CN101254470A - Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same - Google Patents
Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same Download PDFInfo
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- CN101254470A CN101254470A CNA200710010508XA CN200710010508A CN101254470A CN 101254470 A CN101254470 A CN 101254470A CN A200710010508X A CNA200710010508X A CN A200710010508XA CN 200710010508 A CN200710010508 A CN 200710010508A CN 101254470 A CN101254470 A CN 101254470A
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Abstract
The invention discloses a Mo-based catalyst for inverse disproportionate synthesis of propylene from ethylene and butylene and the preparation method thereof. The Mo-based catalyst is characterized in that: the catalyst is composed of A/S, wherein A as major active component is an oxide of molybdenum and S as carrier is a mixture. The preparation method of the catalyst includes the following steps: removing a mesoporous molecular sieve with a templating agent, preparing the carrier mixture S of a certain particle size by using aluminum oxide or a precursor thereof by different methods, immersing the resulting product in a Mo-containing solution, drying, and calcining at 500-800 DEG C for 1-4 hours to obtain the required catalyst. The invention utilizes the composite carrier composed of mesoporous molecular sieve and aluminum oxide. The catalyst has the advantages of simple preparation and excellent stability. Therefore, the catalyst prepared in the invention can be used for the production of propylene with high conversion rate, high selectivity and high stability.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for ethene and butene inverse disproportionation preparation of propene.
Background technology
Propylene is one of important foundation raw material of development petrochemical industry, also is the fastest petroleum chemicals of demand growth in the world, and world's propylene demand expects 2010 and will reach 7,500 ten thousand tons from 1,800 ten thousand tons of nearly 5,000 ten thousand tons of increasing to 2000 in 1980 every year.It with ethene and butene reaction system propylene one of method that increases propone output, because supply exceed demand for butylene at present, especially 2～butylene shortage is effectively utilized approach, so suit measures to local conditions to adopt this course of reaction can reasonably regulate the product layout of ethene, propylene and butylene.There is part to contain the crude ethylene of methane, ethane and small quantity of hydrogen in addition in the product of heavy oil catalytic pyrolysis, itself and butene reaction are made propylene, both can improve the output of propylene, can reduce the energy consumption of cryogenic separation again.This is a process with practicality and novelty, and it is succeeded in developing and can produce remarkable economic efficiency and social benefit.
United States Patent (USP) (USP5,120,894) reported the catalyst of ethene and butene inverse disproportionation system propylene, this catalyst is that Mo, W and Re are compound loaded on carriers such as aluminium oxide, silica, alkali metal oxide and alkaline earth oxide, reaction temperature at 274～343 ℃, pressure at 2.4～3.5MPa.But above-mentioned catalyst is used for the reaction by ethene and butylene system propylene, and its selectivity is relatively poor.
Chinese patent (application number is 01104355.5) has been reported the catalyst of ethene and butene inverse disproportionation system propylene, this catalyst be Mo.W and Re compound loaded molecular sieve comprises Y on the micro porous molecular sieve carrier, Beta, SAPO series, ZSM series and MCM series.Be reflected in fixed bed or the fluidized-bed reactor and carry out, 0～300 ℃ of reaction temperature; Weight space velocity: 0.01～3h
～1C in the reactor feed gas
2H
4/ 2～C
4H
8Ratio: 0.2～4; Reaction pressure: 0.1～2.0MPa, its method for preparing catalyst are comparatively complicated.
Summary of the invention
The purpose of this invention is to provide a kind ofly have high-specific surface area, in order the mesopore molecular sieve and the Mo on the alumina composite carrier of pore passage structure are catalyst based, can be used for than under the low reaction temperatures (80～200 ℃) by ethene and butene inverse disproportionation system propylene.
The invention provides a kind of be used for than under the low reaction temperatures by the catalyst of ethene and butene inverse disproportionation preparation of propene, it consists of A/S, active constituent A is the oxide of molybdenum, its weight loading is 1～20%; Carrier S is the mixture of mesopore molecular sieve and aluminium oxide.
A kind of Mo that is used for ethene and butene inverse disproportionation system propylene is catalyst based, and it is characterized in that: described catalyst consists of A/S, and main active component A is the oxide of molybdenum, and carrier S is a mixture; This Preparation of catalysts method is: at first with mesopore molecular sieve process template removal, prepare the mixture carrier S of certain particle size then with distinct methods with aluminium oxide (or presoma); Flood with the solution that contains molybdenum element then, dry and made required catalyst in 1～4 hour in 500～800 ℃ of roastings.
Described active constituent A is the oxide of molybdenum, and its weight loading is 1～20%.
Described carrier S is a mixture, and wherein main component is mesoporous silicon based molecular sieve, and the aperture is between 2～20nm, and the interpolation component is an aluminium oxide.
Molecular sieve in the described carrier comprises SBA series (SBA～15, SBA～16, SBA～6, SBA～1, SBA～2, SBA～12, SBA～17 etc.), HMS, FSM～16 and FDU series (FDU～1, FDU～2, FDU～5, FDU～12), its specific area is greater than 300m
2/ g must be through template removal, and weight content is more than or equal to 30%.
Prepare the method key step of described catalyst, it is characterized in that:
(a) composite carried catalyst for preparing is at 500～800 ℃ of roastings 2～8 hours, compression molding;
(b),, make required catalyst 100～120 ℃ of following dryings and in 500～800 ℃ of roastings 1～4 hour to the solution impregnation that contains molybdenum element of carrier after the roasting.
Be used for ethene and butene inverse disproportionation preparation of propene Preparation of catalysts method is: at first prepare the mixture carrier of certain granules degree with conventional method, and 500～800 ℃ of roastings 2～8 hours.
The dipping rear catalyst was 500～800 ℃ of roastings 1～4 hour.
The catalyst of preparation is used for ethene and butene inverse disproportionation system propylene, reaction condition: 80～200 ℃, 0.1～2.30MPa, ethylene/butylene mol ratio 1～4.0.
In the activation that need heat up under inert gas atmosphere of catalyst on the fixed bed reactors, the activation condition of catalyst is: 400～700 ℃ of temperature, pressure 0.1～0.3MPa, inert gas are N
2, Ar, one or more mixtures among the He; Has higher activity, selectivity and stability at 80～200 ℃, 0.1～2.3MPa, ethene/2～butylene under than 1～4.0 reaction condition.
Catalyst of the present invention is used for ethene and butene inverse disproportionation preparation of propene time spent, C
4Raw material can be 2～butylene, can be 2～butene content greater than 50% mixed material, also can be 1～butylene.When being raw material with 1～butylene, 1～butylene need at first carry out isomerization reaction, to obtain 1～butylene, 2～butene mixture material near thermodynamic equilibrium value as anti-disproportionation raw material.
Advantage of the present invention:
The present invention adopts the complex carrier of mesopore molecular sieve and aluminium oxide, and this catalyst has the advantages that the preparation method is simple and stability is superior.Therefore use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces propylene.
Description of drawings
The present invention is further detailed explanation below in conjunction with drawings and the embodiments.
Fig. 1 is the reactivity evaluation map over time of the A described in the embodiment, B, three kinds of catalyst of C;
Fig. 2 is the reactivity evaluation map over time of the A described in the embodiment, B, three kinds of catalyst of C.
The specific embodiment
Embodiment 1
Take by weighing 2g SBA series molecular sieve, add the aluminum nitrate of ethanol dissolving, in 120 ℃ of baking ovens, dried by the fire 24 hours behind the carrier natural air drying.Through 550 ℃ of roastings after 2 hours, compression molding obtains the complex carrier of certain particle size under moving air.Take by weighing the SBA-A carrier 2.45g that obtains, add 4 milliliters of ammonium molybdate aqueous solutions, flooded 30 minutes, air drying 24 hours, then above-mentioned sample is put into muffle furnace, under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly make the A catalyst of Mo content 8wt% after the cooling.
Take by weighing 2g SBA series molecular sieve, add the 2g aluminium oxide, behind the mechanical lapping mixing, be placed in the Muffle furnace 550 ℃ of roastings 2 hours, compression molding obtains the complex carrier of certain particle size.Take by weighing the SBA-B carrier 2.45g that obtains, add 4 milliliters of ammonium molybdate aqueous solutions, flooded 30 minutes, air drying 24 hours, then above-mentioned sample is put into muffle furnace, under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly make the B catalyst of Mo content 8wt% after the cooling.
Embodiment 3
Take by weighing 2g SBA series molecular sieve, add the 1g aluminium oxide, in mortar behind the mechanical lapping mixing, be placed in the Muffle furnace the following 550 ℃ of roastings of moving air 2 hours, compression molding obtains the complex carrier of certain particle size.Take by weighing the SBA-C carrier 2.45g that obtains, add 4 milliliters of ammonium molybdate aqueous solutions, flooded 30 minutes, air drying 24 hours, then above-mentioned sample is put into muffle furnace, under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly make the C catalyst of Mo content 8wt% after the cooling.
Embodiment 4
Take by weighing 2g HMS series molecular sieve, add the 1g aluminium oxide, in mortar behind the mechanical lapping mixing, be placed in the Muffle furnace the following 550 ℃ of roastings of moving air 2 hours, compression molding obtains the complex carrier of certain particle size.Take by weighing the HMS carrier 2.45g that obtains, add 4 milliliters of ammonium molybdate aqueous solutions, flooded 30 minutes, air drying 24 hours, then above-mentioned sample is put into muffle furnace, under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly make the D catalyst of Mo content 4wt% after the cooling.
Embodiment 5
Take by weighing 2g FSM series molecular sieve, add the 2g aluminium oxide, in mortar behind the mechanical lapping mixing, be placed in the Muffle furnace the following 550 ℃ of roastings of moving air 2 hours, compression molding obtains the complex carrier of certain particle size.Take by weighing the FSM carrier 2.45g that obtains, add 4 milliliters of ammonium molybdate aqueous solutions, flooded 30 minutes, air drying 24 hours, then above-mentioned sample is put into muffle furnace, under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly make the E catalyst of Mo content 4wt% after the cooling.
Embodiment 6
Take by weighing 2g SBA series molecular sieve, add the 2g aluminium oxide, in mortar behind the mechanical lapping mixing, be placed in the Muffle furnace the following 550 ℃ of roastings of moving air 2 hours, compression molding obtains the complex carrier of certain particle size.Take by weighing the SBA-C carrier 2.45g that obtains, 4 milliliters of the ammonium molybdate aqueous solutions of adding variable concentrations, flooded 30 minutes, air drying 24 hours, then above-mentioned sample is put into muffle furnace, under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly make the catalyst series of different Mo content after the cooling, active as shown in table 2.
Is in the stainless steel fixed bed reactors of 10mm with 2g according to the catalyst of the embodiment method preparation internal diameter of packing into, and at 100-200 ℃, ethene and 2-butylene carry out anti-disproportionated reaction under the 1.0MPa pressure, and keeping the weight space velocity of 2-butylene is 0.8h
-1, switch and begin sample analysis after 20 minutes.A, B, the reactivity of several catalyst of C rule is over time seen Fig. 1, and different carriers sees Table 1 to the influence of disproportionation activity, and different Mo content sees Table 2 to the influence of disproportionation activity.Under higher space velocity, catalyst shows good stability and selectivity, but the preparation method is very big to the stability influence of catalyst.
The foregoing description is the part preferred embodiment, is not the present invention is limited.In fact can realize the present invention so long as meet the condition that summary of the invention partly sets forth, therefore, protection domain of the present invention is as the criterion with the claim of application.
Catalyst based ethene and 4 hours the evaluating data of 2-preparing propylene by butene disproportionation reaction gone up of Mo that the different mesopore molecular sieves of table 1 are carrier loaded
| Catalyst | 2-butene conversion (%) | Propylene selectivity (%) |
| B | 89.4 | 96.0 |
| D | 86.6 | 95.6 |
| E | 84.0 | 95.7 |
Table 2. different Mo content Mo/SBA-Al
2O
34 hours evaluating data of ethene and 2-preparing propylene by butene disproportionation reaction on the catalyst
| Catalyst | 2-butene conversion (%) | Propylene selectivity (%) |
| 4Mo/SBA-Al 2O 3 | 46.1 | 88.2 |
| 8Mo/SBA-Al 2O 3 | 89.4 | 96.0 |
| 16Mo/SBA-Al 2O 3 | 64.2 | 95.0 |
Claims (5)
1. a Mo who is used for ethene and butene inverse disproportionation system propylene is catalyst based, and it is characterized in that: described catalyst consists of A/S;
Described carrier S is mesoporous silicon based molecular sieve and alumina mixture, and wherein main component is mesoporous silicon based molecular sieve, and its weight content is more than or equal to 30%, and the aperture is between 2～20nm;
Described active constituent A is the oxide of molybdenum, and its weight loading is 1～20%.
2. catalyst based according to the described Mo that is used for ethene and butene inverse disproportionation system propylene of claim 1, it is characterized in that: the molecular sieve in the described carrier S comprises that SBA series is selected from SBA～15, SBA～16, SBA～6, SBA～1, SBA～2, SBA～12, SBA～17, HMS, FSM～16 and FDU series are selected from FDU～1, FDU～2, FDU～5, FDU～12, and its specific area is greater than 300m
2/ g must be through template removal.
3. one kind prepares claim 1 or the 2 described methods that are used for ethene and butene inverse disproportionation preparation of propene catalyst, it is characterized in that:
(a) complex carrier for preparing is at 500～800 ℃ of roastings 2～8 hours, compression molding;
(b) to the solution impregnation that contains molybdenum element of carrier after the roasting, 100～120 ℃ of following dryings and in 500～800 ℃ of roastings 1～4 hour.
4. the method for ethene and butene inverse disproportionation system propylene is characterized in that:
Adopt catalyst to consist of A/S; Described carrier S is mesoporous silicon based molecular sieve and alumina mixture, and wherein main component is mesoporous silicon based molecular sieve, and its weight content is more than or equal to 30%, and the aperture is between 2～20nm; Described active constituent A is the oxide of molybdenum, and its weight loading is 1～20%.
Reaction condition: 80～200 ℃, 0.1～2.30MPa, ethylene/butylene mol ratio 1～4.0.
5. according to the method for described ethene of claim 6 and butene inverse disproportionation system propylene, it is characterized in that: in the activation that need under inert gas atmosphere, heat up of catalyst on the fixed bed reactors, the activation condition of catalyst is: 400～700 ℃ of temperature, pressure 0.1～0.3MPa, inert gas are N
2, Ar, one or more among the He.
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| CNA200710010508XA CN101254470A (en) | 2007-02-28 | 2007-02-28 | Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same |
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|---|---|---|---|
| CNA200710010508XA CN101254470A (en) | 2007-02-28 | 2007-02-28 | Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same |
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| CN101940954B (en) * | 2009-07-09 | 2012-10-17 | 中国石油化工股份有限公司 | Method for preparing alumina supporters |
| CN103030507A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
| CN103846084A (en) * | 2014-03-25 | 2014-06-11 | 西安科技大学 | Supported tungsten based catalyst for preparing propylene by 1-butene disproportionation as well as preparation method and application of supported tungsten based catalyst |
| CN104056651A (en) * | 2013-03-22 | 2014-09-24 | 中国科学院大连化学物理研究所 | Molybdenum supported catalyst for 1-butylene disproportionation reaction and preparation method |
| FR3039543A1 (en) * | 2015-07-31 | 2017-02-03 | Ifp Energies Now | OLEFIN METATHESIS METHOD USING A CATALYST CONTAINING ALUMINUM AND MOLYBDENUM INCORPORATED BY MEANS OF AT LEAST TWO PRECURSORS |
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| CN103030507A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
| CN103030507B (en) * | 2011-09-29 | 2015-01-07 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene and ethylene |
| CN104056651B (en) * | 2013-03-22 | 2017-03-15 | 中国科学院大连化学物理研究所 | A kind of molybdenum loaded catalyst and preparation method for the reaction of 1 butylene disproportionation |
| CN104056651A (en) * | 2013-03-22 | 2014-09-24 | 中国科学院大连化学物理研究所 | Molybdenum supported catalyst for 1-butylene disproportionation reaction and preparation method |
| CN103846084A (en) * | 2014-03-25 | 2014-06-11 | 西安科技大学 | Supported tungsten based catalyst for preparing propylene by 1-butene disproportionation as well as preparation method and application of supported tungsten based catalyst |
| US10322983B2 (en) | 2015-07-31 | 2019-06-18 | IFP Energies Nouvelles | Olefin metathesis method using a catalyst containing aluminum and molybdenum |
| FR3039543A1 (en) * | 2015-07-31 | 2017-02-03 | Ifp Energies Now | OLEFIN METATHESIS METHOD USING A CATALYST CONTAINING ALUMINUM AND MOLYBDENUM INCORPORATED BY MEANS OF AT LEAST TWO PRECURSORS |
| WO2017021232A1 (en) * | 2015-07-31 | 2017-02-09 | IFP Energies Nouvelles | Olefin metathesis method using a catalyst containing aluminium and molybdenum incorporated by means of at least two precursors |
| FR3039545A1 (en) * | 2015-07-31 | 2017-02-03 | Ifp Energies Now | PROCESS FOR OLEFIN METATHESIS USING A CATALYST CONTAINING ALUMINUM AND MOLYBDEN |
| WO2017021234A1 (en) * | 2015-07-31 | 2017-02-09 | IFP Energies Nouvelles | Olefin metathesis method using a catalyst containing aluminium and molybdenum |
| CN108137441A (en) * | 2015-07-31 | 2018-06-08 | Ifp 新能源公司 | Use the olefin metathesis method containing aluminium and the catalyst of molybdenum |
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| US10322984B2 (en) | 2015-07-31 | 2019-06-18 | IFP Energies Nouvelles | Olefin metathesis method using a catalyst containing aluminium and molybdenum incorporated by means of at least two precursors |
| CN108059580A (en) * | 2016-11-09 | 2018-05-22 | 中国科学院大连化学物理研究所 | Catalyst of hexene/ethylene and preparation method thereof is prepared from disproportionation for 1- butylene |
| CN108059580B (en) * | 2016-11-09 | 2020-01-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing hexene/ethylene by self-disproportionation of 1-butene and preparation method thereof |
| CN109833915A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | Molybdenum loaded catalyst and preparation method thereof for 1- butylene self disproportionation reaction |
| CN109847791A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation method and the application in butylene disproportionation reaction |
| CN111250153A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation |
| CN111250153B (en) * | 2018-11-30 | 2021-08-10 | 中国科学院大连化学物理研究所 | Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation |
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Application publication date: 20080903 |