CN100368357C - Method for producing ethene, propylene by using naphtha - Google Patents

Method for producing ethene, propylene by using naphtha Download PDF

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Publication number
CN100368357C
CN100368357C CNB2005100287981A CN200510028798A CN100368357C CN 100368357 C CN100368357 C CN 100368357C CN B2005100287981 A CNB2005100287981 A CN B2005100287981A CN 200510028798 A CN200510028798 A CN 200510028798A CN 100368357 C CN100368357 C CN 100368357C
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naphtha
catalyst
propylene
ethylene propylene
span
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CN1915927A (en
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谢在库
姚晖
马广伟
肖景娴
陈亮
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to CNB2005100287981A priority Critical patent/CN100368357C/en
Priority to KR1020060076882A priority patent/KR101270191B1/en
Priority to US11/503,925 priority patent/US20070042904A1/en
Priority to JP2006221462A priority patent/JP5465822B2/en
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Abstract

This invention relates to a method for manufacturing propylene and ethylene by naphtha catalytic cracking. The method adopts C5-10 naphtha as the raw material, which is cracked at 580-650 deg.C, 0-0.2 MPa, catalyst load of 0.1-2 g naphtha/g catalyst .h, and water/naphtha weight ratio of (0.5-3) : 1 to obtain propylene and ethylene. The catalyst uses SiO2, Al2O3 or their mixture as the carrier, and a composition with the chemical formula of Mo1.0BiaVbAcBdOx as the active component. The method solves the problems of high reaction temperature, low catalyst activity at low temperatures and low selectivity, and can be used in propylene and ethylene industrial manufacture by naphtha catalytic cracking.

Description

The method that is used for producing ethene, propylene by using naphtha
Technical field
The present invention relates to a kind of method that is used for the petroleum naphtha preparing ethylene and propylene, particularly about being used for the method for naphtha catalytic pyrolysis preparing ethylene propylene.
Background technology
The main 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 temperature of reaction height, processing condition harshness, to equipment especially furnace tube material requirement height, discharge a large amount of CO 2, shortcoming such as loss is big.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.
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 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 preparing ethylene propylene from catalytic pyrolysis, the diene yield can reach 47%.
In sum, existing preparing ethylene propylene from catalytic pyrolysis technology, temperature of reaction is higher, but that the ethylene, propylene yield increases 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.The invention provides a kind of new method that is used for naphtha catalytic pyrolysis preparing ethylene propylene.Use method preparing ethylene and propylene of the present invention, it is low to have temperature of reaction, and the catalyst activity is good, the advantage that the ethylene, propylene selectivity is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for naphtha catalytic pyrolysis preparing ethylene propylene, and with C 5～C 10Petroleum naphtha be raw material, in temperature of reaction is 580～650 ℃, reaction pressure is 0～0.2MPa, catalyst loading is 0.1～2 gram petroleum naphtha/gram catalyzer hour, water/petroleum naphtha weight ratio is under 0.5～3: 1 the condition, raw material is by the catalyst fluidized bed bed, and wherein said catalyzer contains and is selected from SiO 2, Al 2O 3Or the carrier of its mixture and with the following composition of atomic ratio measuring chemical formula:
Mo 10Bi aV bA cB dO x
A is selected from least a element among VIII family, IB family, IIB family, IA family or the IIA in the formula;
B is selected from least a in the rare earth element;
The span 0.01～0.5 of a;
The span 0.01～0.5 of b;
The span 0.01～0.5 of c;
The span 0.01～0.5 of d;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
The support of the catalyst consumption is 20～80% of catalyst weight by weight percentage.
In the technique scheme, the value preferable range of a is 0.01～0.2; 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 for being selected from Cu, Ag or its mixture; IIB family element preferred version is for being selected from Zn; 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.Support of the catalyst consumption preferable range by weight percentage is 30～50% of a catalyst weight.The temperature of reaction preferable range is 600～650 ℃; The catalyst loading preferable range is 0.5～1.5 gram petroleum naphtha/gram catalyzer hour; Water/petroleum naphtha weight ratio preferable range is 1.0～3: 1; The reaction pressure preferable range is 0.1～0.2MPa.
What the raw material Mo of the catalyzer that uses in the inventive method 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 or soluble halide; What the category-B element was used is corresponding nitrate, oxide compound.
The forming mode of the catalyzer that uses in preparation the inventive method is to have added the slurries of each component element and carrier, carry out spraying drying after 5 hours in reflux in 70～80 ℃ the water-bath, maturing temperature after the shaping is 600～750 ℃, and roasting time is 3～10 hours.
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 in the inventive method.Under 600～650 ℃ of relatively low temperature condition, catalyzer is used for the petroleum naphtha catalytic cracking reaction, makes the diene yield can reach 45.3%, obtains better technical effect.
The catalyzer examination that relates to, raw materials used petroleum naphtha (specific targets see Table 1).The temperature range of reaction is 600～650 ℃, and catalyst loading is 0.5～2 gram petroleum naphtha/gram catalyzer hour, and water/petroleum 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) 65.2
Normal paraffin % 32.5
Naphthenic hydrocarbon % 28.4
Alkene % (weight) 0.17
Aromatic hydrocarbons % (weight) 6.2
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get 5.89 gram Bismuth trinitrates,, get yellow solution with 10 milliliters of dissolvings of 1: 1 concentrated nitric acid.Other gets 30 gram ammonium molybdates and is dissolved in 200 ml waters, is poured into bismuth nitrate solution, stirs, and makes solution (I).
Other gets 3 gram ammonium meta-vanadates, adds 100 ml waters, splashes into 2 milliliter 80% phosphoric acid, adds oxalic acid 3 grams, is heated to the ammonium meta-vanadate dissolving, obtains 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 in 70～80 ℃ of water-baths and heat, add silicon-dioxide 25 grams that weigh up, aluminum oxide 1 gram.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 1.0Bi 0.07V 0.15Co 0.16Ca 0.17Ce 0.08O 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 0.15MPa.Water/petroleum naphtha weight ratio is 3: 1, and the catalyzer loading amount is 20 grams, and load is 1 gram petroleum naphtha/gram catalyzer hour.Collect gaseous product, carry out gas chromatographic analysis, products distribution sees Table 2.
Table 2 cracking primary product distributes and the diene productive rate
Product Content (weight %)
Methane 18.24
Ethane 3.34
Ethene 33.43
Propane 0.46
Propylene 13.89
C 4 4.53
Transformation efficiency 86
Yield of ethene 31.44
Propene yield 13.06
The diene yield 44.50
[embodiment 2]
Make solution (I) and solution (II) with embodiment 1.Get iron nitrate 10.91 grams, nickelous nitrate 3.73 grams, lanthanum nitrate 5.85 grams, saltpetre 1.1 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 25 grams, aluminum oxide 1 gram.
Obtaining the catalyst chemical formula is: Mo 1.0Bi 0.07V 0.15Fe 0.16Ni 0.08K 0.06La 0.08O x+ 30.06% carrier
Other is with embodiment 1, and products distribution sees Table 3.
Table 3 cracking primary product distributes and the diene productive rate
Product Content (weight %)
Methane 18.52
Ethane 2.1
Ethene 38.16
Propane 0.25
Propylene 10.4
C4 3.12
Transformation efficiency 87.7
Yield of ethene 33.48
Propene yield 9.12
The diene yield 42.60
[embodiment 3]
Make solution (I) and solution (II) with embodiment 1.Get Xiao Suangu 7.86 grams, nitrate of baryta 1.68 grams, cerous nitrate 2.79 grams, saltpetre 1.30 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mixed rice.Add silicon-dioxide 30 grams, aluminum oxide 1.5 grams.
Obtaining the catalyst chemical formula is: Mo 1.0Bi 0.07V 0.15Co 0.16Ba 0.04K 0.04Ce 0.08O x+ 37.5% carrier other with embodiment 1, product yield: ethene 29.89%, propylene 7.37%, diene 37.25%.
[embodiment 4]
Make solution (I) and solution (II) with embodiment 1.Get Xiao Suangu 3.73 grams, cupric nitrate 3.10 grams, cerous nitrate 2.79 grams, saltpetre 1.30 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 25 grams, aluminum oxide 1 gram.
Obtaining the catalyst chemical formula is: Mo 1.0Bi 0.07V 0.15Co 0.08Cu 0.08K 0.08Ce 0.04O x+ 34.3% carrier other with embodiment 1, product yield: ethene 25.37%, propylene 15.35%, diene 40.72%.
[embodiment 5]
Make solution (I) and solution (II) with embodiment 1.Get Xiao Suangu 7.86 grams, zinc nitrate 0.8 gram, lanthanum nitrate 5.85 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 25 grams, aluminum oxide 1 gram.
The catalyst chemical formula that obtains is: Mo 1.0Bi 0.07V 0.15Co 0.16Zn 0.02La 0.08O x+ 32.7% carrier other with embodiment 1, product yield: ethene 28.29%, propylene 13.39%, diene 41.68%.
[embodiment 6]
Make solution (I) and solution (II) with embodiment 1.Get Xiao Suangu 7.86 grams, cupric nitrate 3.10 grams, lanthanum nitrate 5.85 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 25 grams, aluminum oxide 1 gram.
The catalyst chemical formula that obtains is: Mo 1.0Bi 0.07V 0.15Co 0.16Cu 0.08La 0.08O x+ 31.8% carrier other with embodiment 1, product yield: ethene 28.73%, propylene 12.26%, diene 41.00%.
[embodiment 7]
Make solution (I) and solution (II) with embodiment 1.Get Xiao Suangu 7.86 grams, chromium nitrate 6.39 grams, cerous nitrate 5.86 grams, saltpetre 2.60 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 25 grams, aluminum oxide 1 gram.
Obtaining the catalyst chemical formula is: Mo 1.0Bi 0.07V 0.15Co 0.16Cr 0.09K 0.15Ce 0.08O x+ 30.6% carrier other with embodiment 1, product yield: ethene 33.55%, propylene 9.77%, diene 43.33%.
[embodiment 8]
Make solution (I) and solution (II) with embodiment 1.Get iron nitrate 10.91 grams, zinc nitrate 0.80 gram, lanthanum trioxide 2.2 grams are dissolved in 250 ml waters, splash into an amount of rare nitric acid, to resolution of precipitate.Get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 25 grams, aluminum oxide 1 gram.
The catalyst chemical formula that obtains is: Mo 1.0Bi 0.07V 0.15Fe 0.16Zn 0.02La 0.08O x+ 33.0% carrier other with embodiment 1, product yield: ethene 32.18%, propylene 7.82%, diene 40.01%.
[embodiment 9]
The Preparation of catalysts method
Get 5.89 gram Bismuth trinitrates,, get yellow solution with 10 milliliters of dissolvings of 1: 1 concentrated nitric acid.Other gets 30 gram ammonium molybdates and is dissolved in 200 ml waters, is poured into bismuth nitrate solution, stirs, and makes solution (I).
Other gets 3 gram ammonium meta-vanadates, adds 100 ml waters, splashes into 2 milliliter 80% phosphoric acid, adds oxalic acid 3 grams, is heated to the ammonium meta-vanadate dissolving, obtains solution (II).
Get nickelous nitrate 7.29 grams again, cerous nitrate 2.79 grams, zinc nitrate 5.6 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 and heat, add silicon-dioxide 25 grams that weigh up, aluminum oxide 1 gram.Refluxed 5 hours, and carried out spraying drying subsequently.
With the exsiccant powder, cross 60 molybdenums sieve, place muffle furnace to be warming up to 740 ℃, calcination 5 hours.After the cooling, in mortar,, cross 100 mesh sieves with the catalyzer grinding powder.
The catalyst chemical formula that obtains is: Mo 1.0Bi 0.07V 0.15Ni 0.15Zn 0.11Ce 0.04O x+ 32.3% carrier
In order to check and rate activity of such catalysts, make reactor with the fluidized-bed of 39 mm dias, catalyzer loading amount 20 grams.Reaction pressure is 0.15MPa.With this understanding, choose different temperature, different catalyst loadings, different water/petroleum naphtha weight ratio is collected the reactant gases product, carries out gas chromatographic analysis.
This catalyzer is at 650 ℃, catalyst loading gram 0.75 gram petroleum naphtha/gram catalyzer hour, and water/petroleum naphtha weight ratio 3: 1, the gas-phase product that obtains distribution and ethylene, propylene yield, listed as table 4.
The gas-phase product of table 4 embodiment 9 distributes and the diene productive rate
Product Content (H 2Volume %, all the other weight %)
Hydrogen (volume %) 17.1
Methane 23.10
Ethane 3.02
Ethene 43.57
Propane 0.37
Propylene 13.29
C4 4.56
Other 12.09
Transformation efficiency 95.3
Yield of ethene 34.14
Propene yield 11.16
The diene yield 45.30
[embodiment 10～13]
The catalyzer that relates in the foregoing description 9, in different temperature of reaction, different catalyst loadings, different water/petroleum naphtha weight ratio, and under the different reaction pressures, the ethylene, propylene yield that obtains, listed as table 5.
The yield of table 5 catalyzer under different condition
Temperature of reaction (℃) Catalyst loading (gram petroleum naphtha/gram catalyzer hour) Water/petroleum naphtha weight ratio Reaction pressure (MPa) Yield (%)
650 1.0 3∶1 0.15 Ethene: 38.14% propylene: 6.65%
630 0.75 2∶1 0.16 Ethene: 37.22% propylene: 2.14%
650 0.5 3∶1 0.13 Ethene: 41.46% propylene: 3.01%
650 0.5 2∶1 0.12 Ethene: 40.43% propylene: 3.5%
[embodiment 14]
Method for preparing catalyst:
Make solution (I) and solution (II) with embodiment 1.Get iron nitrate 10.91 grams, chromium nitrate 10.03 grams, lanthanum nitrate 5.85 grams, saltpetre 1.1 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silicon-dioxide 30 grams, aluminum oxide 1.5 grams.
Obtaining the catalyst chemical formula is: Mo 1.0Bi 0.07V 0.15Fe 0.16Cr 0.15K 0.06La 0.08O x+ 32.1% carrier
In order to check and rate activity of such catalysts, make reactor with the fluidized-bed of 39 mm dias, catalyzer loading amount 20 grams.Reaction pressure is 0.15MPa.With this understanding, choose different temperature, different catalyst loadings, different water/petroleum naphtha weight ratio is collected the reactant gases product, carries out gas chromatographic analysis.
This catalyzer is at 620 ℃, catalyst loading gram 1 gram petroleum naphtha/gram catalyzer hour, and water/petroleum naphtha weight ratio 3: 1, the gas-phase product that obtains distribution and ethylene, propylene yield, listed as table 6.
The gas-phase product of table 6 embodiment 14 distributes and the diene productive rate
Product Content (H 2Volume %, all the other weight %)
Hydrogen (volume %) 15.5
Methane 18.34
Ethane 2.60
Ethene 40.31
Propane 0.46
Propylene 17.10
C4 6.02
Other 15.17
Transformation efficiency 86.46
Yield of ethene 29.45
Propene yield 12.50
The diene yield 41.95
[embodiment 15～18]
The catalyzer that relates in the foregoing description 9, in different temperature of reaction, different catalyst loadings, different water/petroleum naphtha weight ratio, and under the different reaction pressures, the ethylene, propylene yield that obtains, listed as table 7.
The yield of table 7 catalyzer under different condition
Temperature of reaction (℃) Catalyst loading (gram petroleum naphtha/gram catalyzer hour) Water/petroleum naphtha weight ratio Reaction pressure (MPa) Yield (%)
650 1.5 3∶1 0.12 Ethene: 35.30% propylene: 6.27%
640 1.0 2∶1 0.15 Ethene: 32.90% propylene: 8.21%
620 0.75 3∶1 0.16 Ethene: 31.98% propylene: 7.61%
610 0.5 1∶1 0.13 Ethene: 31.04% propylene: 6.22%

Claims (9)

1. method that is used for naphtha catalytic pyrolysis preparing ethylene propylene is with C 5～C 10Petroleum naphtha be raw material, in temperature of reaction is 580～650 ℃, reaction pressure is 0～0.2MPa, catalyst loading is 0.1～2 gram petroleum naphtha/gram catalyzer hour, water/petroleum naphtha weight ratio is under 0.5～3: 1 the condition, raw material is by the catalyst fluidized bed bed, and wherein said catalyzer contains and is selected from SiO 2, Al 2O 3Or the carrier of its mixture and with the following composition of atomic ratio measuring chemical formula:
Mo 1.0Bi aV bA cB dO x
A is selected from least a element among VIII family, IB family, IIB family, IA family or the IIA in the formula;
B is selected from least a in the rare earth element;
The span 0.01～0.5 of a;
The span 0.01～0.5 of b;
The span 0.01～0.5 of c;
The span 0.01～0.5 of d;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
The support of the catalyst consumption is 20～80% of catalyst weight by weight percentage.
2. according to the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, the span that it is characterized in that a is 0.01～0.2, and the span of b is 0.01～0.3, and the span of c is 0.01～0.3, and the span of d is 0.01～0.3.
3. according to the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that VIII family element is selected from least a among Fe, Co or the Ni; IB family element is selected from Cu, Ag or its mixture; IIB family element is selected from Zn; 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.
4. according to the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that rare earth element is selected from least a among La or the Ce.
5. according to the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that the support of the catalyst consumption is 30～50% of a catalyst weight.
6. according to the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that temperature of reaction is 600～650 ℃.
7. according to the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1, it is characterized in that catalyst loading is 0.5～1.5 gram petroleum naphtha/gram catalyzer hour.
8. the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1 is characterized in that the water/petroleum naphtha weight ratio of reacting is 1.0～3: 1.
9. the described method that is used for naphtha catalytic pyrolysis preparing ethylene propylene of claim 1 is characterized in that reaction pressure is 0.1～0.2MPa.
CNB2005100287981A 2005-08-15 2005-08-15 Method for producing ethene, propylene by using naphtha Active CN100368357C (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CNB2005100287981A CN100368357C (en) 2005-08-15 2005-08-15 Method for producing ethene, propylene by using naphtha
KR1020060076882A KR101270191B1 (en) 2005-08-15 2006-08-14 Method for preparation of ethylene and propylene by catalytic cracking using a fluid-bed catalyst
US11/503,925 US20070042904A1 (en) 2005-08-15 2006-08-15 Fluid-bed catalyst for the preparation of ethylene and propylene by catalytic cracking
JP2006221462A JP5465822B2 (en) 2005-08-15 2006-08-15 Fluidized bed catalysts for the production of ethylene and propylene by catalytic cracking.
US12/365,146 US7686942B2 (en) 2005-08-15 2009-02-03 Method for preparation of ethylene and propylene by catalytic cracking using a fluid-bed catalyst

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1519053A (en) * 1998-09-03 2004-08-11 Catalyst compsns
CN1189434C (en) * 2002-12-11 2005-02-16 中国石油化工股份有限公司 Process of catalytically cracking C4 and above olefin to produce propylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1519053A (en) * 1998-09-03 2004-08-11 Catalyst compsns
CN1189434C (en) * 2002-12-11 2005-02-16 中国石油化工股份有限公司 Process of catalytically cracking C4 and above olefin to produce propylene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型乙烯制备技术研究进展. 朱海欧，李文钊，徐恒泳.天然气化工(C1化学与化工)，第3期. 2004 *

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