CN100567228C - The method of preparing olefin by catalytic cracking - Google Patents
The method of preparing olefin by catalytic cracking Download PDFInfo
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- CN100567228C CN100567228C CNB200610118527XA CN200610118527A CN100567228C CN 100567228 C CN100567228 C CN 100567228C CN B200610118527X A CNB200610118527X A CN B200610118527XA CN 200610118527 A CN200610118527 A CN 200610118527A CN 100567228 C CN100567228 C CN 100567228C
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Abstract
The present invention relates to a kind of method of preparing olefin by catalytic cracking, mainly solve the problem that temperature of reaction is higher in naphtha catalytic pyrolysis preparing ethylene and the propylene, catalyst low-temperature activity is low and the ethylene, propylene yield is lower.The present invention is by being C with the component
4～C
10The petroleum naphtha of hydrocarbon is a raw material, is 550～700 ℃ in temperature of reaction, and reaction pressure is 0.001～0.5MPa, and weight space velocity is 0.1～4 hour
-1, water/petroleum naphtha weight ratio is under 0.5～4: 1 the condition, carries out catalytic cracking reaction and generates ethylene, propylene, wherein catalyzer is to be selected from SiO
2Or at least a in the composite molecular screen be carrier, with the following composition of atomic ratio measuring chemical formula: A
aB
bP
cO
xA is selected from least a in the rare earth element, B is selected from least a technical scheme of forming catalyzer for active ingredient among period of element Table VIII, IB, IIB, VIIB, VIB, IA or the IIA, solved this problem preferably, can be used in the industrial production of naphtha catalytic pyrolysis preparing ethylene and propylene.
Description
Technical field
The present invention relates to a kind of method of preparing olefin by catalytic cracking.
Background technology
The topmost method of preparing ethylene and propylene is the steam heat cracking at present.Maximum raw material that adopts is a petroleum naphtha.But the steam heat cracking naphtha exists the temperature of reaction height, and the processing condition harshness requires height, the shortcoming that loss is big to equipment especially furnace tube material.People have carried out various significant researchs for this reason, and wherein catalytic pyrolysis is the most attractive, also are the most promising one.Target is to seek a kind of suitable catalyst for cracking, improves the selectivity of ethylene, propylene, reduces temperature of reaction, simultaneously certain handiness can be arranged on the yield of ethylene, propylene.
From existing literature, how most catalytic pyrolysis investigators make catalytic material with the molecular sieve of high silica alumina ratio, and exchange and flood with the metal ion of high valence state.But it is poor that molecular sieve catalyst has hydrothermal stability, is difficult to the regenerated shortcoming.
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, also belong to simple molecular sieve catalysts basically.
In addition, people make catalyzer with oxide compound.
It is active ingredient that the patent US4620051 of U.S. Phillips company and US4705769 have adopted with manganese oxide or ferric oxide, has added rare-earth elements La, and the oxide catalyst of alkaline-earth metal Mg, cracking C
3, C
4Raw material.Mn, Mg/Al
2O
3Catalyzer is in breadboard fixed-bed reactor, and 700 ℃, the mol ratio of water and butane is 1: 1, and the transformation efficiency of butane can reach 80%, ethene, and the selectivity of propylene is 34% and 20%.These two patents are claimed also can use petroleum naphtha and fluidized-bed reactor.
It is 12CaO7Al that the patent CN1317546A of Italy En Niqiemu company relates to chemical formula
2O
3The steam cracking reaction catalyzer.Raw material can be used petroleum naphtha, 720～800 ℃ of service temperatures, and under 1.1～1.8 normal atmosphere, 0.07～0.2 second duration of contact, the productive rate of ethene and propylene can reach 43%.
The USSR (Union of Soviet Socialist Republics) patent USSR Pat1298240.1987 Zr that is carried on float stone or the pottery
2O
3And potassium vanadate, air speed is 2～5 hours on 660～780 ℃ of middle-scale devices of temperature
-1, water/straight-run spirit weight ratio 1: 1.With normal paraffin C
7～17Hydrocarbon, hexanaphthene, straight-run spirit are raw material, ethylene yield can reach 46%, propylene 8.8%.
Chinese patent CN1480255A introduces a kind of oxide catalyst, is raw material with petroleum naphtha, and at 780 ℃ of following preparing ethylene propylene from catalytic pyrolysis, the diene yield can reach 47%.
In sum, molecular sieve is subject to the people's attention as main catalyst for cracking, but composite molecular screen mixes the example that uses with oxide compound, yet there are no report.
Summary of the invention
Technical problem to be solved by this invention is the problem that temperature of reaction is higher in the prior art preparing ethylene propylene from catalytic pyrolysis, catalyst low-temperature activity is low and the ethylene, propylene yield is lower, and a kind of method of new preparing olefin by catalytic cracking is provided.Use this method catalytic pyrolysis petroleum naphtha preparing ethylene and propylene, have and to reduce the catalytic pyrolysis temperature, and can keep the characteristics of the yield of high ethylene, propylene simultaneously.
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 olefin by catalytic cracking is C with the component
4～C
10The petroleum naphtha of hydrocarbon is a raw material, is 550～700 ℃ in temperature of reaction, and reaction pressure is 0.001～0.5MPa, and weight space velocity is 0.1～4 hour
-1, water/petroleum naphtha weight ratio is under 0.5～4: 1 the condition, carries out catalytic cracking reaction and generates ethylene, propylene, wherein said catalyzer is to be selected from SiO
2Or at least a in the composite molecular screen be carrier, contains with the following composition of atomic ratio measuring chemical formula:
A
aB
bP
cO
x
A is selected from least a in the rare earth element in the formula;
B is selected from least a element among period of element Table VIII, I B, IIB, VIIB, VIB, I A or the IIA;
The span of a is 0.01～0.5;
The span of b is 0.01～0.5;
The span of c is 0.01～0.5;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Composite molecular screen is the mixture that at least two kinds of molecular sieve syntrophism in ZSM-5, Y zeolite, β zeolite, MCM-22, SAPO-34 or the mordenite become;
Wherein, rare earth element is selected from least a among La or the Ce; The element of VIII family is selected from least a among Fe, Co or the Ni; The element of I B is selected from least a among Cu or the Ag; The element of II B is selected from Zn; The element of VIIB is selected from Mn; The element of VIB is selected from least a among Cr or the Mo; The element of I A is selected from least a among Li, Na or the K; The element of IIA is selected from least a among Mg, Ca, Ba or the Sr; The consumption of carrier is 10～70% of catalyst weight by weight percentage in the catalyzer.
In the technique scheme, the value preferable range of a is 0.01～0.3; The value preferable range of b is 0.01～0.3; The value preferable range of c is 0.01～0.3.The preferred version of composite molecular screen is to be selected from least a in ZSM-5/ mordenite, ZSM-5/Y zeolite or the ZSM-5/ β zeolite; The silica alumina ratio SiO of composite molecular screen
2/ Al
2O
3Preferable range is 10～500, and more preferably scope is 20～300; In the catalyzer consumption of composite molecular screen by weight percentage preferable range be 10～60% of catalyst weight, more preferably scope is 20～50%.The temperature of reaction preferable range is 600～650 ℃; The reaction pressure preferable range is 0.02～0.2MPa; Reaction weight space velocity preferable range is 0.5～2 hour
-1Water/petroleum naphtha weight ratio preferable range is 2～3: 1.
The Preparation of Catalyst that the present invention relates to, what used raw material A dvielement was used is corresponding nitrate, oxalate or oxide compound.What the category-B element was used is corresponding nitrate, oxalate, acetate or soluble halide.Used phosphoric derives from phosphoric acid, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate.
In the method for preparing catalyst, active element can be immersed on the composite molecular screen, also can be directly and composite molecular screen uniform mixing aftershaping.The forming mode of preparation catalyzer is to have added the slurries of each component element and carrier, to have carried out spraying drying after 5 hours in reflux in 70～80 ℃ the water-bath.The powder that obtains roasting in muffle furnace, temperature are 600～750 ℃, and roasting time is 3～10 hours.
The present invention is owing to adopted the composite molecular screen with acidity, shape selectivity and high-specific surface area as the cracking auxiliary agent, help hydrocarbon raw material by the cracking of carbonium ion mechanism, low-carbon olefines high-output, cooperate with active constituent with oxidation-reduction quality, produce synergy, under relatively lower temp (580～650 ℃), reach catalytic pyrolysis effect preferably, the ethylene, propylene yield that obtains can reach 46%, has obtained better technical effect.
In order to check and rate catalyst activity involved in the present invention, be raw material with petroleum naphtha (specific targets see Table 1).The temperature range of reaction is 580～650 ℃, and weight space velocity is 0.5～2 hour-1, and water/petroleum naphtha weight ratio is 0.5～3: 1.The internal diameter of fluidized-bed reactor is 39 millimeters, reaction pressure 0～0.2MPa.
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 iron nitrate 16.2 grams, Xiao Suangu 7.86 grams, chromium nitrate 12.23 grams, lanthanum nitrate 2.4 grams are dissolved in them in 250 ml waters together, obtain solution A.Dissolving 4.65 gram Secondary ammonium phosphates are poured in the A solution in 100 ml waters, stir, and obtain slurries B.
Slurries B placed in 70～80 ℃ of water-baths heats, add silicon dioxide gel 50 grams of weight ratio 40% (down with), refluxed 5 hours, with spray drying device with the slurry dried moulding.
With dried powder, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.Get catalyzer after the cooling, again catalyzer is crossed 100 mesh sieves.
Obtaining the catalyst chemical formula is: Fe
0.11Co
0.08Cr
0.08La
0.04P
0.05O
x+ carrier 31.57 weight %
Carry out the catalyst activity evaluation under the following conditions: the fluidized-bed reactor of 39 millimeters internal diameters, 650 ℃ of temperature of reaction, pressure 0.02MPa.Water/petroleum naphtha weight ratio 3: 1, catalyzer loading amount are 20 grams, and weight space velocity is 1 hour
-1Collect gaseous product, carry out gas chromatographic analysis, products distribution and diene yield see Table 2.
Table 2 gas-phase product distributes and the diene productive rate
| Product | Content (H 2Volume %, all the other weight %) |
| Hydrogen (volume %) | 15.5 |
| Methane | 17.08 |
| Ethane | 1.62 |
| Ethene | 42.23 |
| Propane | 0.41 |
| Propylene | 14.72 |
| C 4 | 7.98 |
| Other | 15.96 |
| Transformation efficiency | 76.37 |
| Yield of ethene (weight %) | 32.25 |
| Propene yield (weight %) | 11.24 |
| Ethene+propene yield (weight %) | 43.49 |
[embodiment 2]
Method by embodiment 1 makes slurries B, directly adds same silicon-dioxide, does not need loading process, and the directly spray shaping of back that stirs makes catalyzer and forms with embodiment 1.Press the method examination of embodiment 1, result such as table 3.
[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 30 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, mixing solutions is put into autoclave, 170 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the composite molecular screen of ZSM-5 and mordenite.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes Hydrogen ZSM-5/ mordenite composite molecular sieve after repeating twice.
Method by embodiment 1 makes slurries B, adds SiO
2/ Al
2O
3Mol ratio is 20 ZSM-5/ mordenite composite molecular sieve 15 grams and silicon dioxide gel 12.5 grams, makes catalyzer by identical way again.Press the method examination of embodiment 1, result such as table 3.
[embodiment 4]
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, B solution is slowly poured in the A solution with 100 gram distilled water, the powerful stirring, add 24.4 gram quadrols then, after stirring for some time, regulate the pH value about 12 with dilute sulphuric acid, add 5 gram Y zeolite crystal seeds, the mole proportioning of control colloidal sol is: Si: Al: quadrol: H
2O=1: 0.1: 0.4: 40, mixing solutions is put into autoclave, 150 ℃ of insulations 36 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the composite molecular screen of ZSM-5 and Y zeolite.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes Hydrogen ZSM-5/Y zeolite composite molecular screen after repeating twice.
Method by embodiment 1 makes slurries B, adds SiO
2/ Al
2O
3Mol ratio is 20 ZSM-5/Y zeolite composite molecular screen 15 grams and silicon dioxide gel 12.5 grams, makes catalyzer by identical way again.Press the method examination of embodiment 1, result such as table 3.
[embodiment 5]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 22.2 gram Tai-Ace S 150, make solution B, B solution is slowly poured in the A solution with 100 gram distilled water, the powerful stirring, add 24.4 gram quadrols, 10 gram tetraethyl ammonium hydroxides then, after stirring for some time, regulate the pH value about 11 with dilute sulphuric acid, add 5 gram β zeolite seed crystals, the mole proportioning of control colloidal sol is: Si: Al: quadrol: H
2O=1: 0.0167: 0.4: 40, 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 the composite molecular screen of mordenite and β zeolite.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, roasting then makes h-mordenite/β zeolite composite molecular screen after repeating twice.
Method by embodiment 1 makes slurries B, adds SiO
2/ Al
2O
3Mol ratio is 30 mordenite/beta zeolite composite molecular screen 15 grams and silicon dioxide gel 12.5 grams, makes catalyzer by identical way again.Press the method examination of embodiment 1, result such as table 5.
[embodiment 6]
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/ β zeolite composite molecular screen.
Method by embodiment 1 makes slurries B, adds SiO
2/ Al
2O
3Mol ratio is 40 ZSM-5/ β zeolite composite molecular screen 15 grams and silicon dioxide gel 12.5 grams, makes catalyzer by identical way again.Press the method examination of embodiment 1, result such as table 3.
[embodiment 7]
Method by embodiment 1 makes slurries B, adds 5 gram SiO
2/ Al
2O
3Mol ratio is 20 Hydrogen ZSM-5/Y zeolite composite molecular screen, 10 gram SiO
2/ Al
2O
3Mol ratio is 20 ZSM-5/ mordenite composite molecular sieve and 12.5 gram silicon dioxide gels, makes catalyzer by embodiment 1 identical way again, examination in the same way, result such as table 3.
[embodiment 8]
Method by embodiment 1 makes slurries B, adds the SiO that 12 grams make by the method for embodiment 3
2/ Al
2O
3Mol ratio be 120 Hydrogen ZSM-5/ mordenite composite molecular sieve as carrier, make the constitutional chemistry formula and be: Fe
0.11Co
0.08Cr
0.08La
0.04P
0.05O
xThe catalyzer of+carrier 21.32 (weight %), the method examination of pressing embodiment 1, result such as table 3.
[embodiment 9]
Method by embodiment 1 makes slurries B, adds the SiO that 20 grams make by the method for embodiment 6
2/ Al
2O
3Mol ratio be 60 Hydrogen ZSM-5/ β zeolite composite molecular screen as carrier, make the constitutional chemistry formula and be: Fe
0.11Co
0.08Cr
0.08La
0.04P
0.05O
xThe catalyzer of+carrier 31.6 (weight %), the method examination of pressing embodiment 1, result such as table 3.
Table 3
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Ethene+propene yield (weight %) |
| Embodiment 2 | 32.20 | 11.21 | 43.41 |
| Embodiment 3 | 33.78 | 11.56 | 45.34 |
| Embodiment 4 | 33.40 | 11.82 | 45.22 |
| Embodiment 5 | 33.12 | 11.47 | 44.59 |
| Embodiment 6 | 33.43 | 11.33 | 44.76 |
| Embodiment 7 | 34.45 | 12.08 | 46.59 |
| Embodiment 8 | 34.02 | 11.64 | 45.66 |
| Embodiment 9 | 33.22 | 11.73 | 44.95 |
[embodiment 10]
Method by embodiment 6 makes SiO
2/ Al
2O
3Mol ratio is 200 Hydrogen ZSM-5/ β zeolite composite molecular screen.
Get nickelous nitrate 7.27 grams, chromium nitrate 8.48 grams, cerous nitrate 5.44 grams are dissolved in 250 ml waters, get solution A.Dissolving 6.54 gram Secondary ammonium phosphates are poured in the solution A in 100 ml waters, stir, and obtain slurries B.
Hydrogen ZSM-5/ β zeolite composite molecular screen 17 grams that exchange is good and silicon dioxide gel 12.5 restrain puts into slurries B, and other is with embodiment 1, obtains the catalyst chemical formula and is:
Ni
0.07Cr
0.06Ce
0.09P
0.08O
x+ carrier 44.9%
Evaluating catalyst is with example 1, and pyrolysis product distribution and diene yield see Table 4.
Table 4 gas-phase product distributes and the diene productive rate
| Product | Content (H 2Volume %, all the other weight %) |
| Hydrogen (volume %) | 15.52 |
| Methane | 20.46 |
| Ethane | 2.40 |
| Ethene | 44.00 |
| Propane | 0.37 |
| Propylene | 14.28 |
| C 4 | 5.60 |
| Other | 12.89 |
| Transformation efficiency | 75.26 |
| Yield of ethene (weight %) | 33.11 |
| Propene yield (weight %) | 10.75 |
| Ethene+propene yield (weight %) | 43.86 |
[embodiment 11]
Get Xiao Suangu 5.49 grams, zinc nitrate 5.60 grams, cerous nitrate 5.44 grams, cupric nitrate 6.30 grams are dissolved in 250 ml waters, get solution A.Dissolving 6.54 gram Secondary ammonium phosphates are poured in the solution A in 100 ml waters, stir, and obtain slurries B.
With 10 gram silica alumina ratios is 120 Hydrogen ZSM-5/ mordenite composite molecular sieve, 5 gram SiO
2/ Al
2O
3Mol ratio is that 30 Hydrogen ZSM-5/ β zeolite composite molecular screen and 12.5 gram silicon dioxide gels are put into slurries B, and other is with embodiment 1.
Obtaining the catalyst chemical formula is: Co
0.06Zn
0.06Cu
0.08Ce
0.09P
0.08O
x+ carrier 40.5%.
Product yield sees Table 5.
[embodiment 12]
Get iron nitrate 7.62 grams, zinc nitrate 5.60 grams, cerous nitrate 5.44 grams, nitrocalcite 5.18 grams are dissolved in 250 ml waters, get solution A.Dissolving 6.54 gram Secondary ammonium phosphates are poured in the solution A in 100 ml waters, stir, and obtain slurries B.
With 5 gram SiO
2/ Al
2O
3Mol ratio is 20 Hydrogen ZSM-5/ mordenite composite molecular sieve, 5 gram SiO
2/ Al
2O
3Mol ratio is 40 Hydrogen ZSM-5/Y zeolite composite molecular screen, 5 gram SiO
2/ Al
2O
3Mol ratio is that 30 Hydrogen ZSM-5/ β zeolite composite molecular screen and 12.5 gram silicon dioxide gels are put into solution, and other is with embodiment 1.
Obtaining the catalyst chemical formula is: Fe
0.05Zn
0.06Ce
0.09Ca
0.04P
0.08O
x+ carrier 39.7%.
Product yield sees Table 5.
[embodiment 13]
Get Xiao Suangu 5.49 grams, 50% manganese nitrate solution 10.81 grams, cerous nitrate 5.44 grams are dissolved in 250 ml waters, get solution A.Dissolving 6.54 gram Secondary ammonium phosphates are poured in the solution A in 100 ml waters, stir, and obtain slurries B.
With 20 gram silicon SiO
2/ Al
2O
3Mole is that 20 Hydrogen ZSM-5/ mordenite composite molecular sieve is put into slurries B, and other is with embodiment 1.
Obtaining the catalyst chemical formula is: Mn
0.08Co
0.06Ce
0.09P
0.08O
x+ carrier 46.6%.
Product yield sees Table 5.
[embodiment 14]
Get Xiao Suangu 5.49 grams, 50% manganese nitrate solution 10.81 grams, cerous nitrate 5.44 grams are dissolved in 250 ml waters, get solution A.Dissolving 6.54 gram Secondary ammonium phosphates are poured in the solution A in 100 ml waters, stir, and obtain slurries B.
With 29.4 gram SiO
2/ Al
2O
3Mol ratio is that 40 Hydrogen ZSM-5/ β zeolite composite molecular screen and 12.5 gram silicon dioxide gels are put into slurries B, and other is with embodiment 1.
Obtaining the catalyst chemical formula is: Mn
0.08Co
0.06Ce
0.09P
0.08O
x+ carrier 60.1%.
Product yield sees Table 5.
[embodiment 15]
Get Xiao Suangu 5.49 grams, chromium nitrate 8.48 grams, cerous nitrate 5.44 grams, saltpetre 1.1 grams are dissolved in 250 ml waters, get solution A.Dissolving 6.54 gram Secondary ammonium phosphates are poured in the solution A in 100 ml waters, stir, and obtain slurries B.
With 37.5 gram silicon dioxide gels and 5 gram SiO
2/ Al
2O
3Mol ratio is that 30 mordenite/beta zeolite composite molecular screen is made carrier, puts into slurries B, and other is with embodiment 1.
Obtaining the catalyst chemical formula is: Co
0.06Cr
0.06Ce
0.09K
0.02P
0.08O
x+ 45.1% carrier.
Product yield sees Table 5.
The product yield of table 5 different carriers
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Ethene+propene yield (weight %) |
| Embodiment 11 | 33.02 | 12.37 | 45.39 |
| Embodiment 12 | 33.39 | 13.30 | 46.69 |
| Embodiment 13 | 32.36 | 12.45 | 44.81 |
| Embodiment 14 | 32.15 | 11.49 | 43.64 |
| Embodiment 15 | 31.87 | 11.64 | 39.51 |
[embodiment 16～19]
By the catalyzer that embodiment 3 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 6 under the condition of 670 ℃ and 700 ℃.
[embodiment 20～24]
By the catalyzer that embodiment 4 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 6 under the condition of 0.01MPa.
[embodiment 25～29]
By the catalyzer that embodiment 5 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
-11.2 hour
-10.5 hour
-1With 0.1 hour
-1Condition under check and rate result such as table 6.
[embodiment 30～33]
By the catalyzer that embodiment 8 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 6 under the condition of 2: 1 and 1: 1.
Table 6
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Ethene+propene yield (weight %) |
| Embodiment 16 | 30.75 | 10.57 | 41.32 |
| Embodiment 17 | 31.68 | 11.36 | 43.04 |
| Embodiment 18 | 34.36 | 11.12 | 45.48 |
| Embodiment 19 | 35.87 | 10.69 | 46.56 |
| Embodiment 20 | 32.56 | 9.67 | 42.23 |
| Embodiment 21 | 32.81 | 10.23 | 43.04 |
| Embodiment 22 | 33.20 | 10.72 | 43.92 |
| Embodiment 23 | 33.31 | 11.24 | 44.55 |
| Embodiment 24 | 33.64 | 11.93 | 45.57 |
| Embodiment 25 | 27.56 | 9.18 | 36.74 |
| Embodiment 26 | 30.42 | 9.79 | 40.21 |
| Embodiment 27 | 32.58 | 11.12 | 43.70 |
| Embodiment 28 | 34.24 | 11.05 | 45.29 |
| Embodiment 29 | 35.27 | 8.55 | 43.82 |
| Embodiment 30 | 34.22 | 11.89 | 46.11 |
| Embodiment 31 | 34.14 | 11.73 | 45.87 |
| Embodiment 32 | 34.35 | 11.07 | 45.42 |
| Embodiment 33 | 35.69 | 8.16 | 43.85 |
Claims (7)
1, a kind of method of preparing olefin by catalytic cracking is C with the component
4～C
10The petroleum naphtha of hydrocarbon is a raw material, is 550～700 ℃ in temperature of reaction, and reaction pressure is 0.001～0.5MPa, and weight space velocity is 0.1～4 hour
-1, water/petroleum naphtha weight ratio is under 0.5～4: 1 the condition, carries out catalytic cracking reaction and generates ethylene, propylene, wherein said catalyzer is to be selected from SiO
2Or at least a in the composite molecular screen be carrier, contains with the following composition of atomic ratio measuring chemical formula:
A
aB
bP
cO
x
A is selected from least a in the rare earth element in the formula;
B is selected from least a element among period of element Table VIII, IB, IIB, VIIB, VIB, IA or the IIA;
The span of a is 0.01～0.5;
The span of b is 0.01～0.5;
The span of c is 0.01～0.5;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Composite molecular screen is selected from the mixture that at least two kinds of molecular sieve syntrophism in ZSM-5, Y zeolite, β zeolite, MCM-22, SAPO-34 or the mordenite become;
Wherein, rare earth element is selected from least a among La or the Ce; The element of VIII family is selected from least a among Fe, Co or the Ni; The element of IB is selected from least a among Cu or the Ag; The element of IIB is selected from Zn; The element of VIIB is selected from Mn; The element of VIB is selected from least a among Cr or the Mo; The element of IA is selected from least a among Li, Na or the K; The element of IIA is selected from least a among Mg, Ca, Ba or the Sr; The consumption of carrier is 10～70% of catalyst weight by weight percentage in the catalyzer.
2, according to the method for the described preparing olefin by catalytic cracking of claim 1, the span that it is characterized in that a is 0.01～0.3; The span of b is 0.01～0.3; The span of c is 0.01～0.3.
3,, it is characterized in that composite molecular screen is selected from least a in ZSM-5/ mordenite, ZSM-5/Y zeolite, mordenite/beta zeolite or the ZSM-5/ β zeolite according to the method for the described preparing olefin by catalytic cracking of claim 1; The silica alumina ratio SiO of composite molecular screen
2/ Al
2O
3Be 10～500; The consumption of composite molecular screen is 10～60% of catalyst weight by weight percentage in the catalyzer.
4,, it is characterized in that the silica alumina ratio SiO of composite molecular screen according to the method for the described preparing olefin by catalytic cracking of claim 3
2/ Al
2O
3Be 20～300.
5,, it is characterized in that the consumption of composite molecular screen in the catalyzer is 20～50% of catalyst weight by weight percentage according to the method for the described preparing olefin by catalytic cracking of claim 3.
6,, it is characterized in that temperature of reaction is 600～650 ℃ according to the method for the described preparing olefin by catalytic cracking of claim 1; Reaction pressure is 0.02～0.2MPa.
7, according to the method for the described preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that reacting weight space velocity is 0.5～2 hour
-1Water/petroleum naphtha weight ratio is 2～3: 1.
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