CN100532335C - Method for preparing ethene and propene by fluidized bed catalysis cracking - Google Patents
Method for preparing ethene and propene by fluidized bed catalysis cracking Download PDFInfo
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- CN100532335C CN100532335C CNB2006101185299A CN200610118529A CN100532335C CN 100532335 C CN100532335 C CN 100532335C CN B2006101185299 A CNB2006101185299 A CN B2006101185299A CN 200610118529 A CN200610118529 A CN 200610118529A CN 100532335 C CN100532335 C CN 100532335C
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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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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method of producing ethylene and propylene by fluidized bed catalytic cracking, and mainly solves the problem that when producing the ethylene and the propylene by naphtha catalytic cracking, reaction temperature is high, activity of catalyst is low when at low temperature and yield of ethylene and propylene is low. The invention adopts naphtha of C4-C10 hydrocarbon as raw material to produce the ethylene and the propylene by catalytic cracking in reaction conditions of temperature of 550 - 700 DEG C, reaction pressure of 0.001 to 0.5MPa, weight space velocity of 0.1 to 4h<-1> and weight ration of water to naphtha of 0.5 to 4:1. The catalyst technical proposal is that SiO2 or at least one of compound molecular sieves is adopted as a carrier, containing compound of which a chemical formula based on atomic ratio calculation is Mo1.0VaAbBcCdOx, wherein A is at least one of VIII, IB, IIB, VIIB, VIB, IA or IIA that are selected from periodic table of chemical elements, B is at least one of lanthanons and C is catalyst that is at least one of Bi or P, thereby properly solving the problem. The invention is used for industrial production of the ethylene and the propylene by naphtha catalytic cracking.
Description
Technical field
The present invention relates to the method for a kind of fluid catalytic cracking system ethene and propylene.
Background technology
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.Whole world ethene is raw material with petroleum naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of ultimate production.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard scission 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; Carbon 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.Therefore, seek a kind of suitable catalyst for cracking, overcome above-mentioned shortcoming, more and more become the problem that people are concerned about.
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.
U.S. Pat P6211104 adopts 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.
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%.
Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the molecular sieve of aperture between the 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.
The USSR (Union of Soviet Socialist Republics) patent USSR Pat1298240.1987 Zr that is carried on float stone or the pottery
2O
3, air speed is 2～5 hours on 660～780 ℃ of middle-scale devices of temperature
-1, water/petroleum naphtha weight ratio is 1: 1.With normal paraffin C
7～17, 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 catalytic pyrolysis preparing ethylenes and propylene, the yield that ethene adds propylene can reach 47%.
In sum, existing catalytic pyrolysis preparing ethylene and propylene technology, temperature of reaction is higher, but that ethene and propene yield increase is not obvious.
Summary of the invention
Technical problem to be solved by this invention is to overcome existing catalytic pyrolysis technology to have the temperature of reaction height, the catalyst system therefor low temperature problem that activity is not high down, selectivity is bad, a kind of new fluid catalytic cracking system ethene and the method for propylene are provided, use this method catalytic pyrolysis petroleum naphtha preparing ethylene and propylene, have and to reduce the catalytic pyrolysis temperature, and can keep the advantage of high ethylene, propylene yield simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of fluid catalytic cracking system ethene and propylene 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:
Mo
1.0V
aA
bB
cC
dO
x
A is selected from least a element in period of element Table VIII family, IB family, IIB family, VIIB family, group vib, IA family or the IIA family in the formula;
B is selected from least a in the rare earth element;
C is selected from least a among Bi or the P;
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;
The span of d is 0.01～0.5;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Composite molecular screen is to be selected from the mixture that at least two kinds of molecular sieve syntrophism in ZSM-5, Y, β or the mordenite become;
Wherein the support of the catalyst consumption is 20～80% of catalyst weight by weight percentage; VIII family element preferred version is to be selected from least a among Fe, Co or the Ni; I B family element preferred version is to be selected from least a among Cu or the Ag; IIB family element preferred version is for being selected from Zn; VIIB family element is selected from least a among Mn or the Re; The group vib element is selected from least a among Cr, Mo or the W; IA family element preferred version is to be selected from least a among Li, Na or the K; IIA element preferred version is to be selected from least a among Ca, Mg, Sr or the Ba; The rare earth element preferred version is to be selected from least a among La or the Ce.。
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 value preferable range of d is 0.01～0.3.If when containing Cr during catalyzer is formed, be 1: 0.01～0.5 with atomic ratio measuring Mo: Cr.The preferred version of support of the catalyst is that composite molecular screen is selected from least a in ZSM-5/ mordenite, ZSM-5/Y zeolite or the ZSM-5/ β zeolite.The SiO of composite molecular screen
2/ Al
2O
3It is 10～500 that mol ratio is preferably, more preferably 20～300.Support of the catalyst preferable range consumption is 30～50% of catalyst weight by weight percentage.
The method for preparing catalyst that relates among the present invention is as follows: what raw material Mo used is ammonium molybdate or phospho-molybdic acid; What V used is ammonium meta-vanadate or Vanadium Pentoxide in FLAKES; What Bi used is Bismuth trinitrate; What the category-A element was used is corresponding nitrate, oxalate, acetate, oxide compound or soluble halide; What the category-B element was used is corresponding nitrate, oxalate, acetate, oxide compound or soluble halide; Used phosphoric derives from phosphoric acid, triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate.The molding mode of catalyzer is that the slurries that will add each component element and carrier carry out spraying drying in reflux in 70～80 ℃ the water-bath after 5 hours.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 a series of transition metal and rare earth metals that cryogenic absorption, oxidation-reduction quality and difunctional soda acid position cooperate that have, and it has stronger low temperature active, raw material is played the effect of oxidation catalysis.Under 600～650 ℃ of relatively low temperature condition, catalyzer is used for the petroleum naphtha catalytic cracking reaction, and the ethylene, propylene yield of acquisition can reach 45%, has obtained better technical effect.
In order to check and rate catalyst activity involved in the present invention, 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.It with internal diameter 39 millimeters fluidized-bed reactor examination.The scope of temperature of reaction is 600～650 ℃, and weight space velocity is 0.5～2 hour
-1, water/stock oil weight ratio is 2～3: 1, 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 |
| Contained structure alkane % (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 3 gram ammonium meta-vanadates, add 100 ml waters, splash into 2 milliliter 80% phosphoric acid, add oxalic acid 3 grams, be heated to the ammonium meta-vanadate dissolving, obtain solution (I).
Other gets 5.89 gram Bismuth trinitrates, with 10 milliliters of dissolvings of 1: 1 concentrated nitric acid, gets yellow solution.Other gets 30 gram ammonium molybdates and is dissolved in 200 ml waters, is poured into bismuth nitrate solution, stirs, and makes solution (II).
Get Xiao Suangu 7.86 grams again, cerous nitrate 5.58 grams, nitrocalcite 6.72 grams are dissolved in the three in 250 ml waters together, obtain solution (III).
With solution (I), (II), (III) mix, place heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 26 grams that weigh up, refluxed 5 hours, use the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Co
0.16Ca
0.17Ce
0.08Bi
0.07O
x+ 30.6% carrier
Carry out the catalyst activity evaluation under the following conditions: the fluidized-bed reactor of 39 millimeters internal diameters, temperature of reaction are 650 ℃, and pressure is 0.02MPa.Water/petroleum naphtha weight ratio is 3: 1, and the catalyzer loading amount is 20 grams, and weight space velocity is 1 hour
-1Collect gaseous product, carry out gas chromatographic analysis, products distribution sees Table 2.
Table 2 cracking primary product distributes and the diene yield
| Product | Content (weight %) |
| Methane | 18.32 |
| Ethane | 3.54 |
| Ethene | 33.47 |
| Propane | 0.56 |
| Propylene | 13.53 |
| C 4 | 4.57 |
| Transformation efficiency | 87.5 |
| Yield of ethene (weight %) | 31.53 |
| Propene yield (weight %) | 12.96 |
| Ethene+propene yield (weight %) | 44.49 |
[embodiment 2]
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, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, can make the composite molecular screen of ZSM-5 and mordenite.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, makes Hydrogen ZSM-5/ mordenite composite molecular sieve after repeating twice.
Make solution (I) with embodiment 1.
Other gets 30 gram ammonium molybdates, iron nitrate 7.61 grams, and zinc nitrate 5.88 grams, cerous nitrate 5.60 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silica 15 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 20 above-mentioned Hydrogen ZSM-5/ mordenite composite molecular sieve 21 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Fe
0.11Zn
0.12Ce
0.08P
0.10O
x+ 37.8% carrier
Other is with embodiment 1, and products distribution that obtains and diene yield see Table 3.
The gas-phase product of table 3 embodiment 2 distributes and the diene yield
| Product | Content (H 2Volume %, all the other weight %) |
| Hydrogen (volume %) | 15.06 |
| Methane | 18.08 |
| Ethane | 3.45 |
| Ethene | 32.65 |
| Propane | 0.45 |
| Propylene | 15.33 |
| C 4 | 6.58 |
| Other | 16.42 |
| Transformation efficiency | 84.36 |
| Yield of ethene (weight %) | 30.91 |
| Propene yield (weight %) | 14.52 |
| Ethene+propene yield (weight %) | 45.43 |
[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, B solution is slowly poured in the A solution with 100 gram distilled water, the powerful stirring, add 24.4 gram quadrols then, stir after 30 minutes, regulate the pH value about 11 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, 120 ℃ 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, twice, 550 ℃ of roasting of 70 ℃ of exchanges 3 hours, makes Hydrogen ZSM-5/Y zeolite composite molecular screen after repeating twice.
Make solution (I) with embodiment 1.
Other gets 30 and restrains ammonium molybdates, iron nitrate 7.61 grams, and nickelous nitrate 7.29 grams, lanthanum nitrate 5.60 grams, nitrocalcite 5.18 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silica 15 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 20 above-mentioned Hydrogen ZSM-5/Y composite molecular screen 21 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
Obtaining the catalyst chemical formula is: Mo
1.0V
0.15Fe
0.11Ni
0.15Ca
0.13La
0.08P
0.10O
x+ 35.2% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 27.88%, propylene: 16.54%, ethene+propylene: 44.42%.
[embodiment 4]
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 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.
Make solution (I) with embodiment 1.
Make solution (II) with embodiment 1.
Get Xiao Suangu 7.86 grams again, cerous nitrate 5.58 grams, cupric nitrate 6.76 grams are dissolved in the three in 250 ml waters together, obtain solution (III).
With solution (I), (II), (III) mix, place heated and stirred in 70～80 ℃ of water-baths, add silica 11 gram and the SiO that weighs up
2/ Al
2O
3Mol ratio is 20 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen 15 grams, refluxes 5 hours, uses the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Co
0.16Cu
0.17Ce
0.08Bi
0.07O
x+ 30.4% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 29.95%, propylene: 14.61%, ethene+propylene: 44.56%.
[embodiment 5]
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, 10 gram tetraethyl ammonium hydroxides then, stir after 30 minutes, regulate the pH value about 12 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: 0.1: 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, 550 ℃ of roastings are 3 hours then, makes h-mordenite/β zeolite composite molecular screen after repeating twice.
Make solution (I) with embodiment 1.
Other gets 30 and restrains ammonium molybdates, iron nitrate 7.61 grams, and nickelous nitrate 7.29 grams, cerous nitrate 5.44 grams, cupric nitrate 6.30 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silica 15 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 20 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen 21 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
Obtaining the catalyst chemical formula is: Mo
1.0V
0.15Fe
0.11Ni
0.15Cu
0.15Ce
0.07P
0.10O
x+ 35.2% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 29.65%, propylene: 12.61%, ethene+propylene: 42.26%.
[embodiment 6]
Amount according to the method for embodiment 2 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 100 Hydrogen ZSM-5/ mordenite composite molecular sieve.
Make solution (I) with embodiment 1.
Other gets 30 and restrains ammonium molybdates, Xiao Suangu 5.49 grams, and zinc nitrate 5.60 grams, cerous nitrate 5.44 grams, saltpetre 1.10 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silica 15 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 100 above-mentioned Hydrogen ZSM-5/ mordenite composite molecular sieve 45 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Co
0.11Zn
0.11K
0.06Ce
0.07P
0.10O
x+ 49.1% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 36.64%, propylene: 8.50%, ethene+propylene: 45.14%.
[embodiment 7]
Amount according to the method for embodiment 3 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 50 Hydrogen ZSM-5/Y zeolite composite molecular screen.
Make solution (I) with embodiment 1.
Other gets 30 gram phospho-molybdic acids, and 5.89 restrain Bismuth trinitrates, Xiao Suangu 5.49 grams, and nickelous nitrate 5.32 grams, cerous nitrate 5.44 grams, 50% manganese nitrate solution 10.81 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 20 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 50 above-mentioned Hydrogen ZSM-5/Y composite molecular screen 40 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
Obtaining the catalyst chemical formula is: Mo
1.0V
0.13Co
0.1Ni
0.1Mn
0.16Ce
0.07Bi
0.07P
0.17O
x+ 42% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 36.10%, propylene: 6.74%, ethene+propylene: 42.84%.
[embodiment 8]
Amount according to the method for embodiment 4 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 100 Hydrogen ZSM-5/ β zeolite composite molecular screen.
Make the mixing solutions (II) of mixing solutions (I) and phosphoric acid hydrogen two ammoniums by the method for embodiment 7, place heated and stirred in 70～80 ℃ of water-baths, add and place heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 30 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 100 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen 35 grams, refluxes 5 hours, uses the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
Obtaining the catalyst chemical formula is: Mo
1.0V
0.13Co
0.1Ni
0.1Mn
0.16Ce
0.07Bi
0.07P
0.17O
x+ 46.9% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 36.10%, propylene: 6.74%, ethene+propylene: 42.84%.
[embodiment 9]
Amount according to the method for embodiment 2 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 50 Hydrogen ZSM-5/ mordenite composite molecular sieve.
Make solution (I) with embodiment 1.
Other gets 30 and restrains ammonium molybdates, iron nitrate 7.61 grams, and Silver Nitrate 4.69 grams, SODIUMNITRATE 0.95 gram, lanthanum nitrate 5.60 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 25 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 50 above-mentioned Hydrogen ZSM-5/ mordenite composite molecular sieve 55 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Fe
0.11Ag
0.17Na
0.06La
0.08P
0.10O
x+ 56.3% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 37.15%, propylene: 7.82%, ethene+propylene: 44.97%.
[embodiment 10]
Amount according to the method for embodiment 3 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 100 Hydrogen ZSM-5/Y zeolite composite molecular screen.
Make solution (I) with embodiment 1.
Other gets 30 gram ammonium molybdates, and Xiao Suangu 7.86 restrains, cupric nitrate 6.30 grams, and lithium nitrate 0.75 gram, magnesium nitrate 7.30 grams, lanthanum nitrate 5.60 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 20 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 50 above-mentioned Hydrogen ZSM-5/ mordenite composite molecular sieve 45 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Co
0.11Cu
0.16Li
0.06Mg
0.17La
0.08P
0.10O
x+ 51.1% carrier other with embodiment 1, the product yield that obtains, ethene: 36.64%, propylene: 8.50%, ethene+propylene: 45.14%.
[embodiment 11]
Amount according to the method for embodiment 4 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 50 Hydrogen ZSM-5/ β zeolite composite molecular screen.
Make solution (I) with embodiment 1.
Other gets 30 gram ammonium molybdates, and nickelous nitrate 7.29 restrains, cupric nitrate 6.30 grams, and chromium nitrate 3.40 grams, nitrate of baryta 7.55 grams, cerous nitrate 5.60 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram Secondary ammonium phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 25 gram and the SiO that weigh up
2/ Al
2O
3Mol ratio is 50 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen 55 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.15Ni
0.15Cu
0.17Cr
0.05Ba
0.17Ce
0.08P
0.10O
x+ 56.3% carrier
Other is with embodiment 1, the product yield that obtains, and ethene: 37.15%, propylene: 7.82%, ethene+propylene: 44.97%.
[embodiment 12]
Amount according to the method for embodiment 2 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 40 Hydrogen ZSM-5/ mordenite composite molecular sieve.
Amount according to the method for embodiment 3 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 40 Hydrogen ZSM-5/Y zeolite composite molecular screen.
Make the mixing solutions (II) of mixing solutions (I) and phosphoric acid hydrogen two ammoniums by the method for embodiment 7, place heated and stirred in 70～80 ℃ of water-baths, add silicon-dioxide 20 grams, the SiO that weigh up
2/ Al
2O
3Mol ratio is 40 above-mentioned Hydrogen ZSM-5/ mordenite composite molecular sieve 20 gram and SiO
2/ Al
2O
3Mol ratio is 40 above-mentioned Hydrogen ZSM-5/Y zeolite composite molecular screen 20 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.13Co
0.1Ni
0.1Mn
0.16Ce
0.07Bi
0.07P
0.17O
x+ 42.1% carrier
The examination condition is with embodiment 1, and in the product that obtains, yield of ethene is 36.48%, and propene yield is 7.81%, and the diene total recovery of ethene and propylene is 44.29%.
[embodiment 13]
Amount according to the method for embodiment 2 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 30 Hydrogen ZSM-5/ mordenite composite molecular sieve.
Amount according to the method for embodiment 4 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 20 Hydrogen ZSM-5/ β zeolite composite molecular screen.
Make the mixing solutions (II) of mixing solutions (I) and phosphoric acid hydrogen two ammoniums by the method for embodiment 7, place heated and stirred in 70～80 ℃ of water-baths, add and place heated and stirred in 70～80 ℃ of water-baths, add silica 10 gram, the SiO that weigh up
2/ Al
2O
3Mol ratio is 30 above-mentioned Hydrogen ZSM-5/ mordenite composite molecular sieve 20 gram and SiO
2/ Al
2O
3Mol ratio is 20 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen 20 grams.Refluxed 5 hours, and used the spray-drier dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyzer is sieved.
The catalyst chemical formula that obtains is: Mo
1.0V
0.13Co
0.1Ni
0.1Mn
0.16Ce
0.07Bi
0.07P
0.17O
x+ 37.6% carrier
The examination condition is with embodiment 1, and in the product that obtains, yield of ethene is 36.25%, and propene yield is 8.30%, and the diene total recovery of ethene and propylene is 44.55%.
[embodiment 14]
Amount according to the method for embodiment 3 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 30 Hydrogen ZSM-5/Y zeolite composite molecular screen.
Amount according to the method for embodiment 4 is passed through to change proportioning raw materials, pH value and added crystal seed makes SiO
2/ Al
2O
3Mol ratio is 30 Hydrogen ZSM-5/ β zeolite composite molecular screen.
Method by embodiment 1 makes mixing solutions, adds silica 10 gram, the SiO that weigh up
2/ Al
2O
3Mol ratio is 30 above-mentioned Hydrogen ZSM-5/Y zeolite composite molecular screen 20 gram and SiO
2/ Al
2O
3Mol ratio be 30 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen, 30 grams as carrier, make chemical formula by identical way and be: Mo
1.0V
0.15Co
0.16Ca
0.17Ce
0.08Bi
0.07O
xThe catalyzer of+50.4% carrier.Press the method examination of embodiment 1, in the product that obtains, yield of ethene is 37.17%, and propene yield is 8.25%, and the diene total recovery of ethene and propylene is 45.42%.
[embodiment 15]
Method by embodiment 1 makes mixing solutions, adds 500 gram distilled water dilutings, adds 60 gram SiO
2/ Al
2O
3Mol ratio is the ZSM-5/ mordenite composite molecular sieve of 20 Hydrogens, adds 100 gram SiO
2/ Al
2O
3Mol ratio is 200 Hydrogen ZSM-5/Y zeolite composite molecular screen molecular sieve, adds 40 gram SiO
2/ Al
2O
3Mol ratio is 30 ZSM-5/ β zeolite composite molecular screen, adds 22 gram silicon-dioxide, and making chemical formula by embodiment 1 identical way is Mo
1.0V
0.15Co
0.16Ca
0.17Ce
0.08Bi
0.07O
xThe catalyzer of+79.2% carrier.Press the method examination of embodiment 1, obtaining yield of ethene is 14.35%, and propene yield is 31.09%, and the total recovery of ethene and propylene is 45.44%.
[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 4 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 4 under the condition of 0.01MPa.
[embodiment 25～29]
By the catalyzer that embodiment 6 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 4.
[embodiment 30～33]
By the catalyzer that embodiment 12 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 4 under the condition of 2: 1 and 1: 1.
Table 4
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Ethene+propene yield (weight %) |
| Embodiment 16 | 25.43 | 15.85 | 41.28 |
| Embodiment 17 | 26.68 | 16.36 | 43.04 |
| Embodiment 18 | 29.05 | 16.22 | 45.27 |
| Embodiment 19 | 30.48 | 14.59 | 45.07 |
| Embodiment 20 | 28.05 | 12.15 | 40.20 |
| Embodiment 21 | 28.45 | 12.89 | 41.34 |
| Embodiment 22 | 28.68 | 13.65 | 42.33 |
| Embodiment 23 | 29.05 | 14.88 | 43.93 |
| Embodiment 24 | 30.36 | 14.92 | 45.28 |
| Embodiment 25 | 38.45 | 6.58 | 45.03 |
| Embodiment 26 | 37.84 | 7.15 | 44.99 |
| Embodiment 27 | 37.16 | 7.68 | 44.84 |
| Embodiment 28 | 36.25 | 8.34 | 44.59 |
| Embodiment 29 | 35.88 | 7.85 | 43.73 |
| Embodiment 30 | 38.45 | 6.84 | 45.29 |
| Embodiment 31 | 37.64 | 6.72 | 44.36 |
| Embodiment 32 | 36.05 | 7.52 | 43.57 |
| Embodiment 33 | 35.69 | 7.17 | 42.86 |
Claims (8)
1, the method for a kind of fluid catalytic cracking system ethene and propylene 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:
Mo
1.0V
aA
bB
cC
dO
x
A is selected from least a element in period of element Table VIII family, IB family, IIB family, VIIB family, group vib, IA family or the IIA family in the formula;
B is selected from least a in the rare earth element;
C is selected from least a among Bi or the P;
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;
The span of d is 0.01～0.5;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Composite molecular screen is to be selected from the mixture that at least two kinds of molecular sieve syntrophism in ZSM-5, Y, β or the mordenite become;
Wherein the support of the catalyst consumption is 20～80% of catalyst weight by weight percentage; VIII family element is selected from least a among Fe, Co or the Ni; IB family element is selected from least a among Cu or the Ag; IIB family element is selected from Zn; VIIB family element is selected from least a among Mn or the Re; The group vib element is selected from least a among Cr, Mo or the W; IA family element is selected from least a among Li, Na or the K; The IIA element is selected from least a among Ca, Mg, Sr or the Ba; Rare earth element is selected from least a among La or the Ce.
2, according to the method for described fluid catalytic cracking system ethene of claim 1 and propylene, 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; The span of d is 0.01～0.3.
3,, it is characterized in that composite molecular screen described in the support of the catalyst is selected from least a in ZSM-5/ mordenite, ZSM-5/Y zeolite or the ZSM-5/ β zeolite according to the method for described fluid catalytic cracking system ethene of claim 1 and propylene.
4,, it is characterized in that the silica alumina ratio SiO of described composite molecular screen according to the method for described fluid catalytic cracking system ethene of claim 3 and propylene
2/ Al
2O
3Be 10～500.
5,, it is characterized in that the silica alumina ratio SiO of described composite molecular screen according to the method for described fluid catalytic cracking system ethene of claim 4 and propylene
2/ Al
2O
3Be 20～300.
6,, it is characterized in that the support of the catalyst consumption is 30～50% of catalyst weight by weight percentage according to the method for described fluid catalytic cracking system ethene of claim 1 and propylene.
7,, when it is characterized in that containing Cr in the catalyzer composition, be 1: 0.01～0.5 with atomic ratio measuring Mo: Cr according to the method for described fluid catalytic cracking system ethene of claim 1 and propylene.
8,, it is characterized in that temperature of reaction is 600～650 ℃ according to the method for described fluid catalytic cracking system ethene of claim 1 and propylene; Reaction pressure is 0.02～0.2MPa; The reaction weight space velocity is 0.5～2 hour
-1Water/petroleum naphtha weight ratio is 2～3: 1.
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