CN100548488C - Ethyl benzene oxidizing-dehydrogenation catalyst - Google Patents
Ethyl benzene oxidizing-dehydrogenation catalyst Download PDFInfo
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- CN100548488C CN100548488C CNB2005100016833A CN200510001683A CN100548488C CN 100548488 C CN100548488 C CN 100548488C CN B2005100016833 A CNB2005100016833 A CN B2005100016833A CN 200510001683 A CN200510001683 A CN 200510001683A CN 100548488 C CN100548488 C CN 100548488C
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- molecular sieve
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- vapo
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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
The invention discloses a kind of ethyl benzene oxidizing-dehydrogenation catalyst, it is characterized in that this catalyst mainly is made up of active component and auxiliary agent, said active component is the molecular sieve that contains v element in the skeleton structure, said auxiliary agent is alkali metal or alkaline-earth metal, and the content of auxiliary agent is counted 0.01～3.0mmol with metal oxide in every gram catalyst.
Description
Technical field
The invention relates to a kind of ethyl benzene oxidizing-dehydrogenation catalyst, further saying so is used under the carbon dioxide atmosphere about a kind of, is the catalyst of the preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene of active component, load auxiliary agent with the molecular sieve.
Background technology
Styrene 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 the reaction, the latent heat of vaporization of water vapour is not recycled, so energy consumption is bigger, and this method exists the styrene productive rate to be subjected to the shortcoming of thermodynamics equilibrium limit.In this reaction system, if with CO
2Replace water vapour, 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
9Cal/t reduces to 1.9 * 10
8Cal/t), this 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 demand of new technology, needs supporting development of new catalyst efficiently for this reason.The CO of bibliographical information
2The carrier of selective oxidation preparing styrene from ethylbenzene catalyst has Al
2O
3, ZnO, WO
3, SiO
2, ZrO
2, ZSM-5 and active carbon (AC) etc., active component has the oxide of transition metal such as Fe, V, Cr, Ce, Cu, Ni and Co, auxiliary agent that alkali 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 ferrite, ZrO
2Make catalyst with hydrotalcite type Mg-Al-Fe class material.Wherein dehydrogenation preferably catalyst 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 preparation
2O
3(10wt%)/Al
2O
3(90wt%) catalyst is at 823K, CO
2The mol ratio of/EB is 11, and 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 of study.
Zhang Weiguang etc. are " catalysis journal " 2000, and 21 volumes, have been reported the Fe-Na/AC catalyst of immersion process for preparing at the 1st phase in " ethylbenzene dehydrogenation and the iron of gas conversion coupled reaction/activated-carbon catalyst research against the current " literary composition of 27～30 pages.At the ethylbenzene mass space velocity is 1.28h
-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 (load capacity the is 1.0mmol/g AC) catalyst of immersion process for preparing in " Dehydrogenation of ethylbenzene with an activatedcarbon-supported vanadium catalyst " literary composition of 281～288 pages, 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 active carbon or aluminium oxide is the catalyst 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 zirconia and aluminium oxide is a kind of catalyst that contains vanadium, iron, antimony of preparing carriers, 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%.
(Vislovskiy V P such as Vislovskiy V P, Chang J-S, Park M-S, et al.Ethylbenzene into styrene with carbon dioxide over modifiedvanadia-alumina catalysts[J] .Catal.Commun.2002,3:227～231) reported a kind of V-Mg catalyst, conversion of ethylbenzene is 75%, and cinnamic selectivity is 95.9%, but the less stable of catalyst.
Summary of the invention
We know, improve the decentralization of vanadium species and the specific area of catalyst and help improving its catalytic performance, the inventor is surprised to find that, the molecular sieve that contains vanadium in the skeleton such as VAPO, VS, v element forms the redox center that isolates on framework of molecular sieve, have vanadium component, high-specific surface area and the consistent characteristics such as pore-size distribution of high degree of dispersion, oxidative dehydrogenation of ethylbenzene is had good catalytic activity.
Therefore, ethyl benzene oxidizing-dehydrogenation catalyst provided by the invention, it is characterized in that this catalyst mainly is made up of active component and auxiliary agent, said active component is the molecular sieve that contains v element in the skeleton structure, said auxiliary agent is alkali metal or alkaline-earth metal, and the content of auxiliary agent is 0.01～3.0mmol in every gram catalyst.
Catalyst provided by the invention, wherein said active component are the molecular sieve that contains v element in the skeleton structure, and more particularly, ethyl benzene oxidizing-dehydrogenation catalyst provided by the invention mainly is made up of active component and auxiliary agent; Said active component is the molecular sieve (abbreviate as and contain the vanadium molecular sieve) that contains v element in the skeleton structure, is 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 list of references Vanadosilicate catalysts prepared from different vanadium sources andtheir characteristics in methanol to conversion (A.Miyamoto, D.Medhanavyn and T.Inui, Applied Catalysis, 28 (1986) 89-103), Synthesisand Characterization of the Vanadium-incorporated Molecular SieveVAPO-5 (S.H.Jhung, Y.S.UH and H.Chon, Applied Catalysis 62 (1990) 61-72) and Synthesis, characterization and catalytic properties of vanadiumsilicates with a ZSM-48 structure (A.Tuel and Y.Ben Taarit, AppliedCatalysis A:General, 102 (1993) 201-204)).
Containing in the vanadium molecular sieve, characterize the content of vanadium in the skeleton with the mass percent of vanadium, is benchmark with the molecular sieve, and the mass percent of vanadium is preferably 0.01～10%, more preferably 1～6%.The said vanadium molecular sieve that contains can be V-Si molecular sieve (as VS-1 and VS-2), wherein vanadium and silicon are as backbone element, can be phosphoric acid vanadium aluminum molecular screen (as VAPO-5, VAPO-11, VAPO-31 and VAPO-17 etc.), wherein with vanadium, aluminium, phosphorus as backbone element; Also can be phosphoric acid vanadium Si-Al molecular sieve, the ratio of silicon and aluminium is arbitrarily, and at this moment vanadium, silicon, aluminium and phosphorus are simultaneously as backbone element.
In the catalyst provided by the invention, by adding the Acidity of Aikalinity on auxiliary agent regulating catalyst surfaces such as alkali metal or alkaline-earth metal, make that oxidative dehydrogenation is easier to carry out, suppress catalyst carbon deposit simultaneously, further improve ethylbenzene dehydrogenation conversion ratio, selectivity of styrene and catalyst life.Said auxiliary agent is alkali metal or alkaline-earth metal, the wherein preferred Li of alkali metal, Na or K, preferred Mg of alkaline-earth metal or Ca.The content of the content auxiliary agent of said auxiliary agent is preferably 0.01～1.0mmol in metal oxide in every gram catalyst.
Catalyst provided by the invention, its preparation process are that the presoma with auxiliary agent is made into the solution that concentration is 0.01～3mol/L; In the ratio of active component in the catalyst and auxiliary agent, molecular sieve is impregnated in the solution of auxiliary agent presoma, left standstill behind the dipping 4～36 hours; 383～393K drying 4～24 hours; Roasting is 4～8 hours under 673～873K, and drying obtains.Wherein the presoma of said auxiliary agent is nitrate, sulfate or acetate.
Ethyl benzene oxidizing-dehydrogenation catalyst provided by the invention, wherein vanadium forms the redox center that isolates on framework of molecular sieve, the characteristics of active component with high degree of dispersion and consistent pore-size distribution, improve the specific area of the decentralization and the catalyst of vanadium species, improved the stability of vanadium species on the catalyst; And carrying alkali metal or alkaline-earth metal make the surface of catalyst obtain suitable soda acid coupling, to the vanadium being the oxidative dehydrogenation of ethylbenzene catalytic reaction of active component, have good catalytic activity.
The specific embodiment
Below by embodiment the present invention is done that condition is bright further, but content not thereby limiting the invention.
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 orthophosphoric acid solution (phosphorus acid content 85%, Beijing chemical reagent work produces).Stir after 10 minutes and to add 2.3 gram five water vanadic sulfates (V content 22% is dissolved in the 2g water), continue under the room temperature to stir that the speed with 1mL/min adds 16mL template agent 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 flow air temperature-programmed calcination (120 ℃, 1 hour; 3 ℃/minute are 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 3.3%.
Accurately take by weighing potassium nitrate 0.606g, add water to 20ml, be stirred to potassium nitrate and dissolve fully; Accurately take by weighing 393K VAPO-5 molecular sieve (more than the 40 orders) 20.000g of oven dry down then, the potassium nitrate solution impregnated zeolite with configuring left standstill 24 hours, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the K/VAPO-5 catalyst, note is made catalyst A.Catalyst consist of 0.15mmolK
2O/g VAPO-5.
Embodiment 2
Accurately take by weighing sodium nitrate 0.533g, add water to 20ml, be stirred to sodium nitrate and dissolve fully; Accurately take by weighing 393K VAPO-5 molecular sieve (more than the 40 orders) 20.000g of oven dry down then, the sodium nitrate solution impregnated zeolite with configuring left standstill 24 hours, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the Na/VAPO-5 catalyst, note is made catalyst B.Catalyst consist of 0.01mmolNa
2O/g VAPO-5.
Embodiment 3
Accurately take by weighing lithium nitrate 0.414g, add water to 20ml, be stirred to lithium nitrate and dissolve fully; Accurately take by weighing 393K VAPO-5 molecular sieve (more than the 40 orders) 20.000g of oven dry down then, the lithium nitrate solution impregnated zeolite with configuring left standstill 24 hours, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the Li/VAPO-5 catalyst, note is made catalyst C.Catalyst consist of 0.5mmolLi
2O/g VAPO-5.
Embodiment 4
Accurately weighing magnesium nitrate 3.186g adds water to 20ml, is stirred to magnesium nitrate and dissolves fully; Accurately take by weighing 393K VAPO-5 molecular sieve (more than the 40 orders) 20.000g of oven dry down then, the magnesium nitrate solution impregnated zeolite with configuring left standstill 24 hours, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the Mg/VAPO-5 catalyst, note is made catalyst D.Catalyst consist of 1mmolMgO/g VAPO-5.
Embodiment 5
Accurately take by weighing calcium nitrate 0.618g, add water to 20ml, be stirred to calcium nitrate and dissolve fully; Accurately take by weighing 393K VAPO-5 molecular sieve (more than the 40 orders) 20.000g of oven dry down then, the calcium nitrate solution impregnated zeolite with configuring left standstill 24 hours, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the Ca/VAPO-5 catalyst, note is made catalyst E.Catalyst consist of 1.5mmolCaO/g VAPO-5.
Embodiment 6
Synthesizing of VS-1 molecular sieve: with 1.0 gram V
2O
5Be dissolved in the 50 gram TBAHs, 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 2.6%.
Accurately take by weighing potassium nitrate 0.606g, add water to 20ml, be stirred to potassium nitrate and dissolve fully; Accurately take by weighing 393K VS-1 molecular sieve (more than the 40 orders) 20.000g of oven dry down then,, left standstill 24 hours with above-mentioned solution impregnation molecular sieve, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the K/VS1 catalyst, note is made catalyst F.Catalyst consist of 0.15mmolK
2O/g VAPO-5.。
Embodiment 7
Synthesizing of VS-2 molecular sieve: with 1.8 gram V
2O
5Be dissolved in 30 gram TBAHs 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 4.9%.
Accurately take by weighing potassium nitrate 0.606g, add water to 20ml, be stirred to potassium nitrate and dissolve fully; Accurately take by weighing 393K VS-2 molecular sieve (more than the 40 orders) 20.000g of oven dry down then,, left standstill 24 hours with above-mentioned solution impregnation molecular sieve, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the K/VS-2 catalyst, note is made catalyst G.Catalyst consist of 0.15mmolK2O/g VAPO-5.
Embodiment 8
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 orthophosphoric acid solution (phosphorus acid content 85%, Beijing chemical reagent work produces).Stir after 10 minutes and to add 2.1g five water vanadic 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 agent di-n-propylamine (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 7.8%.
Accurately take by weighing potassium nitrate 0.606g, add water to 20ml, be stirred to potassium nitrate and dissolve fully; Accurately take by weighing 393K VAPO-11 molecular sieve (more than the 40 orders) 20.000g of oven dry down then,, left standstill 24 hours with above-mentioned solution impregnation molecular sieve, 383K is dry 24 hours down in the baking oven, and drier is gone in 773K roasting 3 hours, obtain the K/VAPO-11 catalyst, note is made catalyst H.Catalyst consist of 0.15mmolK
2O/gVAPO-5.
Embodiment 9
Present embodiment illustrates the reaction effect of catalyst provided by the invention.
The method of preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene is as follows: be reflected on the fixed bed reactors and carry out, each experiment catalyst consumption is 10mL, and bed temperature is 673K～873K, and stagnation pressure is 1 atmospheric pressure, CO
2: ethylbenzene (mol ratio)=10, the liquid volume air speed of ethylbenzene is 1.0h
-1
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.The results are shown in Table 1.
Table 1
Embodiment 10
Present embodiment is an example with catalyst D, and the stability of catalyst provided by the invention is described.
Data as a comparison are from Vislovskiy V P, Chang J-S, Park M-S, et al.Ethylbenzene into styrene with carbon dioxide over modifiedvanadia-alumina catalysts[J] .Catal.Commun.2002, the V-Mg catalyst of report in 3:227～231, reaction condition: 595 ℃, EB/CO
2=1/1 (mol ratio), LHSV=1h
-1
The result is as shown in table 2.
Table 2
From table 2 data as can be seen, the stability of catalyst D obviously is better than literature value.
Claims (9)
1. catalyst for phenylethylene dehydrogenation, it is characterized in that this catalyst is made up of active component and auxiliary agent, said active component is the molecular sieve that contains v element in the skeleton structure, said auxiliary agent is alkali metal or alkaline-earth metal, and the content of auxiliary agent is counted 0.01～3.0mmol with metal oxide in every gram catalyst.
2. according to the catalyst of 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 catalyst of claim 2, said phosphoric acid vanadium aluminum molecular screen is VAPO-5 or VAPO-11.
4. according to the catalyst of claim 2, said V-Si molecular sieve is VS-1 or VS-2.
5. according to the catalyst of claim 1, contain in the said skeleton structure in the molecular sieve of v element, the mass percent that with the molecular sieve is the benchmark vanadium is 0.01～10 heavy %.
6. according to the catalyst of claim 5, the mass percent that contains vanadium in the molecular sieve of v element in the said skeleton structure is 1～6%.
7. according to the catalyst of claim 1, the content of said auxiliary agent is 0.01～1.0mmol in every gram catalyst.
8. according to the catalyst of claim 1, said alkali metal is selected from Li, Na or K.
9. according to the catalyst of claim 1, said alkaline-earth metal is selected from Mg or Ca.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100016833A CN100548488C (en) | 2005-02-05 | 2005-02-05 | Ethyl benzene oxidizing-dehydrogenation catalyst |
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|---|---|---|---|
| CNB2005100016833A CN100548488C (en) | 2005-02-05 | 2005-02-05 | Ethyl benzene oxidizing-dehydrogenation catalyst |
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| CN103121919A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation method in presence of mild oxidant |
| CN105817243B (en) * | 2015-01-27 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of carbon-based material, preparation method and use |
| CN106000448B (en) * | 2016-05-26 | 2019-01-29 | 江苏正丹化学工业股份有限公司 | Vinyltoluene production catalyst and preparation method thereof |
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Non-Patent Citations (1)
| Title |
|---|
| 含铁和钒的ZSM-5型分子筛的合成、表征及催化性能. 佟惠娟等.石油化工高等学校学报，第15卷第2期. 2002 * |
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