer 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 petroleum naphtha of hydrocarbon is a raw material, petroleum naphtha physical index such as table 1.With internal diameter is 12 millimeters down examination of fixed-bed reactor normal pressure, is 600～650 ℃ in temperature of reaction, and reaction pressure is 0.001MPa～0.5MPa, weight space velocity 0.25～4 hour
-1, under the condition of water/stock oil weight ratio 1～4: 1, petroleum naphtha being carried out catalytic pyrolysis, the ethylene, propylene yield can reach 55%, 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 |
| Normal paraffin % (weight %) in the alkane | ＞32.5 |
| Naphthenic hydrocarbon % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 33.3 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram quadrols then, after stirring for some time, regulate the pH value 11.5 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: quadrol: H
2O=1: 0.1: 0.4: 40, add the crystal seed that contains ZSM-5 and mordenite presoma, stir and after 30 minutes mixing solutions 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 mordenite, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 and mordenite 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 Starsos, become solution A with 300 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11 with dilute sulphuric 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, mixing solutions 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, 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 Starsos, become solution A with 300 gram dissolved in distilled water, get 33.3 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram quadrols then, stir after 20 minutes, regulate the pH value 11.5 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: quadrol: H
2O=1: 0.1: 0.4: 40, add 2.8 gram Y zeolite crystal seeds, mixing solutions 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 the ZSM-5 of 94.5% weight and the Y zeolite of 5.5% weight in the coexisting molecular sieve as can be known 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 mixture, as shown in table 2.
Table 2
| Embodiment | The coexisting molecular sieve kind | Ratio (weight ratio) | Sample number into spectrum |
| Embodiment 4 | ZSM-5/ mordenite+ZSM-5/ β zeolite | 1∶1 | FH-4 |
| Embodiment 5 | ZSM-5/ mordenite+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/ mordenite+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 proportioning raw materials, 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/ mordenite | 12 | 61.5 | FH-8 |
| Embodiment 9 | The ZSM-5/ mordenite | 16 | 73.6 | FH-9 |
| Embodiment 10 | The ZSM-5/ mordenite | 40 | 85.4 | FH-10 |
| Embodiment 11 | The ZSM-5/ mordenite | 100 | 96.8 | FH-11 |
| Embodiment 12 | The ZSM-5/ mordenite | 300 | 99.2 | FH-12 |
| Embodiment 13 | The ZSM-5/ mordenite | 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 66 milliliters of the zirconium nitrate solutions of 0.05 mol, 33 milliliters of ammonium tungstate solutions that add 0.05 mol, the powerful stirring 10 minutes, add then and get Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen 20 grams that embodiment 1 makes, stir down at 70 ℃, slow evaporate to dryness is put into baking oven then 120 ℃ of dryings 3 hours, put into 650 ℃ of roastings of retort furnace 3 hours again, make WO
3/ ZrO
2The ZSM-5/ mercerization zeolite symbiosis molecular screen catalyzer of solid super-strong acid load.The catalyzer compressing tablet, break into pieces, sieve after, get 20～40 purpose particles and put into fixed-bed reactor, be that 650 ℃, reaction pressure are that 0.02MPa, weight space velocity are 1 hour in temperature of reaction
-1, check and rate under water/condition of 3: 1 of stock oil weight ratio, the results are shown in Table 4.
[embodiment 27～33]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyzer and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 26.
[embodiment 34]
Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 22 makes, 66 milliliters of zirconium nitrates that add 0.05 mol, stir evaporate to dryness at 70 ℃ then, put into baking oven then 120 ℃ of dryings 3 hours, put into 650 ℃ of roastings of retort furnace 3 hours again, take out cooling then after, 33 milliliters of ammonium tungstate solutions that add 0.05 mol again, stir evaporate to dryness at 70 ℃, behind the drying and roasting, make the coexisting molecular sieve catalyzer WO of solid super-strong acid load in a manner described
3/ ZrO
2-ZSM-5/Y zeolite.Method examination according to embodiment 26 the results are shown in Table 4.
[embodiment 35～38]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyzer and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 34.
Table 4
| Embodiment | The sample number into spectrum of used carrier | The super acids type of load and content (weight %) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 26 | FH-1 | 2％WO 3/ZrO 2 | 24.81 | 30.98 | 55.79 |
| Embodiment 27 | FH-2 | 1％WO 3/TiO 2 | 22.98 | 29.29 | 52.27 |
| Embodiment 28 | FH-5 | 10％WO 3/HfO 2 | 25.76 | 30.54 | 56.30 |
| Embodiment 29 | FH-8 | 15％MoO 3/ZrO 2 | 20.83 | 28.09 | 48.92 |
| Embodiment 30 | FH-11 | 20％MoO 3/TiO 2 | 21.98 | 22.93 | 51.91 |
| Embodiment 31 | FH-15 | 0.1％CrO 3/ZrO 2 | 21.78 | 27.51 | 49.29 |
| Embodiment 32 | FH-17 | 0.5％CrO 3/TiO 2 | 19.99 | 28.15 | 48.14 |
| Embodiment 33 | FH-20 | 6％WO 3/ZrO 2 | 19.03 | 26.54 | 45.58 |
| Embodiment 34 | FH-22 | 2％WO 3/ZrO 2 | 23.69 | 25.81 | 49.52 |
| Embodiment 35 | FH-23 | 0.2MoO 3/ZrO 2 | 24.01 | 28.20 | 52.21 |
| Embodiment 36 | FH-3 | 0.6MoO 3/ZrO 2 | 22.36 | 30.95 | 53.33 |
| Embodiment 37 | FH-4 | 4％CrO 3/ZrO 2 | 23.45 | 27.68 | 51.13 |
| Embodiment 38 | FH-7 | 10％CrO 3/TiO 2 | 24.47 | 30.26 | 54.73 |
[embodiment 39]
Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 3 makes, make WO by the method for embodiment 26
3/ ZrO
2The ZSM-5/Y zeolite coexisting molecular sieve of load then as carrier, is pressed the method for embodiment 26 again, makes WO
3/ TiO
2The WO of load
3/ ZrO
2-ZSM-5/Y zeolite coexisting molecular sieve catalyst.Method examination according to embodiment 26 the results are shown in Table 5.
[embodiment 40～50]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyzer and appraisal result is as shown in table 5 according to method modification and the examination of embodiment 39.
Table 5
| Embodiment | The numbering of specimen in use | The type of the super acids of load and content (weight %) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 39 | FH-9 | 2％WO 3/ZrO 2+2％WO 3/TiO 2 | 20.87 | 28.60 | 49.47 |
| Embodiment 40 | FH-10 | 1％MoO 3/ZrO 2+1％MoO 3/TiO 2 | 24.56 | 29.41 | 53.96 |
| Embodiment 41 | FH-12 | 5％CrO 3/ZrO 2+5％CrO 3/TiO 2 | 20.06 | 27.34 | 47.40 |
| Embodiment 42 | FH-13 | 0.1WO 3/ZrO 2+0.5MoO 3/ZrO 2 | 23.10 | 30.14 | 53.24 |
| Embodiment 43 | FH-14 | 10％WO 3/TiO 2+10％MoO 3/ZrO 2 | 24.25 | 28.43 | 52.68 |
| Embodiment 44 | FH-16 | 2％WO 3/ZrO 2+2％WO 3/TiO 2 +2％MoO 3/ZrO 2 | 22.09 | 28.54 | 50.64 |
| Embodiment 45 | FH-18 | 5％MoO 3/ZrO 2+5％MoO 3/TiO 2 +5％WO 3/ZrO 2 | 23.67 | 24.69 | 48.36 |
| Embodiment 46 | FH-21 | 0.2％WO 3/ZrO 2+0.2％MoO 3/ZrO 2 +0.2％CrO 3/TiO 2 | 23.31 | 27.24 | 50.55 |
| Embodiment 47 | FH-24 | 2％WO 3/ZrO 2+2％WO 3/TiO 2+ 2％MoO 3/ZrO 2+2％MoO 3/TiO 2 | 24.38 | 27.92 | 52.30 |
| Embodiment 48 | FH-25 | 0.2％WO 3/ZrO 2+0.2％MoO 3/ZrO 2 +0.2％CrO 3/ZrO 2+0.2％CrO 3/TiO 2 | 29.02 | 27.45 | 56.47 |
| Embodiment 49 | FH-6 | 1％WO 3/ZrO 2+1％WO 3/TiO 2+ 1％MoO 3/ZrO 2+1％MoO 3/TiO 2+ 1％CrO 3/ZrO 2 | 24.21 | 29.78 | 53.99 |
| Embodiment 50 | FH-19 | 2％WO 3/ZrO 2+2％WO 3/TiO 2 +2％MoO 3/ZrO 2+2％MoO 3/TiO 2 +2％CrO 3/ZrO 2+2％CrO 3/TiO 2 | 20.33 | 35.07 | 55.40 |
[embodiment 51]
Get Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen 20 grams that embodiment 1 makes, 33 milliliters of ammonium tungstate solutions that add 0.05 mol, stir down at 70 ℃, slow evaporate to dryness, put into baking oven then 120 ℃ of dryings 3 hours, put into 650 ℃ of roastings of retort furnace 3 hours again, make the ZSM-5/ mercerization zeolite symbiosis molecular screen catalyzer of tungsten load.The catalyzer compressing tablet, break into pieces, sieve after, get 20～40 purpose particles and put into fixed-bed reactor, be that 650 ℃, reaction pressure are that 0.02MPa, weight space velocity are 1 hour in temperature of reaction
-1, check and rate under water/condition of 3: 1 of stock oil weight ratio, the results are shown in Table 6.
[embodiment 52～53]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyzer and appraisal result is as shown in table 6 according to method modification and the examination of embodiment 51.
[embodiment 54～57]
Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyzer and appraisal result is as shown in table 6 according to method modification and the examination of embodiment 34.
Table 6
| Embodiment | The sample number into spectrum of used carrier | Load element type and content (weight %) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 51 | FH-1 | 2％W | 24.60 | 30.46 | 55.06 |
| Embodiment 52 | FH-2 | 0.01％Mo | 22.24 | 30.01 | 52.25 |
| Embodiment 53 | FH-5 | 20％Cr | 27.36 | 28.45 | 55.81 |
| Embodiment 54 | FH-8 | 10％Mo+10％W | 20.62 | 28.10 | 48.72 |
| Embodiment 55 | FH-11 | 2％Cr+2％Mo | 22.02 | 23.11 | 45.13 |
| Embodiment 56 | FH-15 | 0.02％Cr+0.02％Mo | 21.57 | 27.34 | 48.91 |
| Embodiment 57 | FH-17 | 0.5％Cr+0.5％Mo+0.5％W | 20.12 | 28.23 | 48.35 |
[embodiment 58～61]
By the catalyzer that embodiment 26 makes, be 0.02MPa in reaction pressure, the reaction weight space velocity is 1 hour
-1, water/petroleum naphtha weight ratio is 3: 1, temperature of reaction is followed successively by 550 ℃ respectively; 580 ℃; Check and rate result such as table 7 under the condition of 670 ℃ and 700 ℃.
[embodiment 62～66]
By the catalyzer that embodiment 27 makes, be 650 ℃ in temperature of reaction, the reaction weight space velocity is 1 hour
-1, water/petroleum naphtha weight ratio is 3: 1, reaction pressure is followed successively by 0.5MPa respectively; 0.2MPa; 0.05MPa; 0.03MPa and check and rate result such as table 7 under the condition of 0.01MPa.
[embodiment 67～71]
By the catalyzer that embodiment 40 makes, be 650 ℃ in temperature of reaction, reaction pressure is 0.02MPa, and water/petroleum naphtha weight ratio is 3: 1, and the reaction weight space velocity was followed successively by respectively 4 hours
-12 hours
-1; 1.2 hour
-10.5 hour
-1With 0.1 hour
-1Condition under check and rate result such as table 7.
[embodiment 72～75]
By the catalyzer that embodiment 48 makes, be 650 ℃ in temperature of reaction, reaction pressure is 0.02MPa, the reaction weight space velocity is 1 hour
-1, water/petroleum naphtha weight ratio was followed successively by respectively 4: 1; 3.5: 1; Check and rate result such as table 7 under the condition of 2: 1 and 1: 1.
Table 7
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 58 | 19.21 | 26.55 | 45.76 |
| Embodiment 59 | 20.79 | 26.84 | 47.63 |
| Embodiment 60 | 26.68 | 29.26 | 55.94 |
| Embodiment 61 | 30.23 | 24.73 | 54.96 |
| Embodiment 62 | 21.25 | 27.31 | 48.56 |
| Embodiment 63 | 21.76 | 27.89 | 49.65 |
| Embodiment 64 | 22.13 | 28.24 | 50.37 |
| Embodiment 65 | 22.72 | 28.91 | 51.63 |
| Embodiment 66 | 23.34 | 29.62 | 52.96 |
| Embodiment 67 | 20.55 | 24.22 | 44.77 |
| Embodiment 68 | 22.33 | 26.47 | 48.80 |
| Embodiment 69 | 23.96 | 29.15 | 53.11 |
| Embodiment 70 | 26.77 | 28.08 | 54.85 |
| Embodiment 71 | 27.11 | 19.43 | 46.54 |
| Embodiment 72 | 29.25 | 28.21 | 57.46 |
| Embodiment 73 | 29.37 | 27.58 | 56.95 |
| Embodiment 74 | 29.14 | 25.66 | 54.80 |
| Embodiment 75 | 26.59 | 23.27 | 49.86 |
Claims (10)
1, a kind of method of preparing ethylene propylene from catalytic pyrolysis is with C
4～C
10Petroleum naphtha be raw material, be 550～700 ℃ in temperature of reaction, reaction pressure is 0.01～0.5MPa, the reaction weight space velocity be 0.1～4 hour
-1, water/petroleum naphtha weight ratio is under 0.5～4: 1 the condition, and raw material is by beds, and wherein catalyzer comprises following active ingredient 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 mordenite, ZSM-5 and β zeolite or ZSM-5 and Y zeolite; With carry thereon
B) surplus is selected from least a or its oxide compound in periodic table of elements group vib element or group vib element and the IVB family element.
2, according to the method for the described preparing ethylene propylene from catalytic pyrolysis 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,, it is characterized in that the SiO of coexisting molecular sieve according to the method for the described preparing ethylene propylene from catalytic pyrolysis of claim 2
2/ Al
2O
3Mol ratio is 12～50; The weight percentage of ZSM-5 molecular sieve is 80～99%.
4,, it is characterized in that periodic table of elements group vib element is selected from least a or its oxide compound among Cr, Mo or the W according to the method for the described preparing ethylene propylene from catalytic pyrolysis of claim 1; Periodic table of elements IVB family element is selected from least a or its oxide compound among Ti, Zr or the Hf.
5, according to the method for the described preparing ethylene propylene from catalytic pyrolysis of claim 4, it is characterized in that by weight percentage, be selected from periodic table of elements group vib element or its oxide compound consumption is 0.01～20%; Be selected from periodic table of elements NB family's element by weight percentage or its oxide compound consumption is 0.01～20%.
6,, it is characterized in that by weight percentage the consumption that is selected from periodic table of elements group vib element or its oxide compound is 0.1～10% according to the method for the described preparing ethylene propylene from catalytic pyrolysis of claim 5; By weight percentage, the consumption that is selected from periodic table of elements IVB family's element or its oxide compound is 0.1～10%.
7, according to the method for the described preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that temperature of reaction is 550～700 ℃, reaction pressure is 0.01～0.5MPa.
8, according to the method for the described a kind of preparing ethylene propylene from catalytic pyrolysis of claim 7, it is characterized in that temperature of reaction is 600～650 ℃, reaction pressure is 0.02～0.2MPa.
9, according to the method for the described a kind of preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that reacting weight space velocity is 0.1～4 hour
-1, water/petroleum naphtha weight ratio is 0.5～4: 1.
10, according to the method for the described a kind of preparing ethylene propylene from catalytic pyrolysis of claim 9, it is characterized in that reacting weight space velocity is 0.5～2 hour
-1, water/petroleum naphtha weight ratio is 1～3: 1.
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| CN106607075A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Fluid catalyst for preparing olefin and arene and application of fluid catalyst |
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| US6037294A (en) * | 1998-04-15 | 2000-03-14 | Phillips Petroleum Company | Zeolite material, a process of making such zeolite material, a product from such process, and the use thereof in the conversion of hydrocarbons |
| CN1317543A (en) * | 2000-04-07 | 2001-10-17 | 中国石油化工集团公司 | Catalytic thermocracking process of hydrocarbons for higher output of ethylene and prpylene |
| CN1322919C (en) * | 2004-03-31 | 2007-06-27 | 中国石油化工股份有限公司 | Catalyst for producing propylene by C4-C7 olefin pyrolysis |
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| CN106607075A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Fluid catalyst for preparing olefin and arene and application of fluid catalyst |
| CN106607075B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | Prepare fluid catalyst and the application of alkene and aromatic hydrocarbons |
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