CN1814577A - Method for preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene - Google Patents

Method for preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene Download PDF

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CN1814577A
CN1814577A CN 200510001684 CN200510001684A CN1814577A CN 1814577 A CN1814577 A CN 1814577A CN 200510001684 CN200510001684 CN 200510001684 CN 200510001684 A CN200510001684 A CN 200510001684A CN 1814577 A CN1814577 A CN 1814577A
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vanadium
ethylbenzene
molecular sieve
ethyl benzene
catalyzer
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CN100497273C (en
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余少兵
张晓昕
宗保宁
慕旭宏
郑金玉
王宣
张君屹
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses the method used ethyl benzene oxidative dehydrogenation to prepare styrene. Its features are as follows: making ethyl benzene touching with catalyst under carbon dioxide atmosphere; the mol ratio of carbon dioxide and ethyl benzene is 5-15; reacting temperature is 673K-873K; liquid volume airspeed of the ethyl benzene is 0.1-2.0h<SUP>-1</SUP>; the catalyst is molecular sieve contained vanadium. The method can effectively prolong steady running time under high ethyl benzene conversion rate and styrene selectivity.

Description

A kind of method of preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene
Technical field
The invention relates to the method for preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene, more specifically say so about a kind of method of the preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene under carbon dioxide atmosphere.
Background technology
Vinylbenzene is important chemical material, and 90% of its output is made by ethylbenzene direct dehydrogenation on ferric oxide catalyst.This method needs a large amount of superheated vapours, is condensed into liquid after reaction, the latent heat of vaporization of water vapor is not recycled, so energy consumption is bigger, and this method exists the vinylbenzene productive rate to be subjected to the shortcoming of thermodynamics equilibrium limit.In this reaction system,, can increase the equilibrium conversion of ethylbenzene and cut down the consumption of energy that (producing 1 ton of cinnamic energy consumption can be by original 1.5 * 10 if replace water vapor with carbonic acid gas 9Cal/t reduces to 1.9 * 10 8Cal/t), therefore, the method for the ethyl benzene dehydrogenation preparation of styrene under carbon dioxide atmosphere had become the focus of people's research in recent years.
Because the Fe-K series catalysts in the ethylbenzene direct dehydrogenation preparation of styrene industrial production is at CO 2Activity under the atmosphere is very low, can't satisfy the demands, and needs supporting development of new efficiently to adapt to catalyst for application under the carbon dioxide atmosphere for this reason.The carrier of this type of catalyzer of bibliographical information has Al 2O 3, ZnO, WO 3, SiO 2, ZrO 2, ZSM-5 and gac (AC) etc., active ingredient has the oxide compound of transition metal such as Fe, V, Cr, Ce, Cu, Ni and Co, auxiliary agent that basic metal such as Li, Na, K are arranged, rare earth metal such as alkaline-earth metal such as Ca, Mg and La; Also can directly adopt spinel-like wustite, ZrO 2Make catalyzer with hydrotalcite type Mg-Al-Fe class material.Wherein dehydrogenation preferably catalyzer mainly contain Fe system and V series catalysts two big classes.
N.Mimura etc. are " Catalyst Letter " 1999,58 volumes, 59～62 pages " Dehydrogenation of ethylbenzene to styrene over Fe 2O 3/ Al 2O 3Catalystsin the presence of carbon dioxide " reported Fe in the literary composition with the coprecipitation method preparation 2O 3(10wt%)/Al 2O 3(90wt%) catalyzer is at 823K, CO 2The mol ratio of/EB is 11, W/F is under the condition of 3.89g-cat h/mol, and cinnamic yield is 33.2%, and cinnamic selectivity is 95.7% result.
Zhang Weiguang etc. are " catalysis journal " 2000, and 21 volumes, have been reported the Fe-Na/AC catalyzer of immersion process for preparing at the 1st phase in " ethylbenzene dehydrogenation and the iron of gas reforming coupling reaction/activated-carbon catalyst research against the current " literary composition of 27～30 pages.This catalyzer is 1.28 at the ethylbenzene mass space velocity -1, CO 2Flow is under the condition of 38ml/min, and conversion of ethylbenzene is 63.8%, and selectivity of styrene is 93.5%.
Y.Sakurai etc. were " Applied Catalysis A:General " 2000,192 volumes, reported V/AC (charge capacity the is 1.0mmol/g AC) catalyzer of immersion process for preparing in " Dehydrogenation of ethylbenzene with an activatedcarbon-supported vanadium catalyst " literary composition of 281～288 pages, this catalyzer is at 823K, CO 2The mol ratio of/EB is 50～70, and W/F is that activity is the highest under the condition of 70g-cat h/mol, and cinnamic yield is 54.2%, and selectivity is 80.8%, but active relatively poor.
Disclosing among the CN1431045A with gac or aluminum oxide is the catalyzer of the load vanadium of preparing carriers, and conversion of ethylbenzene can reach more than 60%, and cinnamic selectivity is higher than 96%.
Disclosing among the US2003/0166984A1 with zirconium white and aluminum oxide is a kind of catalyzer that contains vanadium, iron, antimony of preparing carriers, and this catalyzer is at 873K, CO 2The mol ratio of/EB is 5, the ethylbenzene mass space velocity is that conversion of ethylbenzene is up to 90.8% under 1 the condition, and cinnamic selectivity is 95.7%.
Up to now, do not see with the vanadium to be the report of the molecular sieve of backbone element as the ethyl benzene dehydrogenation preparation of styrene of catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of under carbon dioxide atmosphere, with the method for the new catalytic ethyl benzene dehydrogenation preparation of styrene of material.
The method of ethyl benzene dehydrogenation preparation of styrene provided by the invention is characterized in that this method is that ethylbenzene is contacted with catalyzer, wherein mol ratio (the CO of carbonic acid gas and ethylbenzene 2/ EB) being 5～15, preferred 7～11, temperature of reaction is 673K～873K, preferred 723K～873K, the liquid volume air speed of ethylbenzene is 0.1～2.0h -1, preferred 0.3～1.0h -1, said catalyzer is the molecular sieve that contains v element in the skeleton structure.
In the method provided by the invention, said catalyzer is the molecular sieve (abbreviate as and contain the vanadium molecular sieve) that contains v element in the skeleton structure, and they are meant that v element enters the skeleton of molecular sieve, with V 4+Form is combined in the framework of molecular sieve, molecular sieve as backbone element, vanadium exist form with FT-IR, the common sign of ESR and NMR determined (but reference Vanadosilicate catalysts prepared from differentvanadium sources and their characteristics in methanol to conversion (A.Miyamoto, D.Medhanavyn and T.Inui, Applied Catalysis, 28 (1986) 89-103), Synthesis and Characterization of the Vanadium-incorporated MolecularSieve VAPO-5 (S.H.Jhung, Y.S.UH and H.Chon, Applied Catalysis 62 (1990) 61-72) and Synthesis, characterization and catalytic properties ofvanadium silicates with a ZSM-48 structure (A.Tuel and Y.Ben Taarit, Applied Catalysis A:General, 102 (1993) 201-204)).
Contain the vanadium molecular sieve and can be V-Si molecular sieve (as VS-1 and VS-2), wherein vanadium and silicon is as backbone element, the mass percent of vanadium preferred 3～6%; Contain the vanadium molecular sieve and also can be phosphoric acid vanadium aluminum molecular screen (as VAPO-5, VAPO-11, VAPO-31 and VAPO-17 etc.), wherein vanadium, aluminium, phosphorus is as backbone element, and is same, the mass percent of vanadium preferred 3～6%; Also can be phosphoric acid vanadium sial, the ratio of silicon and aluminium is arbitrarily, and at this moment sial characterizes the content of vanadium in the skeleton simultaneously as backbone element with the mass percent of vanadium.
Method provided by the invention, to contain the vanadium molecular sieve is that ethyl benzene oxidizing-dehydrogenation catalyst carries out, said containing in the vanadium molecular sieve, v element enters framework of molecular sieve, forms isolated redox center, the active ingredient high dispersing, the pore size distribution unanimity, so the specific surface area of the dispersity of vanadium species and catalyzer is improved, stability is better, when being embodied in the reaction like this, can effectively prolong in high conversion of ethylbenzene and the steady running time (seeing accompanying drawing) under the selectivity of styrene.
Description of drawings
Accompanying drawing be embodiment 1 and with Y.Sakurai etc. " Applied Catalysis A:General " 2000,192 volumes, the comparison diagram of the method for reporting in " Dehydrogenation of ethylbenzene with anactivated carbon-supported vanadium catalyst " literary composition of 281～288 pages of using V/AC (charge capacity is 1.0mmol/g AC) catalyzer, among the figure, (■) represent V/AC, (▲) represents VAPO-5.
Embodiment
The invention will be further described below by embodiment, but content not thereby limiting the invention.
Among the embodiment, said V-Si molecular sieve or phosphoric acid vanadium aluminum molecular screen is elementary composition with the X-ray fluorescence spectra quantitative analysis in the catalyzer, and its crystalline phase and degree of crystallinity are with XRD determining.
Embodiment 1
Synthesizing of VAPO-5 molecular sieve: 15g dry glue powder (Al 2O 3Content 65.8%, the Chang Ling catalyst plant is produced), add water 60mL making beating after 60 minutes to wherein slowly dripping 14g ortho-phosphoric acid solution (phosphorus acid content 85%, Beijing chemical reagent work produces).Stir after 10 minutes and to add 2.3 grams, five water vanadylic sulfates (content of vanadium 22 heavy % are dissolved in the 2g water), continue under the room temperature to stir that the speed with 1mL/min adds 16mL template triethylamine (content 98%, Beijing chemical reagent work produces) after 60 minutes.Continue to stir after 1 hour, placed 175 ℃ of dynamic crystallizations of crystallizing kettle 72 hours.Products therefrom wash with water the back in 80 ℃ of oven dry, sample in flowing air temperature-programmed calcination (120 ℃, 1 hour; 3 ℃/min is warming up to 550 ℃; Keep slow cool to room temperature after 4 hours).The X-ray diffraction of products therefrom (XRD) spectrogram has VAPO-5 molecular sieve feature, and wherein the mass percent of vanadium is 3%, and note is made catalyst A.
The method operational condition of ethyl benzene dehydrogenation preparation of styrene is: temperature of reaction is 813K, and the ethylbenzene air speed is 1.0h -1, CO 2/ EB mol ratio is 10.
The reaction gas-phase product is analyzed with the 13X molecular sieve column, and liquid product adopts the capillary column analysis, and the capillary column model is: Innowax, 30m * 0.25mm * 0.25 μ m, hydrogen flame detector.
Reaction result sees Table 1.
With the catalyst A is example, with Y.Sakurai etc. " Applied Catalysis A:General " 2000,192 volumes, V/AC (charge capacity the is 1.0mmol/g AC) catalyzer of reporting in " Dehydrogenation of ethylbenzene with anactivated carbon-supported vanadium catalyst " literary composition of 281～288 pages compares, and with this stability of the method for the invention provides is described.Reaction conditions is 823K, W/F:70g-cat h/mol, and V is 0.3mmol in every gram catalyst A.
Comparing result is seen accompanying drawing.As can be seen from the figure, method provided by the invention is from all obviously being better than adopting the method for catalyst V/AC on the initial activity of catalyzer still is the steady running time.
Embodiment 2
Different with catalyst A is that the mass percent of vanadium is 1% in the used VAPO-5 molecular sieve, remembers and makes catalyst B.Operational condition is: temperature of reaction is 873K, and the ethylbenzene air speed is 0.6h -1, CO 2/ EB mol ratio is 7, and other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 3
Different with catalyst A is that the mass percent of vanadium is 2% in the used VAPO-5 molecular sieve, remembers and makes catalyzer C.Operational condition is: temperature of reaction is 723K, and the ethylbenzene air speed is 0.3h -1, CO 2/ EB mol ratio is 11.Other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 4
Different with catalyst A is that the mass percent of vanadium is 4% in the used VAPO-5 molecular sieve, remembers and makes catalyzer D.Operational condition is: temperature of reaction is 813K, and the ethylbenzene air speed is 0.6h -1, CO 2/ EB mol ratio is 7.Other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 5
Different with catalyst A is that the mass percent of vanadium is 5% in the used VAPO-5 molecular sieve, remembers and makes catalyzer E.Operational condition is: temperature of reaction is 773K, and the ethylbenzene air speed is 1.0h -1, CO 2/ EB mol ratio is 15.Other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 6
Different with catalyst A is that the mass percent of vanadium is 6% in the used VAPO-5 molecular sieve, remembers and makes catalyzer F.Operational condition is: temperature of reaction is 813K, and the ethylbenzene air speed is 0.1h -1, CO 2/ EB mol ratio is 5.Other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 7
VAPO-11's is synthetic: 15g dry glue powder (Al 2O 3Content 65.8%, the Chang Ling catalyst plant is produced), add water 60mL making beating after 60 minutes to wherein slowly dripping 14g ortho-phosphoric acid solution (phosphorus acid content 85%, Beijing chemical reagent work produces).Stir after 10 minutes and to add 2.1g five water vanadylic sulfates (V content 22% is dissolved in the 2g water), continue under the room temperature to stir that the speed with 1mL/min adds 13.6mL template dipropyl amine (content 98%, Beijing chemical reagent work produces) after 60 minutes.Continue to stir after 1 hour, placed 200 ℃ of dynamic crystallizations of crystallizing kettle 96 hours.The X-ray diffraction of products therefrom (XRD) spectrogram has the feature of VAPO-11 molecular sieve, and the mass percent of vanadium is 3%, and note is made catalyzer G.
Operational condition is: temperature of reaction is 873K, and the ethylbenzene air speed is 2.0h -1, CO 2/ EB mol ratio is 10.Other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 8
VS-1's is synthetic: with 1.0 gram V 2O 5Be dissolved in the 50 gram TBAH, add 15 gram silica gel again and do the silicon source, stir, 160 ℃ of crystallization 10 days, X-ray diffraction (XRD) spectrogram of 530 ℃ of roastings products therefrom after 5 hours has the feature of VS-1 molecular sieve, and the mass percent of vanadium is 3%, and note is made catalyzer H.
Operational condition is: temperature of reaction is 673K, and the ethylbenzene air speed is 0.6h -1, CO 2/ EB mol ratio is 15.Other condition is with embodiment 1.
Reaction result sees Table 1.
Embodiment 9
VS-2's is synthetic: with 1.8 gram V 2O 5Be dissolved in 30 gram TBAH and the 10 gram water, add 15 gram silica gel again and do the silicon source, stir, 180 ℃ of crystallization 10 days, 530 ℃ of roastings were used after 5 hours, obtained former powder, and the X-ray diffraction of products therefrom (XRD) spectrogram has the feature of VS-2 molecular sieve, the mass percent of vanadium is 3%, and note is made catalyst I.
Operational condition is: temperature of reaction is 673K, and the ethylbenzene air speed is 1.0h -1, CO 2/ EB mol ratio is 10.Other condition is with embodiment 1.
Reaction result sees Table 1.
Table 1
Embodiment The catalyzer numbering Conversion of ethylbenzene % Selectivity of styrene % Vinylbenzene yield %
1 2 3 4 5 6 7 8 9 A B C D E F G H I 42.5 30.1 35.1 43.4 43.8 44.4 16.9 9.4 12.0 98.4 95.3 95.8 97.2 98.4 96.9 92.5 90.4 93.1 41.8 28.7 33.6 42.2 43.1 43.0 15.6 8.5 11.2

Claims (7)

1. the method for a preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene, it is characterized in that this method is that ethylbenzene is contacted with catalyzer, wherein the mol ratio of carbonic acid gas and ethylbenzene is 5～15, temperature of reaction is 673K～873K, and the liquid volume air speed of ethylbenzene is 0.1～2.0h -1, said catalyzer is the molecular sieve that contains v element in the skeleton structure.
2. according to the method for claim 1, the molecular sieve that contains v element in the said skeleton structure is phosphoric acid vanadium aluminum molecular screen or V-Si molecular sieve.
3. according to the method for claim 2, said phosphoric acid vanadium aluminum molecular screen is selected from one or more among VAPO-5, VAPO-11, VAPO-17 and the VAPO-34.
4. according to the method for claim 3, said phosphoric acid vanadium aluminum molecular screen be with vanadium, aluminium, phosphorus as backbone element, the mass percent of vanadium is 3～6%.
5. according to the method for claim 2, said V-Si molecular sieve is VS-1 and/or VS-2.
6. according to the method for claim 5, said V-Si molecular sieve be vanadium and silicon as backbone element, the mass percent of vanadium is 3～6%.
7. according to the method for claim 1, it is characterized in that this method is that the liquid volume air speed that mol ratio at carbonic acid gas and ethylbenzene is 7～11, temperature of reaction is 723K～873K, ethylbenzene is 0.3～1.0h -1Under carry out.
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