CN105854859A - Efficient bifunctional catalyst as well as preparation and application thereof - Google Patents

Efficient bifunctional catalyst as well as preparation and application thereof Download PDF

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CN105854859A
CN105854859A CN201610268475.8A CN201610268475A CN105854859A CN 105854859 A CN105854859 A CN 105854859A CN 201610268475 A CN201610268475 A CN 201610268475A CN 105854859 A CN105854859 A CN 105854859A
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sio
catalyst
preparation
ethanol
roasting
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门勇
黄小雄
王金果
王远强
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Shanghai University of Engineering Science
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Shanghai University of Engineering Science
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/14—Silica and magnesia
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2521/14—Silica and magnesia
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention relates to an efficient bifunctional catalyst as well as a preparation and an application thereof. The composition of the catalyst is MxSiyOz, wherein M is one of Cu, Mg, Zn, Ca, Co, Zr, BA, K or Na; x and y are both positive integers; x:y =(1:100)-(100:1); z is determined by the valence state of element of M and the proportion of x and y; the charge balance of the catalyst is ensured. A preparation method comprises the following steps: weighing the oxide or hydroxide of the metal element M, mixing with SiO2 so that the mole ratio of M to Si in the mixture is x:y; drying and roasting; and screening, thereby acquiring a binary compound oxide catalyst. Compared with the prior art, the efficient bifunctional catalyst has the advantages of simple and convenient process route, low cost, higher butadiene yield of the prepared catalyst and potential industrial application prospect.

Description

A kind of efficiently bifunctional catalyst and preparation thereof and application
Technical field
The present invention relates to a kind of metal oxide catalyst and preparation and application, especially relate to a kind of efficient Bifunctional catalyst and preparation thereof and application.
Background technology
In recent years, both at home and abroad achieving important breakthrough with biomass in terms of the process route of raw material production ethanol, The source of ethanol is gradually enriched so that had broad prospects by the technology path of ethanol synthesis butadiene.
1,3-butadiene is important Organic Chemicals, has extensively in the field such as synthetic rubber and synthetic resin Application.It is mainly used in synthesizing butylbenzene, producing along chemical industry such as fourth, polybutadiene rubber, ABS, SBS, MBS Product.Currently, the production method of butadiene mainly has two kinds: butane butylene dehydrogenation method and ethylene by-product extraction process, But the development of these two kinds of methods is largely restricted by petroleum resources.Ethanol Method prepares 1,3-butadiene Being succeeded in developing by the Lebedev of the former Soviet Union, this process is with ethanol as raw material, at silica gel load copper oxide as urging Under the effect of agent, reaction temperature, at about 350 DEG C, occurs dehydrogenation dehydration to prepare butadiene, and fourth two The ultimate yield of alkene can reach more than 25%.
Alcohol catalysis Butadiene Extraction Process receives significant attention as the new technology of resources effective utilization, is permitted both at home and abroad This has all been carried out detailed research by many laboratorys.At present, research work is concentrated mainly on the soda acid of Study of Catalyst The character impact on its activity and the reaction mechanism mechanism of reaction of catalytic process thereof.By between catalyst acid alkalescence matter and activity The research of relation and reaction mechanism clear and definite, learn the catalyst property needed for often step reaction, to catalyst Soda acid character carries out effective modulation, carries out catalyst choice and exploitation targetedly.Patent US2423681 The composite oxides MgO-SiO of preparation2, the ZrO of patent US 2436125 preparation2、ThO2And SiO2Composite oxygen Compound, has soda acid bifunctional catalyst direct catalysis ethanol one step and converts butadiene processed.Patent disclosed above In technology, it is the physical mixed of routine, wet mixing method that catalysis ethanol one step converts the method for preparing catalyst of butadiene processed With coprecipitation etc., the selectivity of its ethanol conversion and butadiene all ratios are relatively low.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide one the most difunctional Catalyst and preparation thereof and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of efficiently bifunctional catalyst, this catalyst consist of MxSiyOz, wherein, described M be Cu, One in Mg, Zn, Ca, Co, Zr, Ba, K or Na, x and y is positive integer, and x:y=1:100～ 100:1, z are by the element valence of M, and the ratio-dependent of x, y, and ensure the charge balance of catalyst.
Described M is the one in Zn, Cu, Ca, Mg or Ba element；
Described catalyst MxSiyOzIn, x:y=1:20～20:1.
The efficiently preparation method of bifunctional catalyst, comprises the following steps: weigh metallic element M oxide or Hydroxide, with SiO2Mixing so that in mixture, the mol ratio of M Yu Si is x:y, dry, roasting, I.e. obtain purpose product.
Described SiO2Particle diameter be 20nm-500nm.SiO in this particle size range2Advantageously in preparation During the oxide etc. of the M dispersing uniformity on its surface, thus improve the last catalyst prepared and produce The catalytic performance of product.
The oxide of metallic element M or hydroxide and SiO2Mixed method be physical mixed method, wet mixing method, Coprecipitation or infusion process；
The process conditions being dried are: be dried 8～24h at 100～150 DEG C；
The process conditions of roasting are: roasting 2～6h at 200～600 DEG C.
Oxide or the hydroxide of metallic element M are prepared from by following steps: weigh and comprise metallic element The precursor salt of M, prepares oxide or the hydroxide of metallic element M, or continues metallic element M The further roasting of hydroxide obtain the oxide of M；
SiO2It is prepared from by following steps: under room temperature, alcoholic solvent, catalyst and water mixing, adds silicon Source, stirs, filters, washs, after drying, obtains SiO2。
In the oxide of metallic element M or the preparation of hydroxide:
Precursor salt is subcarbonate, hydroxide, nitrate, sulfate, chlorate, ethylate or acetic acid One or more of salt；
The process conditions of roasting are: roasting 2～6h at 100～600 DEG C；
The method of oxide or hydroxide that precursor salt prepares metallic element M is hydro-thermal method, the sedimentation method, molten Glue-gel method or thermal decomposition method；
SiO2Preparation in:
The volume ratio of the interpolation in alcoholic solvent, catalyst, water and silicon source is 1:(0.05-1): (0.1-1): (0.05-1)；
Described alcoholic solvent be ethanol, isopropanol, ethylene glycol one or more；
Described catalyst is ammonia, urea liquid or sodium hydroxide solution；Urea liquid and sodium hydroxide solution Concentration is preferably 5mol/L；
The described one that silicon source is tetraethyl orthosilicate, methyl silicate, tetraethoxysilane, tetramethoxy-silicane Or it is multiple.
Efficiently bifunctional catalyst is for ethanol butadiene the most processed.
During butadiene the most processed for catalysis ethanol, its process conditions are: the pressure of 1～50 atmospheric pressure, 200～600 DEG C Temperature range, gas phase air speed 102～106h-1。
The present invention, by optimizing method for preparing catalyst, will improve the interaction between metal-oxide further, Improve catalysis activity and the heat stability of catalyst.The present invention is by optimizing single oxide or hydroxide precursor Preparation method so that it is there is big specific surface area, suitable particle size and surface acidic-basic property, pass through further Optimize mixed method and prepare catalyst MxSiyOzSo that between two components, mixing is more uniformly distributed, wherein by optimizing Single oxide that preparation method prepares or the crystal grain of hydroxide are at SiO2On more disperse, shape between two components Become more suitable catalyst surface acidic site and the quantity of basic sites and relative intensity, promote the catalysis of ethanol The efficiency converted, the beneficially generation of butadiene.
Compared with prior art, the invention have the advantages that
(1) present invention prepares two tuples by the preparation method and both mixed methods optimizing single oxide Divide composite oxide catalysts, change element valence simultaneously and optimize basic sites with acidic site quantity with relative with composition Intensity, reaches suitable acid-base balance, promotes the multiple catalysis of dehydrogenation-be condensed-be dehydrated organically to be coupled in one.
(2) method for preparing catalyst technique is simple, and raw material is single, with low cost, converts fourth processed at alcohol catalysis Two alkene reactions have the selectivity of higher ethanol conversion and butadiene, uses this catalyst to carry out ethanol system 1,3- Butadiene, its more than Transformation efficiency is up to 90 %, the yield of butadiene can reach more than 70%, is suitable to industry metaplasia Produce and application, there is preferable market prospect.
Accompanying drawing explanation
Fig. 1 is the MgO-SiO of magnesium oxide synthesis prepared by distinct methods2Binary composite oxide catalysts is used for second The butadiene productivity figure of alcohol butadiene；
Fig. 2 is the butadiene productivity figure of different types of binary composite oxide catalysts；
Fig. 3 is the butadiene productivity figure of binary composite oxide catalysts prepared by different mixing modes.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (thermal decomposition method)
By 10g C4Mg4O12·H2MgO2·XH2O is placed in Muffle furnace, roasting calcining 16h at 450 DEG C, Prepare MgO.
Take the 0.26g MgO and 0.21g SiO of above-mentioned preparation2It is placed in mortar, mechanical mixture 10 minutes, gained Solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 2
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (hydro-thermal method)
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Take the 0.26g MgO and 0.21g SiO of above-mentioned preparation2It is placed in mortar, mechanical mixture 10 minutes, gained Solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 3
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (sedimentation method)
By 2.45g MgSO4·7H2O is dissolved in the deionized water of 100mL, stirs until completely dissolved, then Ammonia spirit is dropwise added drop-wise in above-mentioned solution, to PH=12, then solution is poured in rustless steel water heating kettle, After screwing hermetic in the baking oven of 160 DEG C constant temperature 5h, naturally cool to room temperature, centrifugal, be washed with deionized, 12h it is dried in the vacuum drying oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare MgO.
Take the 0.26g MgO and 0.21g SiO of above-mentioned preparation2It is placed in mortar, mechanical mixture 10 minutes, gained Solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 4
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (sol-gel process)
By 5.72g Mg (OC2H5)2It is dissolved in deionized water and the 50mL alcohol mixed solution of 4.5mL, then Oxalic acid solution is dropwise added drop-wise in above-mentioned solution, to PH=5, stirs 80 DEG C of condensing reflux 24h to forming gel, Then the gel of gained is dried in 70 DEG C of baking ovens 12h；At 500 DEG C, calcine 2h again, prepare MgO.
Take the 0.26g MgO and 0.21g SiO of above-mentioned preparation2It is placed in mortar, mechanical mixture 10 minutes, gained Solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 5
Ethanol butadiene binary composite oxide catalysts ZnO-SiO2Preparation
By 1.32g Zn (CH3COO)2Being dissolved in the deionized water of 20mL, stirring until completely dissolved, then will 9mL NaOH (5mol/mL) is dropwise added drop-wise in above-mentioned solution；Again the deionized water of 11mL is poured into above-mentioned mixed Close in solution, then solution is poured in the rustless steel water heating kettle of 50mL, at the baking oven of 160 DEG C after screwing hermetic Middle constant temperature 12h, naturally cools to room temperature, centrifugal, is washed with deionized, and is dried in the vacuum drying oven of 60 DEG C 12h；At 500 DEG C, calcine 2h again, prepare ZnO.
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Take the 0.53g ZnO and 0.21g SiO of above-mentioned preparation2It is dissolved in 50mL deionized water, above-mentioned solution is existed 50 DEG C of stirring 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two Component composite oxide catalysts ZnO-SiO2。
Embodiment 6
Ethanol butadiene binary composite oxide catalysts CuO-SiO2Preparation
By 1.5g CuSO4·5H2O is dissolved in the deionized water of 100mL, stirs until completely dissolved, by 10mL Ethylene glycol and 10mL NaOH (2mol/L) are added in above-mentioned solution, and then solution poured into the rustless steel of 150mL In water heating kettle, after screwing hermetic in the baking oven of 160 DEG C constant temperature 12h, naturally cool to room temperature, centrifugal, spend Ionized water washs, and is dried 12h in the vacuum drying oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare CuO.
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Take the 0.52g CuO and 0.21g SiO of above-mentioned preparation2It is dissolved in 50mL deionized water, above-mentioned solution is existed 50 DEG C of stirring 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two Component composite oxide catalysts CuO-SiO2。
Embodiment 7
Ethanol butadiene binary composite oxide catalysts MgO-SiO2
By 8.3g Mg (NO3)2·6H2Si (the OC of O and 3.6mL2H5)4Be dissolved in 24.3mL dehydrated alcohol and In the mixed solution of the deionized water of 14.5mL, being stirred by above-mentioned solution at 50 DEG C, the nitric acid with 68% regulates PH=2, at 50 DEG C stir 3h, afterwards at 100 DEG C stirring to be dried, gained solid through 500 DEG C of roasting 5h, Cool down and i.e. obtain two component composite oxide catalysts MgO-SiO2。
Embodiment 8
Ethanol butadiene binary composite oxide catalysts CaO-SiO2Preparation
By 1.5g CaCl2It is dissolved in the deionized water of 100mL, stirs until completely dissolved, by 10mL second two Alcohol and 10mL NaOH (2mol/L) are added in above-mentioned solution, and then solution poured into the rustless steel hydro-thermal of 150mL In still, after screwing hermetic in the baking oven of 160 DEG C constant temperature 12h, naturally cool to room temperature, centrifugal, use deionization Water washs, and is dried 12h in the vacuum drying oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare CaO.
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Take the 0.364g CaO and 0.21g SiO of above-mentioned preparation2It is dissolved in 50mL deionized water, above-mentioned solution is existed 50 DEG C of stirring 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two Component composite oxide catalysts CaO-SiO2。
Embodiment 9
Ethanol butadiene binary composite oxide catalysts BaO-SiO2Preparation
By 2.5g Ba (NO3)2It is dissolved in the deionized water of 100mL, stirs until completely dissolved, by 10mL second Glycol and 10mL NaOH (2mol/L) are added in above-mentioned solution, and then solution poured into the stainless steel water of 150mL In hot still, after screwing hermetic in the baking oven of 160 DEG C constant temperature 12h, naturally cool to room temperature, centrifugal, spend from Sub-water washs, and is dried 12h in the vacuum drying oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare BaO.
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Take the 1g BaO and 0.21g SiO of above-mentioned preparation2It is dissolved in 50mL deionized water, by above-mentioned solution at 50 DEG C Stirring 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two components Composite oxide catalysts BaO-SiO2。
Embodiment 10
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (mechanical agitation mixing)
By 10g C4Mg4O12·H2MgO2·XH2O is placed in Muffle furnace, roasting calcining 16h at 450 DEG C, Prepare MgO.
Take the 0.28g MgO and 0.21g SiO of above-mentioned preparation2It is placed in mortar, mechanical agitation mixing 10min, institute Solid through 500 DEG C of roasting 5h, cool down and i.e. obtain two component composite oxide catalysts MgO-SiO2。
Embodiment 11
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (co-precipitation mixing)
By 2.56g Mg (NO3)2·6H2O and 2.08g Si (OC2H5)4It is dissolved in the deionized water of 500mL, stirs Mix until completely dissolved, NaOH (2mol/L) is dropwise added drop-wise in above-mentioned mixed solution, to PH ＞ 13, holds Continuous stirring 2h, after suspension precipitation, cooling, is dried 12h in the baking oven of 100 DEG C；Forge at 500 DEG C again Burn 2h, prepare MgO-SiO2。
Embodiment 12
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (infusion process mixing)
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
By 1.28g Mg (NO3)2·6H2O is dissolved in the deionized water of 0.3ml, and stirring until completely dissolved, will Gained solution is added drop-wise to 0.2g SiO2The surface of solids, impregnates 12h, is then dried 12h in the baking oven of 100 DEG C,； At 500 DEG C, calcine 2h again, prepare MgO-SiO2。
Embodiment 13
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation (wet mixing method mixing)
By 10g C4Mg4O12·H2MgO2·XH2O is placed in Muffle furnace, roasting calcining 16h at 450 DEG C, Prepare MgO.
Take the 0.26g MgO and 0.21g SiO of above-mentioned preparation2It is dissolved in 50mL deionized water, above-mentioned solution is existed 50 DEG C of stirring 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two Component composite oxide catalysts MgO-SiO2。
Embodiment 14
Ethanol butadiene binary composite oxide catalysts ZrO2-SiO2Preparation
By 1.065g Zr (SO4)2·4H2O is dissolved in the deionized water of 36mL, and stirring until completely dissolved, adds Enter 0.18g C2H3NaO2, stirring is with ultrasonic to being completely dissolved；Then solution is poured into the rustless steel hydro-thermal of 50mL In still, after screwing hermetic in the baking oven of 200 DEG C constant temperature 6h, naturally cool to room temperature, centrifugal, use deionized water Washing, is dried 12h in the vacuum drying oven of 60 DEG C；At 600 DEG C, calcine 6h again, prepare ZrO2.By volume Mix and be sufficiently stirred for than dehydrated alcohol, deionized water and the ammonia for 25:15:3.14, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Take the 0.80g ZrO of above-mentioned preparation2With 0.21g SiO2It is dissolved in 50mL deionized water, above-mentioned solution is existed 50 DEG C of stirring 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid, through 500 DEG C of roasting 5h, cools down and i.e. obtains two Component composite oxide catalysts ZrO2-SiO2。
Embodiment 15
Ethanol butadiene binary composite oxide catalysts Co3O4-SiO2Preparation
By 2.38g CoCl2·6H2O and 1.34g Na2C2O4It is placed in agate mortar, is fully ground 30min, connect At 85 DEG C, be dried 5h, then at 400 DEG C, calcine 2h, prepare Co3O4。
Take the 1.56g Co of above-mentioned preparation3O4With 0.21g SiO2It is dissolved in 50mL deionized water, by above-mentioned solution Stirring 5h at 50 DEG C, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C of roasting 5h, and cooling is i.e. Obtain two component composite oxide catalysts Co3O4-SiO2。
Embodiment 16
Ethanol butadiene binary composite oxide catalysts Na2O-SiO2Preparation
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Being dissolved in the deionized water of 0.3ml by 0.52g NaOH, gained solution until completely dissolved, is dripped by stirring It is added to 0.2g SiO2The surface of solids, impregnates 12h, is then dried 12h in the baking oven of 100 DEG C,；Again at 500 DEG C Lower calcining 2h, prepares Na2O-SiO2。
Embodiment 17
Ethanol butadiene binary composite oxide catalysts K2O-SiO2Preparation
25ml dehydrated alcohol, 15ml deionized water and 3.14ml ammonia are mixed and are sufficiently stirred for, then by 3.75g Si(OC2H5)4Dropwise it is added drop-wise in above-mentioned mixed solution, above-mentioned solution is stirred at room temperature 4h, centrifugal, by nothing Water-ethanol washs, and is dried 12h in the baking oven of 60 DEG C；At 500 DEG C, calcine 2h again, prepare SiO2。
Being dissolved in the deionized water of 0.3ml by 0.73g KOH, gained solution until completely dissolved, is dripped by stirring To 0.2g SiO2The surface of solids, impregnates 12h, is then dried 12h in the baking oven of 100 DEG C,；Again at 500 DEG C Calcining 2h, prepares K2O-SiO2。
Embodiment 18
Ethanol butadiene binary composite oxide catalysts catalysis ethanol butadiene
The binary composite oxide catalysts that above-described embodiment prepares is screened out 40-60 mesh catalyst granules respectively, Load fixed bed reactors.Ethanol raw material is passed through in reactor reaction in a nitrogen atmosphere, in the pressure of 10 atmospheric pressure Power, the reaction temperature of 400 DEG C and 50000h-1Under gas phase space velocities, a step catalysis ethanol converts butadiene processed, Product is analyzed by online gas chromatogram.Reaction result is as shown in accompanying drawing 1,2 and 3, and Fig. 1 is embodiment 1-4 Magnesium oxide prepared by middle distinct methods is for synthesizing MgO-SiO2The ethanol fourth two of binary composite oxide catalysts The butadiene productivity figure of alkene, Fig. 2 is the different ethanol butadiene binary that embodiment 2 prepares from embodiment 5-8 The butadiene productivity figure of composite oxide catalysts, Fig. 3 is the different mixed method system that embodiment 10-13 represents The butadiene productivity figure of standby ethanol butadiene binary composite oxide catalysts.
Comparative example 1
Contrast patent US2423681 is used to prepare composite oxides MgO-SiO2, and used and embodiment 18 identical experimental techniques, test one step catalysis ethanol converts the productivity of butadiene processed, obtains its productivity and be about About 48%.
Comparative example 2
Use ZrO prepared by contrast patent US24361252、ThO2And SiO2Composite oxides, and adopted With the experimental technique identical with embodiment 18, test one step catalysis ethanol converts the productivity of butadiene processed, obtains Its productivity is about about 40%.
Embodiment 19
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Dehydrated alcohol, deionized water and ammonia are mixed and is sufficiently stirred for, then by Si (OC2H5)4Dropwise it is added drop-wise to In above-mentioned mixed solution, meet last dehydrated alcohol, ammonia, water and Si (OC2H5)4The volume ratio of interpolation be 1:0.05:0.1:0.05, is stirred at room temperature 4h by above-mentioned solution, centrifugal, with absolute ethanol washing, at 60 DEG C Baking oven in be dried 12h；At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 1:100 takes above-mentioned preparation according to the mol ratio of Mg and Si2, be dissolved in 50mL go from In sub-water, above-mentioned solution is stirred 5h at 50 DEG C, at 150 DEG C, stir 8h be afterwards extremely dried, gained solid warp 600 DEG C of roasting 2h, cool down and i.e. obtain two component composite oxide catalysts MgO-SiO2。
Embodiment 20
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Dehydrated alcohol, deionized water and ammonia are mixed and is sufficiently stirred for, then by Si (OC2H5)4Dropwise it is added drop-wise to In above-mentioned mixed solution, meet last dehydrated alcohol, ammonia, water and Si (OC2H5)4The volume ratio of interpolation be 1:1:0.5:0.4, is stirred at room temperature 4h by above-mentioned solution, centrifugal, with absolute ethanol washing, at 60 DEG C Baking oven is dried 12h；At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 100:1 takes above-mentioned preparation according to the mol ratio of Mg and Si2, be dissolved in 50mL go from In sub-water, above-mentioned solution is stirred 5h at 50 DEG C, at 120 DEG C, stir 24h be afterwards extremely dried, gained solid Through 200 DEG C of roasting 6h, cool down and i.e. obtain two component composite oxide catalysts MgO-SiO2。
Embodiment 21
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Dehydrated alcohol, deionized water and ammonia are mixed and is sufficiently stirred for, then by Si (OC2H5)4Dropwise it is added drop-wise to In above-mentioned mixed solution, meet last dehydrated alcohol, ammonia, water and Si (OC2H5)4The volume ratio of interpolation be 1:0.3:1:1, is stirred at room temperature 4h by above-mentioned solution, centrifugal, with absolute ethanol washing, at 60 DEG C Baking oven is dried 12h；At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 1:1 takes above-mentioned preparation according to the mol ratio of Mg and Si2, it is dissolved in 50mL deionization In water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 22
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Ethylene glycol, deionized water and urea liquid (5mol/L) are mixed and be sufficiently stirred for, then by positive silicic acid first Ester is dropwise added drop-wise in above-mentioned mixed solution, meets last ethylene glycol, urea liquid, water and methyl silicate The volume ratio added is 1:0.3:1:1, and above-mentioned solution is stirred at room temperature 4h, and centrifugal, spent glycol is washed Wash, the baking oven of 60 DEG C is dried 12h；At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 2:1 takes above-mentioned preparation according to the mol ratio of Mg and Si2, it is dissolved in 50mL deionization In water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 23
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Isopropanol, deionized water and sodium hydroxide solution (5mol/L) are mixed and are sufficiently stirred for, then by tetrem TMOS is dropwise added drop-wise in above-mentioned mixed solution, meets last isopropanol, sodium hydroxide solution, water and four The volume ratio of the interpolation of Ethoxysilane is 1:0.3:1:1, and above-mentioned solution is stirred at room temperature 4h, centrifugal, Wash with isopropanol, the baking oven of 60 DEG C is dried 12h；At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 1:2 takes above-mentioned preparation according to the mol ratio of Mg and Si2, it is dissolved in 50mL deionization In water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 24
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
By alcoholic solvent (ethanol mixes with ethylene glycol 1:1 by volume), deionized water and sodium hydroxide solution (5mol/L) mix and be sufficiently stirred for, then tetramethoxy-silicane being dropwise added drop-wise in above-mentioned mixed solution, full The volume ratio of the interpolation of alcoholic solvent, sodium hydroxide solution, water and tetramethoxy-silicane that foot is last is 1:0.3:1: 1, above-mentioned solution is stirred at room temperature 4h, centrifugal, wash with alcoholic solvent, the baking oven of 60 DEG C is dried 12h； At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 20:1 takes above-mentioned preparation according to the mol ratio of Mg and Si2, be dissolved in 50mL go from In sub-water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 25
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Isopropanol, deionized water and sodium hydroxide solution (5mol/L) are mixed and are sufficiently stirred for, then by silicon source (tetraethyl orthosilicate mixes with methyl silicate 1:1 in mass ratio) is dropwise added drop-wise in above-mentioned mixed solution, meets The volume ratio of the interpolation in last isopropanol, sodium hydroxide solution, water and silicon source is 1:0.3:1:1, by above-mentioned Solution is stirred at room temperature 4h, centrifugal, washs with isopropanol, is dried 12h in the baking oven of 60 DEG C；Again at 500 DEG C Lower calcining 2h, prepares SiO2。
It is MgO and SiO that 1:20 takes above-mentioned preparation according to the mol ratio of Mg and Si2, be dissolved in 50mL go from In sub-water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 26
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
Isopropanol, deionized water and sodium hydroxide solution (5mol/L) are mixed and are sufficiently stirred for, then by silicon source (tetraethyl orthosilicate, tetraethoxysilane and methyl silicate 1:1:1 in mass ratio mixing) is dropwise added drop-wise to above-mentioned In mixed solution, the volume ratio of the interpolation meeting last isopropanol, sodium hydroxide solution, water and silicon source is 1: 0.3:1:1, is stirred at room temperature 4h by above-mentioned solution, centrifugal, washs with isopropanol, in the baking oven of 60 DEG C It is dried 12h；At 500 DEG C, calcine 2h again, prepare SiO2。
It is MgO and SiO that 1:1 takes above-mentioned preparation according to the mol ratio of Mg and Si2, it is dissolved in 50mL deionization In water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 27
Ethanol butadiene binary composite oxide catalysts MgO-SiO2Preparation
32g carbamide is dissolved in the magnesium chloride brine of 5000mL (1.0mol/L), 75 DEG C of stirring in water bath 3h, It is washed with deionized, the precipitate of washes clean is placed in 90 DEG C of baking ovens and is dried 12h, then forge at 450 DEG C Burn 2h, prepare MgO.
By molten to alcoholic solvent (ethanol, isopropanol and ethylene glycol 1:1:1 by volume mixing), deionized water and carbamide Liquid (5mol/L) mixes and is sufficiently stirred for, and is then dropwise added drop-wise to by methyl silicate in above-mentioned mixed solution, full The volume ratio of the interpolation of alcoholic solvent, urea liquid, water and methyl silicate that foot is last is 1:0.3:1:1, will Above-mentioned solution is stirred at room temperature 4h, centrifugal, washs with alcoholic solvent, is dried 12h in the baking oven of 60 DEG C；Again At 500 DEG C, calcine 2h, prepare SiO2。
It is MgO and SiO that 2:1 takes above-mentioned preparation according to the mol ratio of Mg and Si2, it is dissolved in 50mL deionization In water, at 50 DEG C, above-mentioned solution being stirred 5h, at 100 DEG C, stirring is to being dried afterwards, and gained solid is through 500 DEG C Roasting 5h, cools down and i.e. obtains two component composite oxide catalysts MgO-SiO2。
Embodiment 28
Ethanol butadiene binary composite oxide catalysts catalysis ethanol butadiene
The binary composite oxide catalysts that above-described embodiment 19-23 prepares is screened out 40-60 mesh catalyst respectively Granule, loads fixed bed reactors.Ethanol raw material is passed through in reactor reaction in a nitrogen atmosphere, at 50 air The pressure of pressure, the reaction temperature of 450 DEG C and 106h-1Under gas phase space velocities, a step catalysis ethanol converts fourth two processed Alkene, product is analyzed by online gas chromatogram.Acquired results table specific as follows 1.
The productivity of the catalyst that table 1 embodiment 19-23 prepares
Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23
Productivity (%) 68 62 67 65 72
Embodiment 28
Ethanol butadiene binary composite oxide catalysts catalysis ethanol butadiene
The binary composite oxide catalysts that above-described embodiment 19-23 prepares is screened out 40-60 mesh catalyst respectively Granule, loads fixed bed reactors.Ethanol raw material is passed through in reactor reaction in a nitrogen atmosphere, at 1 atmospheric pressure Pressure, the reaction temperature of 350 DEG C and 102h-1Under gas phase space velocities, a step catalysis ethanol converts butadiene processed, Product is analyzed by online gas chromatogram.Acquired results table specific as follows 2.
The productivity of the catalyst that table 2 embodiment 24-27 prepares
Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27
Productivity (%) 64 61 59 63
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use to send out Bright.These embodiments obviously easily can be made various amendment by person skilled in the art, and at this The General Principle illustrated is applied in other embodiments without through performing creative labour.Therefore, the present invention does not limits In above-described embodiment, those skilled in the art are according to the announcement of the present invention, without departing from changing that scope is made Entering and revise all should be within protection scope of the present invention.

Claims (9)

1. an efficient bifunctional catalyst, it is characterised in that the chemical constitution formula of this catalyst is MxSiyOz, Wherein, described M is the one in Cu, Mg, Zn, Ca, Co, Zr, Ba, K or Na, x and y Being positive integer, and x:y=1:100～100:1, z is by the element valence of M, and the ratio-dependent of x, y, And ensure the charge balance of catalyst.
The efficient bifunctional catalyst of one the most according to claim 1, it is characterised in that described M is One in Zn, Cu, Ca, Mg or Ba element；
Described catalyst MxSiyOzIn, x:y=1:20～20:1.
3. the preparation method of efficiently bifunctional catalyst as claimed in claim 1 or 2, it is characterised in that bag Include following steps: weigh oxide or the hydroxide of metallic element M, with SiO2Mixing so that in mixture The mol ratio of M Yu Si is x:y, dry, roasting, i.e. obtains purpose product.
The preparation method of a kind of efficient bifunctional catalyst the most according to claim 3, it is characterised in that Described SiO2Particle diameter be 20nm-500nm.
The preparation method of a kind of efficient bifunctional catalyst the most according to claim 3, it is characterised in that The oxide of metallic element M or hydroxide and SiO2Mixed method be physical mixed method, wet mixing method, coprecipitated Shallow lake method or infusion process；
The process conditions being dried are: be dried 8～24h at 100～150 DEG C；
The process conditions of roasting are: roasting 2～6h at 200～600 DEG C.
The preparation method of a kind of efficient bifunctional catalyst the most according to claim 3, it is characterised in that Oxide or the hydroxide of metallic element M are prepared from by following steps: weigh and comprise metallic element M's Precursor salt, prepares oxide or the hydroxide of metallic element M, or continues the hydrogen of metallic element M The further roasting of oxide obtains the oxide of M；
SiO2It is prepared from by following steps: under room temperature, alcoholic solvent, catalyst and water mixing, adds silicon Source, stirs, filters, washs, after drying, obtains SiO2。
The preparation method of a kind of efficient bifunctional catalyst the most according to claim 6, it is characterised in that In the oxide of metallic element M or the preparation of hydroxide:
Precursor salt is subcarbonate, hydroxide, nitrate, sulfate, chlorate, ethylate or acetic acid One or more of salt；
The process conditions of roasting are: roasting 2～6h at 100～600 DEG C；
The method of oxide or hydroxide that precursor salt prepares metallic element M is hydro-thermal method, the sedimentation method, molten Glue-gel method or thermal decomposition method；
SiO2Preparation in:
The volume ratio of the interpolation in alcoholic solvent, catalyst, water and silicon source is 1:(0.05-1): (0.1-1): (0.05-1)；
Described alcoholic solvent be ethanol, isopropanol, ethylene glycol one or more；
Described catalyst is ammonia, urea liquid or sodium hydroxide solution；
The described one that silicon source is tetraethyl orthosilicate, methyl silicate, tetraethoxysilane, tetramethoxy-silicane Or it is multiple.
8. the efficient bifunctional catalyst as described in claims 1 to 3 is arbitrary is used for ethanol butadiene the most processed.
The application of efficient bifunctional catalyst the most according to claim 8, it is characterised in that be used for being catalyzed During ethanol butadiene the most processed, its process conditions are: the pressure of 1～50 atmospheric pressure, the temperature range of 200～600 DEG C, Gas phase air speed 102～106h-1。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106831287A (en) * 2017-01-09 2017-06-13 北京化工大学 A kind of system and method for preparing bio-based butadiene
JP2020132550A (en) * 2019-02-15 2020-08-31 株式会社ダイセル Method for producing 1,3-butadiene
CN113557085A (en) * 2019-02-13 2021-10-26 艾斯希吉化工有限公司 Process and catalyst for the production of 1, 3-butadiene from ethanol
CN114433059A (en) * 2022-01-20 2022-05-06 上海工程技术大学 CO2Catalyst for synthesizing low-carbon olefin compound by hydrogenation, preparation and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB573631A (en) * 1941-12-15 1945-11-29 Waclaw Szukiewicz Manufacture of butadiene
JP2015034151A (en) * 2013-08-09 2015-02-19 株式会社ダイセル BUTADIENE SYNTHESIS METHOD FROM ETHANOL BY METAL-ADDED SiO2-MgO CATALYST PREPARED BY HYDROTHERMAL SYNTHESIS METHOD
CN105263621A (en) * 2013-05-07 2016-01-20 西索斯公司 Process for the production of 1,3-butadiene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB573631A (en) * 1941-12-15 1945-11-29 Waclaw Szukiewicz Manufacture of butadiene
CN105263621A (en) * 2013-05-07 2016-01-20 西索斯公司 Process for the production of 1,3-butadiene
JP2015034151A (en) * 2013-08-09 2015-02-19 株式会社ダイセル BUTADIENE SYNTHESIS METHOD FROM ETHANOL BY METAL-ADDED SiO2-MgO CATALYST PREPARED BY HYDROTHERMAL SYNTHESIS METHOD

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CARLO ANGELICI ET AL.: ""Effect of Preparation Method and CuO Promotion in the Conversion of Ethanol into 1,3-Butadiene over SiO2-MgO Catalysts"", 《CHEM. SUS. CHEM.》 *
E.V. MAKSHINA ET AL.: ""Catalytic study of the conversion of ethanol into 1,3-butadiene"", 《CATALYSIS TODAY》 *
RYUICHIRO OHNISHI ET AL.: ""Pronounced Catalytic Activity and Selectivity of MgO-SiO2-Na20 for Synthesis of Buta-1,3-diene from Ethanol"", 《JOURNAL OF CHEMICAL SOCIETY,CHEMICAL COMMUNICATIONS》 *
S. KVISLE ET AL.: ""Transformation of Ethanol into 1,3-Butadiene over Magnesium Oxide/Silica Catalysts"", 《APPLIED CATALYSIS》 *
全跃等: "《镁质材料生产与应用》", 29 February 2008 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106831287A (en) * 2017-01-09 2017-06-13 北京化工大学 A kind of system and method for preparing bio-based butadiene
CN106831287B (en) * 2017-01-09 2020-07-03 北京化工大学 System and method for preparing bio-based butadiene
CN113557085A (en) * 2019-02-13 2021-10-26 艾斯希吉化工有限公司 Process and catalyst for the production of 1, 3-butadiene from ethanol
JP2020132550A (en) * 2019-02-15 2020-08-31 株式会社ダイセル Method for producing 1,3-butadiene
JP7316801B2 (en) 2019-02-15 2023-07-28 株式会社ダイセル Method for producing 1,3-butadiene
CN114433059A (en) * 2022-01-20 2022-05-06 上海工程技术大学 CO2Catalyst for synthesizing low-carbon olefin compound by hydrogenation, preparation and application thereof

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