CN101190411B - Fluid bed catalyst for producing ethylene and propylene by catalytic cracking method - Google Patents
Fluid bed catalyst for producing ethylene and propylene by catalytic cracking method Download PDFInfo
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- CN101190411B CN101190411B CN200610118530A CN200610118530A CN101190411B CN 101190411 B CN101190411 B CN 101190411B CN 200610118530 A CN200610118530 A CN 200610118530A CN 200610118530 A CN200610118530 A CN 200610118530A CN 101190411 B CN101190411 B CN 101190411B
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Abstract
The invention relates to a fluidized bed activator used for preparing ethene and propylene by catalyzing and cracking, mainly solving the problems of high temperature, low low-temperature activity ofactivator and low yield of ethene and propylene in the reaction in which ethene and ropylene are prepared by catalyzing and cracking with naphtha. The invention adopts at least one from SiO2 or composite molecular sieve as the carrier and contains the following compounds with chemical formula measured by atom ratio: Mo1.0VaAbBcCdOx; wherein, B is chosen from at least one of lanthanon; A is chosenfrom at least one out of VIII, IB, IIB, VIIB, VIB, IA or IIA in element periodic table; C is chosen from at least one activator technical proposal of Bi or P; the invention well solves the problems and can be applied in the industrial production, in which ethene and propylene are prepared by catalyzing and cracking with naphtha.
Description
Technical field
The present invention relates to the fluid catalyst of a kind of catalytic pyrolysis preparing ethylene and propylene.
Background technology
Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half.Whole world ethene is raw material with naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of total output.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard cracking reactions, and therefore than common steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; CO2 emission also can reduce, and can adjust the product mix flexibly, can increase the total recovery of ethene and propylene, and production cost of ethylene reduces significantly.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 component that the patent US4620051 of U.S. Phillips company and US4705769 have adopted with manganese oxide or iron 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
3Catalyst is in breadboard fixed bed reactors, and 700 ℃, the mol ratio of water and butane is 1: 1, and the conversion ratio of butane can reach 80%, ethene, and the selectivity of propylene is 34% and 20%.These two patents are claimed also can use 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 catalyst, to the various raw materials of traditional steam heat cracking, the activity, the especially ethene that well are converted into light olefin have been demonstrated.With molecular sieve be by 0～25 weight %Y zeolite of high silica alumina ratio or have the ZSM molecular sieve of MFI structure, form by phosphorus/Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyst and yield are not high.
It is 12CaO7Al that the patent CN1317546A of Italy En Niqiemu company relates to chemical formula
2O
3The steam cracking reaction catalyst.Raw material can be used naphtha, 720～800 ℃ of operating temperatures, and under 1.1～1.8 atmospheric pressure, 0.07～0.2 second time 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 catalyst, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower.
Exxon Mobil (00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550-600 ℃, and conversion of raw material is lower.
The patent USSR Pat1298240.1987 of the former Soviet Union 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/naphtha weight ratio is 1: 1.With n-alkane C
7～17, cyclohexane, direct steaming gasoline are raw material, ethylene yield can reach 46%, propylene 8.8%.
Chinese patent CN1480255A introduces a kind of oxide catalyst, is raw material with 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, reaction temperature 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 reaction temperature height, the catalyst system therefor low temperature problem that activity is not high down, yield is low.The invention provides a kind of new catalytic pyrolysis preparing ethylene and the fluid catalyst of propylene, it is low that this catalyst has reaction temperature, and the catalyst activity is good, can keep ethene and the high advantage of propene yield simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the fluid catalyst of a kind of catalytic pyrolysis preparing ethylene and propylene, and to be selected from composite molecular screen or composite molecular screen and SiO
2Mixture be carrier, contain 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 or the group vib 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 0～0.5;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Composite molecular screen is to be selected from the compound that at least two kinds of molecular sieves in ZSM-5, β or the modenite grow into jointly;
Wherein the catalyst carrier consumption is 20～80% of catalyst weight by weight percentage.
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.VIII family element preferred version is to be selected from least a among Fe, Co or the Ni; IB 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 or the W.The rare earth element preferred version is to be selected from least a among La or the Ce.If when containing Cr during catalyst is formed, be 1: 0.01～0.5 with atomic ratio measuring Mo: Cr.The preferred version of catalyst carrier is that composite molecular screen is selected from least a in ZSM-5/ modenite or the ZSM-5/ β zeolite.The SiO of composite molecular screen
2/ Al
2O
3Mol ratio preferably is 10～500, more preferably is 20～300.Catalyst carrier 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 phosphomolybdic acid; What V used is ammonium metavanadate or vanadic anhydride; What Bi used is bismuth nitrate; What the category-A element was used is corresponding nitrate, oxalates, acetate, oxide or soluble halide; What the category-B element was used is corresponding nitrate, oxalates, acetate, oxide or soluble halide; Used P elements derives from phosphoric acid, triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).To be the slurries that will add each component element and carrier carry out spray-drying adding hot reflux in 70～80 ℃ the water-bath to the molding mode of catalyst 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, it has stronger low temperature active, raw material is played the effect of oxidation catalysis. under 600～650 ℃ of relatively low temperature conditions, catalyst is used for the naphtha catalytic cracking reaction, make ethene and propylene total recovery can reach 45.5%, obtained better technical effect.
The catalyst examination that relates to, raw materials used naphtha (specific targets see Table 1).The temperature range of reaction is 600～650 ℃, and weight space velocity is 1 hour
-1, water/naphtha weight ratio is 1.5～3: 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 |
| Contained n-alkane % (weight %) in the alkane | ＞32.5 |
| Cycloalkane % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get 3 gram ammonium metavanadates, add 100 ml waters, splash into 2 milliliter 80% phosphoric acid, add oxalic acid 3 grams, be heated to the ammonium metavanadate dissolving, obtain solution (I).
Other gets 5.89 gram bismuth nitrates, with 10 milliliters of dissolvings of 1: 1 red fuming nitric acid (RFNA), 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 cobalt nitrate 7.86 grams again, cerous nitrate 5.58 grams, calcium nitrate 6.72 grams are dissolved in the three in 250 ml waters together, obtain solution (III).
With solution (I), (II), (III) mix, place in 70～80 ℃ of water-baths to add thermal agitation, add silica 26 grams that weigh up, refluxed 5 hours, use the spray dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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, reaction temperature are 650 ℃, and pressure is that 0.02MPa. water/naphtha weight ratio is 3: 1, and the catalyst loading amount is 20 grams, and weight space velocity is 1 hour
-1Collect gaseous product, carry out gas chromatographic analysis, product distributes and 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 |
| Conversion ratio | 87.5 |
| Yield of ethene (weight %) | 31.53 |
| Propene yield (weight %) | 12.96 |
| Ethene+propene yield (weight %) | 44.49 |
[embodiment 2]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, stir after 30 minutes, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, mixed solution is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, can make the composite molecular screen of ZSM-5 and modenite.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, ferric 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 diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 the product that obtains distributes and the diene yield sees 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 |
| Conversion ratio | 84.36 |
| Yield of ethene (weight %) | 30.91 |
| Propene yield (weight %) | 14.52 |
| Ethene+propene yield (weight %) | 45.43 |
[embodiment 3]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B, B solution is slowly poured in the A solution with 100 gram distilled water, the powerful stirring, add 24.4 gram ethylenediamines then, stir after 30 minutes, regulate the pH value about 11 with dilute sulfuric acid, add 5 gram Y zeolite seed crystals, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, mixed solution 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, ferric nitrate 7.61 grams, and nickel nitrate 7.29 grams, lanthanum nitrate 5.60 grams, calcium nitrate 5.18 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, 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 dryer dry forming again. and behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours. after the cooling, again catalyst 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 sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 16.7 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram ethylenediamines and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring a period of time, regulate the pH value 11 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.05: 0.4: 40, add 2.8 gram β zeolite seed crystals, mixed solution is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ beta zeolite coexisting molecular sieve.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 cobalt nitrate 7.86 grams again, cerous nitrate 5.58 grams, copper nitrate 6.76 grams are dissolved in the three in 250 ml waters together, obtain solution (III).
With solution (I), (II), (III) mix, place in 70～80 ℃ of water-baths to add thermal agitation, 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B, B solution is slowly poured in the A solution with 100 gram distilled water, the powerful stirring, add 24.4 gram ethylenediamines, 10 gram tetraethyl ammonium hydroxides then, stir after 30 minutes, regulate the pH value about 12 with dilute sulfuric acid, add 5 gram β zeolite seed crystals, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H
2O=1: 0.1: 0.4: 40, mixed solution is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the composite molecular screen of modenite 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, ferric nitrate 7.61 grams, and nickel nitrate 7.29 grams, cerous nitrate 5.44 grams, copper nitrate 6.30 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, add silica 15 gram and the silicon SiO that weigh up
2/ Al
2O
3Mole is 20 above-mentioned Hydrogen ZSM-5/ β zeolite composite molecular screen 21 grams.Refluxed 5 hours, and used the spray dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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, cobalt nitrate 5.49 grams, and zinc nitrate 5.60 grams, cerous nitrate 5.44 grams, potassium nitrate 1.10 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 phosphomolybdic acids, and 5.89 restrain bismuth nitrates, cobalt nitrate 5.49 grams, and nickel 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 diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, add silica 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 mixed solution (II) of mixed solution (I) and phosphoric acid hydrogen two ammoniums by the method for embodiment 7, place in 70～80 ℃ of water-baths to add thermal agitation, add to place in 70～80 ℃ of water-baths and add thermal agitation, add silica 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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, ferric nitrate 7.61 grams, and silver nitrate 4.69 grams, sodium nitrate 0.95 gram, lanthanum nitrate 5.60 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, add silica 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 cobalt nitrate 7.86 restrains, copper 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 diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, add silica 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 nickel nitrate 7.29 restrains, copper nitrate 6.30 grams, and chromic nitrate 3.40 grams, barium nitrate 7.55 grams, cerous nitrate 5.60 grams are dissolved in 250 ml waters, get solution (II).Dissolving 2.24 gram diammonium hydrogen phosphates are poured into solution (II) in 100 ml waters, (I) pours (II) into solution, places in 70～80 ℃ of water-baths to add thermal agitation, add silica 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 raw material proportioning, 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 mixed solution (II) of mixed solution (I) and phosphoric acid hydrogen two ammoniums by the method for embodiment 7, place in 70～80 ℃ of water-baths to add thermal agitation, add silica 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 raw material proportioning, 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 mixed solution (II) of mixed solution (I) and phosphoric acid hydrogen two ammoniums by the method for embodiment 7, place in 70～80 ℃ of water-baths to add thermal agitation, add to place in 70～80 ℃ of water-baths and add thermal agitation, 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 dryer dry forming again.Behind the gained powder sieving, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, again catalyst 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 raw material proportioning, 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 raw material proportioning, 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 mixed solution, 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 catalyst 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 mixed solution, 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 silica, and making chemical formula by embodiment 1 identical way is Mo
1.0V
0.15Co
0.16Ca
0.17Ce
0.08Bi
0.07O
xThe catalyst 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%.
Claims (9)
1. the fluid catalyst of catalytic pyrolysis preparing ethylene and propylene is to be selected from composite molecular screen or composite molecular screen and SiO
2Mixture be carrier, contain 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 or the group vib 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 0～0.5;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Composite molecular screen is to be selected from the compound that at least two kinds of molecular sieves in ZSM-5, β or the modenite grow into jointly;
Wherein the catalyst carrier consumption is 20～80% of catalyst weight by weight percentage.
2. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene 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. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 1 and propylene, it is characterized in that VIII family element is selected from least a among Fe, Co or the Ni; I B family element is selected from least a among Cu or the Ag; II B 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 or the W.
4. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 1 and propylene, it is characterized in that rare earth element is selected from least a among La or the Ce.
5. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 1 and propylene, it is characterized in that composite molecular screen described in the catalyst carrier is selected from least a in ZSM-5/ modenite or the ZSM-5/ β zeolite.
6. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 5 and propylene, it is characterized in that the silica alumina ratio SiO of described composite molecular screen
2/ Al
2O
3Be 10～500.
7. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 6 and propylene, it is characterized in that the silica alumina ratio SiO of described composite molecular screen
2/ Al
2O
3Be 20～300.
8. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 1 and propylene, it is characterized in that the catalyst carrier consumption is 30～50% of catalyst weight by weight percentage.
9. according to the fluid catalyst of described catalytic pyrolysis preparing ethylene of claim 1 and propylene, when it is characterized in that containing Cr in the catalyst composition, be 1: 0.01～0.5 with atomic ratio measuring Mo: Cr.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215932A (en) * | 1997-10-23 | 1999-05-05 | 株式会社村田制作所 | Dielectric line switch and antenna device |
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2006
- 2006-11-21 CN CN200610118530A patent/CN101190411B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215932A (en) * | 1997-10-23 | 1999-05-05 | 株式会社村田制作所 | Dielectric line switch and antenna device |
Non-Patent Citations (2)
| Title |
|---|
| 陈洪林,申宝剑,潘惠芳.ZSM-5/Y复合分子筛的酸性及其重油催化裂化性能.催化学报25 9.2004,25(9),715-720. |
| 陈洪林,申宝剑,潘惠芳.ZSM-5/Y复合分子筛的酸性及其重油催化裂化性能.催化学报25 9.2004,25(9),715-720. * |
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