CN1233604C - Alkyl aromatics dehydrogenating catalyst and its prepn. - Google Patents

Alkyl aromatics dehydrogenating catalyst and its prepn. Download PDF

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Publication number
CN1233604C
CN1233604C CNB011083832A CN01108383A CN1233604C CN 1233604 C CN1233604 C CN 1233604C CN B011083832 A CNB011083832 A CN B011083832A CN 01108383 A CN01108383 A CN 01108383A CN 1233604 C CN1233604 C CN 1233604C
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iron oxide
catalyzer
iron
dehydrogenating catalyst
stratiform
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CN1323767A (en
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颉伟
辛国萍
黄立本
王继龙
黄德华
王福善
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Lanzhou Petrochemical Institute Of China Petrochemical Corp
Petrochina Lanzhou Petrochemical Co
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Lanzhou Petrochemical Institute Of China Petrochemical Corp
Petrochina Lanzhou Petrochemical Co
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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

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Abstract

The present invention relates to an alkyl aromatic dehydrogenating catalyst and a preparing method thereof. The alkyl aromatic dehydrogenating catalyst uses Fe-K-Ce-Mo-Mg as a main system, wherein Fe is added in four different iron oxide forms. When a micro quantity combination system is added and a four-section pulse temperature controlling activating technique is used, the alkyl aromatic dehydrogenating catalyst has good performance; when in a low water ratio, the alkyl aromatic dehydrogenating catalyst still has high reactivity selectivity. The alkyl aromatic dehydrogenating catalyst has the advantages of simple preparation technology and large operation flexibility.

Description

A kind of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst and preparation method thereof
The present invention relates to a kind of alkyl aromatics dehydrogenation and produce alkyl alkenyl arene catalyst system therefor and preparation method thereof, be specially adapted to ethylbenzene, diethylbenzene or ethyltoluene dehydrogenation and generate vinylbenzene, divinylbenzene, perhaps the dehydrogenating technology process of vinyl toluene.
For many years, the production of alkenyl arene is mainly undertaken by alkyl aromatics dehydrogenation, and one of key of this production technology is exactly a dehydrogenation catalyst.The reactivity worth of catalyzer mainly is subjected to the influence of potassium content in the catalyzer, and potassium and iron are formed the activity of such catalysts center jointly, and the kind of iron, molecular structure, adding mode directly influence the formation in active centre.
Catalyzer is by early stage Fe 2O 3System and ZnO are two big classes, through the differentiation of Fe-K-Cr and Fe-K-Ce-Mo system, developed into Fe-K-Ce-Mo-Mg be main body be the 4th generation catalyzer.As disclosed: EP502510, DE3442636, Ru1267657, WO9710898 and CN87100517, be characterized in using in the catalyzer single ferric oxide or two kinds of ferric oxide, it is red iron oxide, iron oxide yellow, existing in addition catalyzer all adopts single hop or two stage activation technology, and the catalyzer principal crystalline phase is with α-Fe 2O 3Be main.Transformation efficiency 75-76%, selectivity all is not more than 94%, and makes the water ratio generally more than 1.5, and energy consumption is big.
The object of the present invention is to provide a kind of is the catalyzer of main body system with iron-potassium-cerium-molybdenum-magnesium, by regulating the adding form of ferro element, to promote the K of catalyst active center 2Fe 2O 4Formation, the performance and the work-ing life of improving catalyzer.
For achieving the above object, contain active constituent (in the oxide compound of reactive metal, weight percent): Fe in the composition of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of the present invention 2O 330-75% is preferably 55～65%, K 2O 5-25% is preferably 5-15%, Ce 2O 35-30% is preferably 10-20%, and MgO 0.01-10% is preferably 0.5-10%, MoO 30.1-6% is preferably 0.5-5%, and pore-creating agent 1～5%, specific surface are 2.0-3.5ml/g, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is with K 2Fe 2O 4Be main.
Iron in the catalyzer is in the form of ferric oxide, the ferric oxide that uses among the present invention is by red iron oxide, iron oxide yellow, iron oxide black, any three kinds or four kinds combine in the technical grade stratiform iron-stone rock, when red iron oxide, iron oxide yellow exist simultaneously, red iron oxide, iron oxide yellow proportioning are: 1-10: 4, the iron oxide black add-on is 0.2～2%, stratiform iron-stone rock 0-5%; Used potassium can potassium salt form adds, and used cerium can vitriol, nitrate or oxalate form add, molybdenum can molybdate or the double salt form add, magnesium can oxide compound, oxyhydroxide or magnesium salts form add.Be rich in iron in the stratiform iron-stone rock, with Fe 2+, Fe 3+Form exists.
Also can contain trace assistant in the catalyzer of the present invention, form by the metal in one or more IB～VIIIB, IIIA～VA family, as can being that the combination of oxides of some kinds of elements among Zr, Rb, Sr, Ti, V, W, Mn, Co, Ni, Pt, Cu, Ag, Zn, Sn, Pb, the Cd forms, consumption is 0～1%, and best add-on is 0.01-1wt%.
The adding of multiple ferric oxide has improved the degree of combining closely of Fe and K, and helps the K of catalyst active center 2Fe 2O 4Formation, in the catalyzer use, slow down since under hot conditions K 2Fe 2O 4Decomposition cause the phenomenon that reduces in catalyst performance and work-ing life.Activity of such catalysts, regenerability are improved, have prolonged work-ing life.
Catalyzer among the present invention is because principal crystalline phase is K 2Fe 2O 4, the active centre demonstrates extremely strong activity, and has pind down the migration of K, avoided the loss of K, therefore use the potassium amount very low, under the condition of suitable specific surface, pore volume, pore size distribution, can demonstrate high activity, the catalyzer life cycle is long, active, selectivity is stablized, for cooperating the characteristics of low potassium type, when selecting Ce, its content is higher relatively, to satisfy the needs to catalyst performance.
Also can further improve selectivity of catalyst and stability as containing trace assistant in the catalyzer of the present invention.
Preparation is during catalyzer, and the adding of active ingredient can be the oxide compound of metal, also can be the salt etc. of metal monomer, metal, is the compound that finally obtains metal oxide by certain approach in a word, and the adding of K can be KOH, K 2CO 3, Potassium ethanoate or the like.
Pore-creating agent of the present invention can use conventional polystyrene microsphere, graphite, carboxymethyl cellulose; Caking agent can be known cement.
The present invention also provides a kind of method for preparing this catalyzer, has adopted the fairly simple co-precipitation extrusion process of technology.
Preparation of catalysts method of the present invention is:
To add in the container respectively by active ingredient, trace assistant, cement, the deionized water of proportioning weighing and stir, extrusion molding, dry in room temperature or drying baker, dried mixture activates in stoving oven, and reactivation process is that four sections pulse temperature controls activate continuously:
One section: 50～100 ℃ of 0.5～2h
Two sections: 100～300 ℃ of 0.5～2h
Three sections: 300～700 ℃ of 3～7h
Four sections: 700～900 ℃ of 0.5～1h
After reactivation process is finished, promptly get catalyzer of the present invention.
Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of the present invention and preparation method thereof, not only the preparation method is simple, and catalyzer has very high activity, selectivity and stability.When using catalyzer of the present invention to be used for ethyl benzene dehydrogenation preparation of styrene, normal pressure, isothermal, 620 ℃, under the condition of water hydrocarbon than (water/ethylbenzene) 2.0,1.0 liters of ethylbenzene of liquid air speed/rise catalyzer hour, conversion of ethylbenzene is the highest can be up to more than 80%, selectivity of styrene is greater than 95%, and the life cycle of catalyzer is 2 years.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The invention is further illustrated by the following examples, and activity rating of catalyst carries out in the isotherm formula fixed bed, and its evaluation procedure is summarized as follows:
After the deionized water of volume pump output and ethylbenzene enter preheater and carry out preheating and mix, be gaseous state and enter reactor, reactor adopts the nichrome wire heating, temperature control is to preset temperature, reactor is the stainless steel tube of Φ 32mm, apparatus with catalyst inside 100ml, the product after the dehydrogenation use its composition of gas chromatographic analysis after condensation separation.
Dehydrogenation catalyst of the present invention can be applicable to fully that ethylbenzene, diethylbenzene, the dehydrogenation of toluene ethyl generate vinylbenzene, divinylbenzene and vinyl toluene.
Embodiment 1
With red iron oxide 106g, iron oxide yellow 192g, iron oxide black 5g, stratiform iron-stone rock 2g, Sodium orthomolybdate 16g, magnesium hydroxide 22g, cement 35g, 105gK 2CO 3, the cerous nitrate of 110g, 100g deionized water and trace assistant system 2.5g are (by TiO 20.3g, V 2O 50.5g, CoO 0.3g, NiO 0.2g, MnO 20.2g, CuO 0.8g, SnO 0.2g form), be added in the kneader and stir, take out the particle that the extrusion pelletizing becomes the long 7～10mm of φ 3mm, place activation furnace by 80 ℃ 1h180 ℃ 1h580 ℃ 6h850 ℃ 0.5h, program animation, specific surface are 2.1～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is with K 2Fe 2O 4Be main.With the 100ml catalyzer isothermal evaluating apparatus of packing into, appreciation condition is: reaction pressure is a normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyzer. hour, 620 ℃ of temperature of reaction, water is than (water/ethylbenzene) 2.0 (weight ratio), evaluation result: conversion of ethylbenzene 81.2%, selectivity of styrene 95.9%.
Embodiment 2
With red iron oxide 140g, iron oxide yellow 140g, iron oxide black 10g, stratiform iron-stone rock 5g, ammonium molybdate 22g, magnesium hydroxide 15g, cement 30g, 2.7g is (by V for the trace assistant system 2O 51.0g, CoO 0.6g, WO 30.4g, PbO 20.2g, NiO 0.2g, SnO 20.3g form), K 2CO 3110g, adds kneader respectively and mixes and stir fully at the cerous nitrate of 135g, deionized water, and back extrusion pelletizing activates with following condition: 60 ℃ 2h→ 200 ℃ 2h→ 700 ℃ 4h→ 9O0 ° 0.5hObtain finished catalyst, specific surface is 2.2～3.5g/ml, and pore volume is 160～210 , bulk density 1.12g/ml, and the principal crystalline phase of catalyzer is with K 2Fe 2O 4Be main.Estimate under the normal pressure isothermal condition, 620 ℃ of temperature of reaction, water is than (water/ethylbenzene) 1.3 o'clock, 1.0 liters of ethylbenzene of liquid air speed/rise catalyzer, and conversion of ethylbenzene can reach 80.6%, and selectivity of styrene is 96.1%.
Embodiment 3
With red iron oxide 185g, iron oxide yellow 115g, iron oxide black 8g, stratiform iron-stone rock 15g, ammonium molybdate 30g, magnesium hydroxide 26g, cement 35g, trace assistant system 2.2g is (by CoO 0.3g, Li 2O 0.2g, Rb 2O 0.3g, SrO 0.4g, MnO 20.6g, V 2O 50.4g form), K 2CO 365g, the cerous nitrate of 140g makes catalyzer by embodiment 1 method, obtains finished catalyst, and specific surface is 2.2～3.4g/ml, and pore volume is 160～210 , bulk density 1.18g/ml, the principal crystalline phase of catalyzer is with K 2Fe 2O 4Be main.Appreciation condition by embodiment 1 is estimated, evaluation result: conversion of ethylbenzene 80.96%, selectivity of styrene 95.75%.
Embodiment 4
Press embodiment 1 prescription, trace assistant is become 1.5g (by CoO 0.5g, V 2O 50.5g, MnO 20.5g form), make catalyzer by the method for embodiment 1, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 80.16%, selectivity 95.91%.
Embodiment 5
Press embodiment 1 prescription, remove trace assistant, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 77.8%, selectivity 95.21% by the method for embodiment 1.
Embodiment 6
Press the prescription of embodiment 1, only remove stratiform iron-stone rock, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 79.85%, selectivity of styrene 95.7% by the method for embodiment 1.
Embodiment 7
Press the prescription of embodiment 1, only remove red iron oxide, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 80.05%, selectivity of styrene 95.8% by the method for embodiment 1.
Comparative Examples 1
Press the prescription of embodiment 1, only remove iron oxide black and stratiform iron-stone rock, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 78.4%, selectivity of styrene 95.9% by the method for embodiment 1.
Comparative Examples 2
Press the prescription of embodiment 1, only remove and iron oxide yellow and iron oxide black, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 78.45%, selectivity of styrene 95.1% by the method for embodiment 1.
Comparative Examples 3
Press the prescription of embodiment 1, only remove red iron oxide and iron oxide black, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 77.85%, selectivity of styrene 95.5% by the method for embodiment 1.
Comparative Examples 4
Press the prescription of embodiment 1, only remove iron oxide yellow and stratiform iron-stone rock, make catalyzer, estimate evaluation result by the appreciation condition of embodiment 1: conversion of ethylbenzene 77.45%, selectivity of styrene 94.9% by the method for embodiment 1.
Comparative Examples 5
Behind the shaping of catalyst that makes by embodiment 1 prescription, activate by 580 ℃, the condition of 6h, the catalyzer principal crystalline phase that makes is with Fe 2O 3Be main.Estimate evaluation result again by the appreciation condition of embodiment 1: conversion of ethylbenzene 75.5%, selectivity 95.5%.

Claims (4)

1. Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst is characterized in that containing active ingredient: Fe in the composition of catalyzer 2O 330～75wt%, K 2O5～25wt%, Ce 2O 35～30wt%, MgO0.01～10wt%, MoO 30.1～6wt%, wherein ferric oxide is by red iron oxide, iron oxide yellow, iron oxide black, any three kinds or four kinds combine in the technical grade stratiform iron-stone rock, when red iron oxide, iron oxide yellow exist simultaneously, red iron oxide, iron oxide yellow proportioning are: 1～10: 4, the iron oxide black add-on is 0.2～2wt%, stratiform iron-stone rock 0～5wt%; Pore-creating agent 1～5wt%; Specific surface is 2.0～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is K 2Fe 2O 4
2. Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst according to claim 1 is characterized in that also containing trace assistant in the composition of catalyzer, is the metal in one or more IB～VIIIB, IIIA～VA family, and its consumption is 0.01～1wt%.
3. catalyzer according to claim 2 is characterized in that containing active ingredient: Fe in the composition of catalyzer 2O 355～65wt%, K 2O5～15wt%, Ce 2O 310～20wt%, MgO0.5～10wt%, MoO 30.2～5wt%, wherein ferric oxide is by red iron oxide, iron oxide yellow, iron oxide black, and any three kinds or four kinds combine in the technical grade stratiform iron-stone rock, and red iron oxide, iron oxide yellow proportioning are: 1～10: 4, the iron oxide black add-on is 0.2～2wt%, stratiform iron-stone rock 0.5～5wt%; Trace assistant is the metal in one or more IB～VIIIB, IIIA～VA family, and its consumption is 0.01～1wt%; Pore-creating agent 1～5wt%; Specific surface is 2.0～3.5g/ml, and pore volume is 160～210 , and the principal crystalline phase of catalyzer is K 2Fe 2O 4
4. the preparation method of the described Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 1, it is characterized in that to add in the container respectively by active ingredient, trace assistant, cement, pore-creating agent, the deionized water of proportioning weighing and stir, extrusion molding, dry in room temperature or drying baker, dried mixture activates in stoving oven, and reactivation process is that four sections pulse temperature controls activate continuously:
One section: 50～100 ℃ of 0.5～2h
Two sections: 100～300 ℃ of 0.5～2h
Three sections: 300～700 ℃ of 3～7h
Four sections: 700～900 ℃ of 0.5～1h
After reactivation process was finished, the principal crystalline phase of catalyzer was K 2Fe 2O 4, promptly get catalyzer of the present invention.
CNB011083832A 2001-03-14 2001-03-14 Alkyl aromatics dehydrogenating catalyst and its prepn. Expired - Fee Related CN1233604C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100418937C (en) * 2005-08-15 2008-09-17 中国石油化工股份有限公司 Method for producing diethylbenzene through dehydrogenation of diethyl benzene
CN101279263B (en) * 2007-04-04 2010-07-21 中国石油化工股份有限公司 Catalyst for preparation of styrene by ethylbenzene dehydrogenation
CN102909017B (en) * 2011-08-01 2014-07-23 中国石油化工股份有限公司 Method for stepwise activating dehydrogenation catalyst by using synthesis gas and CO-containing gas
CN104003836B (en) * 2014-06-24 2015-07-22 江苏常青树新材料科技有限公司 Method for producing 3-Methylstyrene and p-Methylstyrene
CN115487833B (en) * 2021-06-18 2024-03-26 中国石油化工股份有限公司 Catalyst for dehydrogenation in low water ratio environment, preparation method and application thereof and ethylbenzene dehydrogenation method

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