CN1263542C - Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation - Google Patents

Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation Download PDF

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CN1263542C
CN1263542C CNB031507212A CN03150721A CN1263542C CN 1263542 C CN1263542 C CN 1263542C CN B031507212 A CNB031507212 A CN B031507212A CN 03150721 A CN03150721 A CN 03150721A CN 1263542 C CN1263542 C CN 1263542C
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catalyst
oxide catalyst
styrene
oxide
dehydrogenation
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CN1589964A (en
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廖仕杰
杨诚
朱敏
缪长喜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
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    • 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 oxide catalyst for preparing styrene from ethylbenzene dehydrogenation, which mainly solves the problems which exist in former technologies that the activity and the selectivity of a catalyst are bad, and by-products can not be efficiently reduced in a reaction process. The oxide catalyst better solves the problems by adopting the technical scheme that the raw material source of a precursor of iron, which is chosen from at least one of FeC13, Fe2 (SO4)3, Fe2 (C2O4)3 or Fe2 (CO3)3, is changed in an iron-potassium-cerium-molybdenum system, and the oxide catalyst can be used in industrial production. For preparing styrene from ethylbenzene dehydrogenation.

Description

The oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene
Technical field
The present invention relates to a kind of catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene, particularly about being used for the oxide catalyst of ethyl benzene dehydrogenation preparation of styrene.
Background technology
The manufacturing of industrial alkenyl arene realizes by alkyl aromatics dehydrogenation.Catalyst system therefor basic composition is major catalyst, co-catalyst and pore-foaming agent, reinforcing agent etc.The catalyst 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 4467046,4684619, European patent 0195252A2, though such activity of such catalysts and stability are better, but owing to more or less there is the oxide of Cr in forming, thereby can cause certain environmental pollution in Preparation of Catalyst, operation and the dead catalyst processing procedure, 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 5190906,4804799, world patent 09839278A1, this type of catalyst substitutes Cr with Ce, Mo, make catalyst keep on the basis of original stability, active also have by a relatively large margin raising than the former, adopted by countries in the world production of styrene producer, its main existing problems are that selectivity of styrene is not high, by-product benzene content is more, brings difficulty for principal product output and later separation step.Therefore, seek a kind of alkenyl arene of high selectivity and produce catalyst, improve the yield of principal product alkenyl arene, be the very interested problems of people always.
Summary of the invention
Subject matter to be solved by this invention is to exist activity of such catalysts, selectivity not good in the conventional art, can not effectively reduce the problem that accessory substance generates in the course of reaction, and a kind of new oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene is provided.This catalyst has can improve catalyst activity, selectivity, keeps the characteristics of better stability simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene comprises following active constituent by weight percentage:
A) 48～80% Fe 2O 3
B) 3～30% K 2O;
C) 0.5～7% MoO 3
D) 3～15% CeO 2
Be binding agent with kaolin, diatomite or cement in the catalyst, the consumption of binding agent is 0.1～10% of a catalyst weight;
Fe wherein 2O 3Presoma be selected from FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3In at least a.
Fe in the technique scheme 2O 3The presoma preferred version for being selected from Fe 2(C 2O 4) 3Preferred version is for also containing alkaline earth oxide in the catalyst activity component by weight percentage, and its consumption is 0.05～8%; The alkaline earth oxide preferred version is a magnesia.
Catalyst provided by the invention is with Fe 2O 3, K 2O, CeO 2, MoO 3Be main body, added metal oxide simultaneously from alkaline-earth metal, IB-VIII family and IIIA-VIA family as auxiliary agent (they can be selected for use) and binding agent, perforating agent.Fe in the patent in the past 2O 3Main iron oxide yellow and iron oxide red or both mixing use of adopting industrial production, Fe of the present invention 2O 3Be to be prepared from the predecessor that contains iron oxide.
Specifically, dehydrogenation of the present invention comprises and consists of (percentage by weight): Fe 2O 348～80%, K 2O 3～30%, Ce 2O 33～15%, MoO 30.5～7%.Wherein Fe is with Fe 2O 3Form add preparation Fe 2O 3Used salt be to be selected from FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3In at least a composition, potassium adds with potassium salt form; Used cerium adds with oxide, hydroxide or cerium salt; Mo adds with its salt or oxide; Oxides additive MgO adds with oxide form; The consumption of perforating agent is 1～4% of the preceding raw material gross weight of catalyst roasting, can be selected from graphite, polystyrene microsphere or carboxymethyl cellulose; All the other are binding agent, available cement.
Preparation of catalysts method of the present invention is as follows: after will evenly mixing by Fe, K, Ce, Mo, oxides additive, adhesive, the perforating agent of proportioning weighing, add an amount of deionized water, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 60～120 ℃ of dryings 4 hours, 400～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
The catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed, for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Deionized water and ethylbenzene are imported preheating mixer through measuring pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters, particle diameter is 3 millimeters a catalyst.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
Figure C0315072100041
Figure C0315072100042
The preparation method of iron oxide is as follows: under the room temperature, choose a certain amount of FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3One or more, add the HNO of requirement 3Dissolve, filter, the solution after filtering is placed spent the night, add the NaOH solution of reaction needed amount, control solution pH value is 9～10, filters siccative is air-dry, carries out roasting 1～3 hour under 200～500 ℃, and cool to room temperature promptly obtains iron oxide.
The evaluating catalyst condition is as follows: reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyst hour, 620 ℃ of reaction temperatures, water are than (water/ethylbenzene) 2.0 (weight ratio).
Pass through among the present invention to adopt in iron-potassium-cerium-molybdenum catalyst system and catalyzing, change the precursor material source of iron, the inventor is surprised to find that when catalyst that this technical scheme makes is used for ethyl benzene dehydrogenation preparation of styrene, catalyst has higher activity, product styrene has higher selectivity and yield, and has stability preferably.The same catalyst of forming is formed, and conversion ratio is the highest to be improved closely 3%, and selectivity is the highest to improve 3%, has obtained better technical effect.
The composition of catalyst among the present invention is not subjected to the restriction of open scope, adds other active constituent, and activity of such catalysts, selectivity can further improve.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene dehydrogenation generate styrene, divinylbenzene and AMS.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 620.2 gram FeCl 3Preparation method according to above-mentioned iron oxide prepares iron oxide, 59.6 gram potash, 30.2 gram cerium oxide, 23.2 gram molybdenum oxides, 15.1 gram magnesia and cement, carboxymethyl cellulose stirred in kneading machine 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 8～10 millimeters of length, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, placed muffle furnace then, made catalyst in 4 hours in 900 ℃ of roastings.Its inventory situation sees Table 1, and the percentage by weight composition of gained catalyst sees Table 5, and the catalyst dehydrogenation sees Table 7.
Table 1 embodiment 1
Raw material FeCl 3 K 2CO 3 Cement Carboxymethyl cellulose MgO MoO 3 CeO 2
Inventory (gram) 620.2 59.6 60.4 25.7 15.1 23.2 30.2
[embodiment 2～4]
The preparation method of embodiment 2,3,4 is the preparation predecessor difference of iron oxide with embodiment 1, and wherein embodiment 1 is with FeCl 3Be predecessor, embodiment 2 is with Fe 2(C 2O 4) 3Be predecessor, embodiment 3 is with Fe 2(SO 4) 3Be predecessor, embodiment 4 is with Fe 2(CO 3) 3Be predecessor.The inventory situation of embodiment 2 sees Table 2, and the percentage by weight composition of gained catalyst sees Table 5, and the catalyst dehydrogenation sees Table 7, and the steadiness of catalyst sees Table 8.The embodiment 3 and 4 the situation that feeds intake see Table 3 and table 4 respectively, and the percentage by weight of gained catalyst is formed and seen Table 5, and the catalyst dehydrogenation sees Table 7.
Table 2 embodiment 2
Raw material Fe 2(C 2O 4) 3 K 2CO 3 Cement Carboxymethyl cellulose MgO MoO 3 CeO 2
Inventory (gram) 721.9 59.6 60.4 25.7 15.1 23.2 30.2
Table 3 embodiment 3
Raw material Fe 2(SO 4) 3 K 2CO 3 Cement Carboxymethyl cellulose MgO MoO 3 CeO 2
Inventory (gram) 768.0 59.6 60.4 25.7 15.1 23.2 30.2
Table 4 embodiment 4
Raw material Fe 2(CO 3) 3 k 2CO 3 Cement Carboxymethyl cellulose MgO MoO 3 CeO 2
Inventory (gram) 560.4 59.6 60.4 25.7 15.1 23.2 30.2
The weight percent of table 5 gained catalyst activity component is composed as follows
Form Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Fe 2O 3 K 2O MgO MoO 3 CeO 2 72.2 11.0 3.6 6.0 7.2 72.2 11.0 3.6 6.0 7.2 72.2 11.0 3.6 6.0 7.2 72.2 11.0 3.6 6.0 7.2
[comparative example 1～3]
The method for preparing catalyst of comparative example is with embodiment 1, and comparative example 1 all adopts iron oxide reds, comparative example 2 usefulness be iron oxide yellow, 3 of comparative examples are that iron oxide red, iron oxide yellow respectively account for half, concrete inventory is:
Table 6
Raw material Comparative example 1 Inventory, gram comparative example 2 Comparative example 3
Fe 2O 3.H 2O Fe 2O 3 K 2CO 3Cement carboxymethyl cellulose MgO MoO 3 CeO 2 307.2 59.6 60.4 25.7 15.1 23.2 30.2 341.8 59.6 60.4 25.7 15.1 23.2 30.2 170.9 153.6 59.6 60.4 25.7 15.1 23.2 30.2
The composition of gained catalyst is identical with embodiment 1～4.
All by aforesaid reaction condition and device examination, appraisal result is as follows for the catalyst of above-mentioned gained:
Table 7 catalyst dehydrogenation
Catalyst Conversion ratio % Selectivity % Single % that receives
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 comparative examples 1 comparative example 2 comparative examples 3 72.6 74.7 71.6 72.5 69.2 68.6 70.3 95.6 95.5 95.5 95.6 94.3 92.3 94.3 69.4 70.6 68.4 69.3 65.3 63.3 66.3
The stability result of table 8 embodiment 2 catalyst
Reaction time
50 hours 100 hours 200 hours 300 hours 400 hours 500 hours
Con (％) Sel (％) Con (％) Sel (％) Con (％) Sel (％) Con (％) Sel (％) Con (％) Sel (％) Con (％) Sel (％)
74.6 95.6 74.4 95.5 74.5 94.4 74.4 95.5 74.3 95.3 74.4 95.7
Wherein Con is a conversion of ethylbenzene, and Sel is a selectivity of styrene.
From implementation, catalyst of the present invention, its basic composition is with Fe 2O 3, K 2O, CeO 2, MoO 3, MgO is main component, suitably selects Fe 2O 3Predecessor, prepare Fe 2O 3, made dehydrogenation had both had high activity, selectivity, and good stability is arranged again.

Claims (4)

1, a kind of oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene comprises following active constituent by weight percentage:
A) 48～80% Fe 2O 3
B) 3～30% K 2O;
C) 0.5～7% MoO 3
D) 3～15% CeO 2
Be binding agent with kaolin, diatomite or cement in the catalyst, the consumption of binding agent is 0.1～10% of a catalyst weight;
Fe wherein 2O 3Presoma be selected from FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3In at least a.
2, according to the described oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that Fe 2O 3Presoma be selected from Fe 2(C 2O 4) 3
3, according to the described oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that also containing alkaline earth oxide in the catalyst activity component by weight percentage, its consumption is 0.05～8%.
4,, it is characterized in that alkaline earth oxide is a magnesia according to the described oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 3.
CNB031507212A 2003-09-03 2003-09-03 Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation Expired - Lifetime CN1263542C (en)

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