CN100443168C - Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking - Google Patents

Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking Download PDF

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CN100443168C
CN100443168C CNB2005100287962A CN200510028796A CN100443168C CN 100443168 C CN100443168 C CN 100443168C CN B2005100287962 A CNB2005100287962 A CN B2005100287962A CN 200510028796 A CN200510028796 A CN 200510028796A CN 100443168 C CN100443168 C CN 100443168C
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propylene
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CN1915493A (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 CNB2005100287962A priority Critical patent/CN100443168C/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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    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

A catalyst for preparing ethene and propene by catalytic cracking of petroleum naphtha on fluidized bed is composed of the carrier chosen from SiO2, Al2O3 and their mixture and the active component Mo1.0BiaVbAcBdOx. It has high low-temp activity, selectivity and low reaction temp.

Description

The fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis
Technical field
The present invention relates to a kind of fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis.
Background technology
The main method of preparing ethylene and propylene is the steam heat cracking at present.Maximum raw material that adopts is a naphtha.But the steam heat cracking naphtha exists reaction temperature height, process conditions 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 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.
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%.
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 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 CN14802255A introduces a kind of oxide catalyst, is raw material with 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, reaction temperature 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 reaction temperature height, and the catalyst system therefor low temperature problem that activity is not high down, selectivity is bad provides a kind of new fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis.It is low to use this catalyst to have reaction temperature, good catalyst activity, 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 fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis, contain and be 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, I B family, II B family, I A family or the II A in the formula;
B is selected from least a in the rare earth element;
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 oxygen atom sum of each element valence in the catalyst;
Wherein the catalyst carrier consumption is 20～80% of catalyst weight by weight percentage.VIII family element is selected from least a among Fe or the Co, and I B family element is selected from Cu, Ag or its mixture, and II B family element is selected from Zn, and I A family element is selected from least a among Li, Na or the K, and II A element is selected from least a among Ca, Mg, Sr or the Ba.
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.The rare earth element preferred version is to be selected from least a among La or the Ce.Catalyst also contains Cr in forming, and is 1: 0.01～0.5 with atomic ratio measuring Mo: Cr.Catalyst carrier consumption preferable range by weight percentage is 30～50% of a catalyst weight.
What the raw material Mo of preparation catalyst 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 or soluble halide; What the category-B element was used is corresponding nitrate, oxide.
The forming mode of preparation catalyst is to have added the slurries of each component element and carrier, carries out spray-drying after 5 hours adding hot reflux in 70～80 ℃ the water-bath.The powder that obtains roasting in muffle furnace, temperature are 600～750 ℃, and roasting time is 3～10 hours.
The present invention is owing to adopted 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 conditions, catalyst is used for the naphtha catalytic cracking reaction, makes the diene yield can reach 44.50%, obtains better technical effect.
Catalyst reaction temperatures should be between 580～750 ℃, and preferable range is 600～650 ℃, and catalyst loading should be 0.5～2 gram naphtha/gram catalyst hour.
The catalyst examination that relates to, raw materials used naphtha (specific targets see Table 1).Range of reaction temperature is 600～650 ℃, and catalyst loading is 0.5～2 gram naphtha/gram catalyst hour, and water/naphtha weight ratio is 1.5～3: 1.The internal diameter of fluidized-bed reactor is 39 millimeters, reaction pressure 0.15MPa.
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
N-alkane % 32.5
Cycloalkane % 28.4
Alkene % (weight) 0.17
Aromatic hydrocarbons % (weight) 6.2
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get 5.89 gram bismuth nitrates,, get yellow solution with 10 milliliters of dissolvings of 1: 1 red fuming nitric acid (RFNA).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 metavanadates, adds 100 ml waters, splashes into 2 milliliter 80% phosphoric acid, adds oxalic acid 3 grams, is heated to the ammonium metavanadate dissolving, obtains 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 and heat, add silica 25 grams that weigh up, aluminium oxide 1 gram.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 1.0Bi 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, reaction temperature are 650 ℃, and pressure is 0.15MPa.Water/naphtha weight ratio is 3: 1, and the catalyst loading amount is 20 grams, and load is 1 gram naphtha/gram catalyst hour.Collect gaseous product, carry out gas chromatographic analysis, product distributes and 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
Conversion ratio 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 ferric nitrate 10.91 grams, nickel nitrate 3.73 grams, lanthanum nitrate 5.85 grams, potassium nitrate 1.1 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silica 25 grams, aluminium 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 product distributes and 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
Conversion ratio 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 cobalt nitrate 7.86 grams, barium nitrate 1.68 grams, cerous nitrate 2.79 grams, potassium nitrate 1.30 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silica 30 grams, aluminium 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 cobalt nitrate 3.73 grams, copper nitrate 3.10 grams, cerous nitrate 2.79 grams, potassium nitrate 1.30 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silica 25 grams, aluminium 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 cobalt nitrate 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 silica 25 grams, aluminium 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 cobalt nitrate 7.86 grams, copper 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 silica 25 grams, aluminium 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 cobalt nitrate 7.86 grams, chromic nitrate 6.39 grams, cerous nitrate 5.86 grams, potassium nitrate 2.60 grams are dissolved in 250 ml waters, get solution (III).
With solution (I) (II) (III) mix.Add silica 25 grams, aluminium 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 ferric nitrate 10.91 grams, zinc nitrate 0.80 gram, lanthana 2.2 grams are dissolved in 250 ml waters, splash into an amount of rare nitric acid, to the precipitation dissolving.Get solution (III).
With solution (I) (II) (III) mix.Add silica 25 grams, aluminium 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%.

Claims (5)

1, a kind of fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis 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, I B family, II B family, I A family or the II A in the formula;
B is selected from least a in the rare earth element;
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 oxygen atom sum of each element valence in the catalyst;
Wherein the catalyst carrier consumption is 20～80% of catalyst weight by weight percentage; VIII family element is selected from least a among Fe or the Co, and I B family element is selected from Cu, Ag or its mixture, and II B family element is selected from Zn, and I A family element is selected from least a among Li, Na or the K, and II A element is selected from least a among Ca, Mg, Sr or the Ba.
2, according to the described fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis of claim 1, the span that it is characterized in that a is 0.01～0.2; 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 rare earth element is selected from least a among La or the Ce according to the described fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis of claim 1.
4, according to the described fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis of claim 1, it is characterized in that catalyst also contains Cr in forming, be 1: 0.01～0.5 with atomic ratio measuring Mo: Cr.
5,, it is characterized in that the catalyst carrier consumption is 30～50% of catalyst weight by weight percentage according to the described fluid catalyst that is used for preparing ethylene propylene from catalytic pyrolysis of claim 1.
CNB2005100287962A 2005-08-15 2005-08-15 Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking Active CN100443168C (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CNB2005100287962A CN100443168C (en) 2005-08-15 2005-08-15 Catalyst of fluid bed in use for preparing ethane, propylene through catalytic cracking
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101279285B (en) * 2007-04-04 2010-05-19 中国石油化工股份有限公司 Naphtha catalytic pyrolysis catalyst for preparing ethylene propylene
CN111203225B (en) * 2020-01-09 2023-07-04 中国石油大学(华东) Catalyst for preparing low-carbon olefin by hydrocarbon catalytic pyrolysis and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705769A (en) * 1985-07-25 1987-11-10 Phillips Petroleum Company Composition of matter for conversion of C3 and C4 hydrocarbons
CN1219532A (en) * 1997-12-11 1999-06-16 中国石油化工总公司 Catalyst for propylene and isobutylene ammoxidation fluidized bed

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705769A (en) * 1985-07-25 1987-11-10 Phillips Petroleum Company Composition of matter for conversion of C3 and C4 hydrocarbons
CN1219532A (en) * 1997-12-11 1999-06-16 中国石油化工总公司 Catalyst for propylene and isobutylene ammoxidation fluidized bed

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