CN1226091C - Deoxidizing catalyst for producing alkyl thiazolinyl aromatic hydrocarbon - Google Patents

Deoxidizing catalyst for producing alkyl thiazolinyl aromatic hydrocarbon Download PDF

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CN1226091C
CN1226091C CNB021374481A CN02137448A CN1226091C CN 1226091 C CN1226091 C CN 1226091C CN B021374481 A CNB021374481 A CN B021374481A CN 02137448 A CN02137448 A CN 02137448A CN 1226091 C CN1226091 C CN 1226091C
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catalyst
catalyzer
dehydrogenation catalyst
present
alkenyl arene
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CN1490083A (en
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毛连生
范勤
倪军平
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China Petroleum Chemical Co Shanghai Petrochemical
Engineering Research Institute
China Petroleum and Chemical Corp
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China Petroleum Chemical Co Shanghai Petrochemical
Engineering Research Institute
China Petroleum and Chemical Corp
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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 a dehydrogenation catalyst for preparing alkyl thiazolinyl aromatic. The present invention mainly solves the problems that when the catalyst in the prior art is in use, the active components easily run off, the strength of the catalyst is poor and influenced; the present invention favorably solves the problems by adopting the technical scheme that barium components are added in a ferrum-potassium-cerium-molybdenum catalytic system. The present invention can be used for the industrial production of alkyl thiazolinyl aromatic.

Description

The dehydrogenation catalyst of preparation alkyl alkenyl arene
Technical field
The present invention relates to a kind of dehydrogenation catalyst for preparing alkyl alkenyl arene, particularly about preparation vinylbenzene, the catalyzer of divinylbenzene or alpha-methyl styrene.
Background technology
The manufacturing of industrial alkyl alkenyl arene realizes by alkyl aromatics dehydrogenation.Catalyst system therefor basic composition is Primary Catalysts, promotor and pore-creating agent, toughener etc.The catalyzer of patent report can be divided into two big classes.One class is the Fe-K series catalysts that contains Cr, as laid-open U.S. Patents US4467046, US4684619 and European patent EP 0195252A 2Deng.Though such activity of such catalysts and stability are better, owing to more or less have the oxide compound of Cr in forming, thereby can cause certain environmental pollution in Preparation of catalysts, operation and the spent catalyst treating processes, eliminated gradually.Another kind of is the Fe-K-Ce-Mo series of succeeding in developing the beginning of the eighties, as laid-open U.S. Patents US5190906, US4804799, world patent WO09839278A 1Deng.This type of catalyzer substitutes Cr with Ce, Mo, makes catalyzer keep on the basis of original stability, and active also have by a relatively large margin raising than the former, adopted by countries in the world production of styrene producer.The subject matter that it exists is that the major ingredient loss in use of this class catalyzer is very fast, and the anti-fluctuating nature of catalyzer is poor, and catalyst strength is poor, directly influences the work-ing life of catalyzer.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past in the document catalyzer in use, and active constituent easily runs off, and catalyst strength is poor, influences the problem of catalyst life, and a kind of dehydrogenation catalyst of new preparation alkyl alkenyl arene is provided.This catalyzer has the selectivity height of alkyl alkenyl arene, alkyl alkenyl arene yield height, and catalyst strength is good, and the good characteristics of catalyst stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of dehydrogenation catalyst for preparing alkyl alkenyl arene comprises following active constituent by weight percentage:
A) 55～85% Fe 2O 3
B) 4～20% K 2O;
C) 4～12% Ce 2O 3
D) 0.3～4% MoO 3
E) 0.1～4% BaO;
F) 0.001～5% at least a oxide compound that is selected from Mg, Cu, Zn, Ti, Zr, W, Mn, Ni or V;
Fe wherein 2O 3By Fe 2O 3And Fe 2O 3H 2O forms, by weight Fe 2O 3: Fe 2O 3H 2O is 0.2～5: 1.
In the technique scheme, the consumption preferable range of BaO is 0.1～2% by weight percentage, and more preferably scope is 0.1～1.2%, by weight Fe 2O 3: Fe 2O 3H 2The O preferable range is 1.0～4: 1.By weight percentage, active constituent also comprises 0.01～5% CaO, and preferable range is 1.5～4%.By weight percentage, the consumption preferable range of the oxide compound of at least a Mg of being selected from, Cu, Zn, Ti, Zr, W, Mn, Ni or V is 0.1～3.5%.
The used raw material of catalyst component is as follows among the present invention:
Potassium adds with potassium salt form; Cerium adds with oxide compound, oxyhydroxide or cerium salt; Molybdenum adds with its salt or oxide compound; Barium adds with its vitriol, oxide compound or oxyhydroxide, and calcium adds with its calcium oxide or calcium hydroxide; The element that is selected from Mg, Cu, Zn, Ti, Zr, W, Mn, Ni or V adds with its salt or oxide form, and ferriferous oxide adds with red iron oxide and iron oxide yellow form.
Catalyzer of the present invention also can comprise perforating agent in preparation, its consumption is 1～4% of a catalyst weight, can choose from graphite, polystyrene microsphere, carboxymethyl cellulose etc.Also have binding agent in addition, generally use cement, its consumption is 0.1～10% of a catalyst weight.
Method for preparing catalyst of the present invention:
At first desired raw material is carried out pre-treatment,, make its particle reach 150 orders comprising the coarse grain oxide compound of selecting for use is pulverized.Behind other promotor component that will add, tackiness agent, the perforating agent uniform mixing by Fe, K, Ce, Mo, Ba and the need of proportioning weighing, add proper amount of deionized water, make the dough of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 5～8 millimeters particle, in 80～120 ℃ of dryings 1～10 hour, 600～1000 ℃ of following roastings 1～8 hour, just can obtain finished catalyst then.
Dehydrogenation catalyst of the present invention under certain process conditions, can be applicable to fully by ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene and make vinylbenzene, divinylbenzene and alpha-methyl styrene.
The catalyzer that makes as stated above carries out activity rating in small-sized insulation fix bed reactor, for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Ethylbenzene and water are entered first adiabatic reactor through volume pump input preheater and water by water vapor gaseous state after mixing that volume pump input high temperature heater (HTH) produces respectively, the gaseous phase materials of first reactor outlet enters second adiabatic reactor again after being heated to preset temperature, two reactors are that internal diameter is 50 millimeters a stainless steel tube, can load 750 milliliters of particle diameters respectively and be 3.0 millimeters catalyzer.Analyzing it with gas chromatograph by the dehydrogenation product of reactor outflow behind water condensation forms.
The evaluating catalyst condition is as follows in the insulation fix bed reactor: reactor inlet temperature: 610 ℃ of first reactors, and 615 ℃ of second reactors, reaction pressure is that 50KPa, liquid air speed are that 0.5 hour-1, water ratio are that water/ethylbenzene (weight) is 1.3.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
Figure C0213744800051
The present invention is owing to introduce the barium element in the Fe-K-Ce-Mo catalyst system, make the easier formation ferripotassium of this catalyzer spinel structure, make catalyzer can under lower temperature, keep the better conversion rate, in this system, add a small amount of several metal oxides and perforating agent thereof in addition, make catalyzer keep the better active while, can keep higher selectivity again.Add calcium oxide and little metal oxide compound in the catalyzer, help improving the physical strength and the water resistance of catalyzer.Among the present invention, by in the Fe-K-Ce-Mo system, adding other metal oxides, make the catalyzer potassium content when 9～10% (weight) left and right sides, anti-615 ℃ of the anti-610 ℃/II of reactor inlet temperature I, reaction pressure 50KPaA, liquid air speed 0.5 hour-1 o'clock, water/ethylbenzene ratio is to react under 1.3 (weight) condition, its vinylbenzene yield reaches 68%, catalyst strength reaches 2.4 kilograms/millimeter, and rate of wear is 0.4% only, and catalyzer is tested through aging condition, stability has better obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
2130 gram red iron oxides, 1329 gram iron oxide yellow, 642 gram vitriolate of tartar, cerous nitrates, 850 grams, ammonium molybdate 152 grams, magnesium oxide 85 grams, barium carbonate 75 grams, cement 230 grams, carboxymethyl cellulose 100 grams, cupric oxide 20 grams and Manganse Dioxide 15 grams are mixed in container stirred 1.5 hours, add suitable quantity of water, mixed and stirred again 2 hours, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5 millimeters of length, put into baking oven 80 ℃ of bakings 2 hours, 120 ℃ were dried by the fire 2 hours, then 750 ℃ of roastings of high temperature 4 hours, after the cooling, promptly make catalyzer.The evaluating catalyst condition is as follows: the catalyzer of 3 millimeters of 1500 milliliters, particle diameter is divided in two parts of (each 750 milliliters) laboratory adiabatic reactors of packing into, and reaction pressure is that 50KPaA, liquid air speed are 0.5 hour -1, first reactor inlet temperature is 610 ℃, second reactor inlet temperature is 615 ℃.Crush strength uses DL-II type granule strength determinator to measure.The results are shown in Table 1, table 2, table 3.
[embodiment 2～3]
Each step according to embodiment 1 prepares catalyzer, only changes the content of catalyst component, uses embodiment 1 with the quadrat method evaluation then, and it the results are shown in Table 1, table 2, table 3.
[comparative example 1]
Each step according to embodiment 1 prepares catalyzer, and component does not add barium sulfate, uses embodiment 1 with the quadrat method evaluation then, and it the results are shown in Table 1, table 2, table 3.
The concrete charging capacity of table 1
Charging capacity, gram
Raw material Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Fe 2O 3 2130 2130 2130 2130
Fe 2O 3·H 2O 1329 1329 1329 1329
K 2CO 3 642 642 642 642
Ce(NO 3) 3·6H 2O 850 850 850 850
(NH 4) 6Mo 7O 24·4H 2O 152 152 152 152
MgO 85 85 85 85
Cement 230 230 230 230
Carboxymethyl cellulose 100 100 100 100
CuO 20 20 20 20
MnO 2 15 15 15 15
BaCO 3 75 50 25
Table 2 catalyzer is formed
Form Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Fe 2O 3 72.0 72.7 72.6 73.0
K 2CO 3 9.5 9.5 9.5 9.6
Ce 2O 3 6.9 6.9 6.9 6.9
MoO 3 2.6 2.6 2.6 2.6
MgO 1.8 1.8 1.8 1.8
CaO 3.0 3.0 3.0 3.0
CuO 0.4 0.4 0.4 0.4
MnO 2 0.3 0.3 0.3 0.3
BaO 1.2 0.8 0.4
The contrast of table 3 catalyst performance
Catalyzer Conversion of ethylbenzene % Selectivity of styrene % The vinylbenzene list is received % Intensity kilogram/millimeter
Embodiment 1 64.5 96.8 62.4 2.4
Embodiment 2 66.5 97.4 64.7 2.4
Embodiment 3 65.5 97.0 63.5 2.4
Comparative example 1 63.5 96.5 61.3 2.0
From the embodiment data as can be known, catalyzer of the present invention, in the Fe-K-Ce-Mo system, add ba oxide and several metal oxide auxiliary agent, add perforating agent and binding agent, made dehydrogenation catalyst promptly has high activity and high selectivity, also has good crush strength simultaneously, is a kind of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst efficiently.

Claims (7)

1, a kind of dehydrogenation catalyst for preparing alkyl alkenyl arene comprises following active constituent by weight percentage:
A) 55～85% Fe 2O 3
B) 4～20% K 2O;
C) 4～12% Ce 2O 3
D) 0.3～4% MoO 3
E) 0.01～4% BaO;
F) 0.001～5% at least a oxide compound that is selected from Mg, Cu, Zn, Ti, Zr, W, Mn, Ni or V;
Fe wherein 2O 3By Fe 2O 3And Fe 2O 3H 2O forms, by weight Fe 2O 3: Fe 2O 3H 2O is 0.2～5: 1.
2,, it is characterized in that the consumption of BaO is 0.1～2% by weight percentage according to the dehydrogenation catalyst of the described preparation alkyl alkenyl arene of claim 1.
3,, it is characterized in that the consumption of BaO is 0.1～1.2% by weight percentage according to the dehydrogenation catalyst of the described preparation alkyl alkenyl arene of claim 2.
4,, it is characterized in that Fe by weight according to the dehydrogenation catalyst of the described preparation alkyl alkenyl arene of claim 1 2O 3: Fe 2O 3H 2O is 1.0～4: 1.
5,, it is characterized in that active constituent also comprises 0.01～5% CaO by weight percentage according to the dehydrogenation catalyst of the described preparation alkyl alkenyl arene of claim 1.
6,, it is characterized in that the amount of active constituent CaO is 1.5～4.0% by weight percentage according to the dehydrogenation catalyst of the described preparation alkyl alkenyl arene of claim 5.
7, according to the dehydrogenation catalyst of the described preparation alkyl alkenyl arene of claim 1, the consumption that it is characterized in that the oxide compound of at least a by weight percentage Mg of being selected from, Cu, Zn, Ti, Zr, W, Mn, Ni or V is 0.1～3.5%.
CNB021374481A 2002-10-16 2002-10-16 Deoxidizing catalyst for producing alkyl thiazolinyl aromatic hydrocarbon Expired - Lifetime CN1226091C (en)

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Publication number Priority date Publication date Assignee Title
CN100358632C (en) * 2005-01-26 2008-01-02 中国石油化工股份有限公司 Alkyl arene dehydrogenating catalyst
CN101279267B (en) * 2007-04-04 2011-07-13 中国石油化工股份有限公司 Energy-saving catalyst for phenylethylene dehydrogenation
CN102000587B (en) * 2010-11-25 2012-05-23 同济大学 Catalyst for methyl ethylbenzene dehydrogenation to prepare alpha methyl styrene

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