CN110560155A - Preparation method and application of composite catalyst for directly producing propylene by bioethanol one-step method - Google Patents

Preparation method and application of composite catalyst for directly producing propylene by bioethanol one-step method Download PDF

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CN110560155A
CN110560155A CN201910877256.3A CN201910877256A CN110560155A CN 110560155 A CN110560155 A CN 110560155A CN 201910877256 A CN201910877256 A CN 201910877256A CN 110560155 A CN110560155 A CN 110560155A
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molecular sieve
catalyst
zinc
zeolite molecular
cerium
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张维萍
徐禄禄
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Dalian University of Technology
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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 preparation method and application of a metal oxide and microporous zeolite molecular sieve composite catalyst for directly producing propylene with high selectivity by a bioethanol one-step method. The invention compounds zinc cerium oxide and H-Beta molecular sieve according to a certain mass ratio to obtain the composite catalyst, and the method obtains the multifunctional catalyst with acid-alkaline sites and oxidation-reduction property. The catalyst is applied to the conversion reaction of bioethanol, the one-step direct high-selectivity production of propylene from bioethanol is realized, the preparation raw materials of the catalyst are environment-friendly, cheap and easily available, the preparation method is simple, the reaction operation process is short and easy to amplify, and the catalyst has a good application prospect.

Description

Preparation method and application of composite catalyst for directly producing propylene by bioethanol one-step method
Technical Field
The invention relates to a preparation method and application of a catalyst for directly synthesizing propylene by a bioethanol one-step method, in particular to a composite catalyst for preparing propylene with high selectivity after compounding metal oxide and a microporous zeolite molecular sieve.
Background
Propylene (Propene) is one of the most important basic organic raw materials in the petrochemical industry, and is mainly used for producing chemical products such as polypropylene, acrylonitrile, propylene oxide, isopropanol and the like. The annual demand of propylene in China is increased to 6.3%, and the current propylene production mainly comprises the technologies supported by fossil energy, such as the production of ethylene and propylene by naphtha steam cracking, the catalytic cracking of byproduct propylene, propane dehydrogenation, ethylene and 2-butene disproportionation, the preparation of olefin from synthesis gas, methanol conversion and the like. Since fossil energy is not renewable and excessive mining causes environmental deterioration. In recent years, the development of new propylene production processes has attracted much attention. Compared with fossil energy, the preparation of bulk chemical products with high added value, such as ethylene (Ethene), propylene, Isobutene (Isobutene) and the like, by conversion of renewable bioethanol (EtOH) has great advantages. The conversion of bioethanol to propylene is a sustainable non-fossil energy route, and has important practical value and strategic significance.
The conversion of ethanol to prepare propylene is divided into a multi-step method and a one-step method. 2013, a Chinese patent (CN102875309A) reported a multi-step process in which ethanol was first dehydrated over an acidic catalyst to form ethylene, which was then reacted with isomerized tetraolefins in WO3/SiO3Propylene is produced on a disproportionation catalyst. The method has long and complicated process flow, needs more than three catalysts and is not beneficial to industrial production.
In a reaction system for preparing propylene by one-step ethanol direct conversion, two paths are mainly provided, one is that under the condition of acid site catalysis, ethanol is dehydrated to generate ethylene, and the ethylene generates propylene through processes such as polymerization and splitting; secondly, under the action of an alkaline site or an oxidation site, ethanol is dehydrogenated to generate acetaldehyde (Aldehyde), then the acetaldehyde is oxidized to generate Acetic acid (Acetic acid), then ketonization is performed to generate Acetone (Acetone), the Acetone is continuously reacted to generate propylene, but the Acetone is continuously polymerized to generate a byproduct isopropylidene Acetone (mesityl oxide), and Methane (Methane) and Carbon dioxide (Carbon dioxide) are generated under a high-temperature condition. It can be seen that the acidity, basicity and redox properties of the catalyst have a great influence on both product selectivity and reaction activity. 2011 of a chinese patent (CN102274748A) reported that a composite molecular sieve catalyst composed of two or more of MOR, ZSM-5, H-Beta, SAPO-34 and other molecular sieves had an ethanol conversion rate of 100% and a propylene selectivity of 26.4% at the highest. A Chinese patent (CN107649173A) in 2017 reports modification of phosphorusThe chiral HZSM-5 molecular sieve catalyzes an ethanol reaction, the number of strong acid centers on the molecular sieve is reduced after phosphorus modification, the number of weak acid centers is increased, and the propylene selectivity is about 28 percent. In other reported catalysts in the literature, such as molecular sieves (Applied Catalysis B: Environmental,2011,107, 68-76; Fule Processing Technology,2013,108,31-40) such as ZSM-5 and SAPO-34, and metal-loaded mesoporous material MCM-41(ChemSusChem,2011,4,1055-1058), the yield of propylene is only 20-30%, and the deactivation is rapid due to the fact that the molecular sieves are high in acid content and strong in acidity and carbon is easily deposited in the reaction process. In addition, there have been few studies on the production of propylene from ethanol by the catalysis of metal oxides. Iwamoto et al reported Y/CeO2As a catalytic performance in the case of a catalyst (ACSCatalysis,2013,3,14-17), a propylene yield of 30% can be obtained; subsequently Sc/In for the subject group2O3A34% yield of propylene was obtained for the catalyst (Chemistry-A European Journal,2013,19,7214-7220) only by feeding H into the reaction gas at 550 ℃ temperature2A 60% propylene yield was obtained.
In prepared by deposition-precipitation method of Hua et al2O3HBeta catalyst (Greenchemistry,2017,19,5582-5590) giving 50% yield of propylene, but In2O3The precursor indium nitrate is expensive and has certain toxicity. Therefore, the search for an environment-friendly and cheap composite catalyst of metal oxide and microporous zeolite molecular sieve is important for preparing propylene by high-efficiency conversion of bioethanol.
Disclosure of Invention
The invention relates to a preparation method of a simple, environment-friendly and cheap metal oxide and microporous zeolite molecular sieve composite catalyst and application thereof in a reaction for preparing propylene by one-step high-selectivity conversion of bioethanol.
The invention provides a preparation method of a metal oxide and microporous zeolite molecular sieve composite catalyst for directly producing propylene in a high selectivity manner by a one-step method, which comprises the steps of preparing a required metal oxide by using metal salt as a precursor, and compounding the metal oxide and a microporous zeolite molecular sieve according to a mass ratio of 1 (0.1-5) to prepare the metal oxide-microporous zeolite molecular sieve composite catalyst, wherein the obtained composite catalyst is a multifunctional composite catalyst with acid-base sites and redox capability.
According to the technical scheme, preferably, the catalyst is a metal oxide and microporous zeolite molecular sieve composite catalyst, the metal oxide is zinc cerium oxide, and the metal salt precursor comprises a metal zinc salt precursor and a metal cerium salt precursor; the microporous zeolite molecular sieve has a CHA, MFI, FAU or BEA type molecular sieve structure and the like.
According to the above technical solution, preferably, the metal salt precursor includes a metal zinc salt precursor and a metal cerium salt precursor, the metal zinc salt precursor is zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, etc., and the metal cerium salt precursor is cerium nitrate, cerium chloride, cerium acetate, etc.
According to the technical scheme, the catalyst is preferably a composite catalyst of metal oxide and microporous zeolite molecular sieve, and the zinc cerium oxide can be prepared by a coprecipitation method, an impregnation method, a sol-gel method and the like.
According to the above technical solution, preferably, the catalyst is a composite catalyst of metal oxide and microporous zeolite molecular sieve, and the microporous zeolite molecular sieve comprises a pretreatment process of: pretreating a zeolite molecular sieve with Si/Al of 10-20 to obtain the zeolite molecular sieve with Si/Al of 30-90.
According to the technical scheme, the catalyst is preferably a composite catalyst of metal oxide and a microporous zeolite molecular sieve, and the pretreatment process of the microporous zeolite molecular sieve can be carried out by high-temperature roasting, strong acid heating treatment such as concentrated nitric acid, concentrated sulfuric acid and the like, or hydrothermal treatment and the like.
according to the technical scheme, the catalyst is preferably a composite catalyst of metal oxide and microporous zeolite molecular sieve, and the composite catalyst can be prepared by a deposition precipitation method, a sol-gel method, a mechanical mixing method and the like.
According to the above technical solution, preferably, the composite catalyst is a composite catalyst of metal oxide and microporous zeolite molecular sieve, and the preparation method of the composite catalyst comprises the following steps:
(1) Preparation of zinc cerium oxide
Dropwise adding 3-8M ammonia water into a mixed salt solution of zinc salt and cerium salt under the stirring condition until the pH value is 8-10 to obtain a mixed hydroxide suspension, stirring at 25-80 ℃ for 10-24 h, performing suction filtration and washing, drying at 80-110 ℃ for 20-24 h, and roasting at 400-600 ℃ for 5-8 h to obtain zinc cerium oxide;
Wherein the molar ratio of the metal zinc, the metal cerium and the water in the mixed salt solution is 1: (0.5-10): 6;
(2) pretreatment of microporous zeolite molecular sieves
Roasting the microporous zeolite molecular sieve with Si/Al of 10-20 at 600-700 ℃ for 10-14 h to obtain a zeolite molecular sieve, wherein the Si/Al of the pretreated microporous zeolite molecular sieve is 30-90;
(3) Preparation of composite catalyst
Mixing the zinc cerium oxide obtained in the step (1) and the microporous zeolite molecular sieve pretreated in the step (2) according to the ratio of 1: (0.1-5), grinding for 0.5-1 h, and roasting at 400-600 ℃ for 4-6 h.
According to the technical scheme, the zinc salt is preferably zinc sulfate, zinc nitrate, zinc chloride, zinc acetate and the like, and the cerium salt is preferably cerium nitrate, cerium chloride and cerium acetate.
The invention also relates to application of the metal oxide and microporous zeolite molecular sieve composite catalyst prepared by the method in the reaction for preparing propylene by one-step high-selectivity conversion of bioethanol.
According to the technical scheme, the application of the metal oxide and microporous zeolite molecular sieve composite catalyst in the reaction of preparing propylene by one-step high-selectivity conversion of bioethanol preferably also comprises a pretreatment process.
According to the technical scheme, preferably, in the pretreatment process of the metal oxide and microporous zeolite molecular sieve composite catalyst, the pretreatment atmosphere is one of nitrogen, argon or helium, the flow rate of the atmosphere is 20-50 ml/min, the pretreatment temperature is 300-500 ℃, the pretreatment time is 0.5-3 h, and the heating rate is 1-10 ℃/min.
According to the technical scheme, preferably, the metal oxide and microporous zeolite molecular sieve composite catalyst is applied to the reaction of preparing propylene through one-step high-selectivity conversion of bioethanol, water and ethanol enter a reactor simultaneously, and the molar ratio of the water to the ethanol is 0-5: 1, preferably H2O/EtOH＝0.5～3：1。
According to the technical scheme, preferably, the metal oxide and microporous zeolite molecular sieve composite catalyst is applied to the reaction of preparing propylene by one-step high-selectivity conversion of bioethanol, water and ethanol enter a reactor simultaneously, and water (H) is used2the dosage of O, ethanol (EtOH) and the composite catalyst is (0-5 mol): 1 mol: (0.05-1 g), preferably (0.5-3): 1: (0.1-0.4 g).
According to the technical scheme, preferably, the metal oxide and microporous zeolite molecular sieve composite catalyst is applied to the reaction of preparing propylene through one-step high-selectivity conversion of bioethanol, and the reaction temperature is 350-550 ℃, preferably 400-500 ℃; the ethanol partial pressure is 10 to 50KPa, preferably 20 to 40 KPa; the volume space velocity of the ethanol is 200-2000 h-1Preferably 500 to 1000 hours-1。
The application conditions of the catalyst of the invention are as follows: pretreating with 20-50 ml/min of one of nitrogen, argon or helium, wherein the pretreatment temperature is 300-500 ℃, the pretreatment time is 0.5-3 h, and the temperature programming rate is 1-10 ℃/min; molar ratio of reactants (H)2O/EtOH) is 0-5, and the reaction temperature is 350-550 ℃; the partial pressure of the ethanol is 10-50 KPa; the volume space velocity of the ethanol is 200-2000 h-1。
The invention has the following advantages:
From the catalyst preparation aspect: the composite catalyst has the advantages of environment-friendly preparation raw materials, low price and easy obtainment, simple preparation method, easy operation, easy amplification and good application prospect.
In the aspect of the reaction for preparing propylene by converting bioethanol: the composite catalyst can directly synthesize propylene by one-step method, has short reaction flow, has propylene selectivity as high as more than 50 percent, and has good stability.
Drawings
FIG. 1 is an XRD spectrum of a composite catalyst with different mass ratios of zinc cerium oxide and zeolite molecular sieve.
FIG. 2 shows the effect of different mass ratios of zinc cerium oxide and zeolite molecular sieve on the reaction performance.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Examples
As described in detail below with respect to the whole process by way of examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
1. preparation of zinc cerium oxide and zeolite molecular sieve composite catalyst
Example 1
Take 0.5gZn (NO)3)、3.6gCe(NO3)2Adding into a container containing 100ml of water, adjusting the pH value of the mixed aqueous solution with 6mol/l of ammonia water under the stirring condition, stabilizing the pH value to 9 to obtain a mixed hydroxide suspension, and stirring for 24 hours at room temperature. And filtering and washing the mixed hydroxide suspension, drying at 110 ℃ for 24h, and roasting in a muffle furnace at 500 ℃ for 6h to obtain the metal oxide catalyst. The prepared metal oxide catalyst is Zn1Ce5O2XRD of the crystal is shown in FIG. 1, which shows that ZnO is dispersed in CeO more uniformly2The above.
Example 2
The Si/Al ═ 18H-Beta (18) molecular sieve (BEA structure, available from catalyst works at southern kayak university) was calcined in a muffle furnace at 650 ℃ for 10H to give Si/Al ═ 43 molecular sieve H-Beta (43) whose XRD is shown in fig. 1, indicating that the H-Beta molecular sieve after high temperature calcination still retained its characteristic diffraction peak.
example 3
1g of Zn prepared in example 1 above was taken1Ce5O2And 0.05g of the H-Beta (43) molecular sieve prepared in the example 2 are mechanically and uniformly mixed, the mixture is ground for 0.5 to 1 hour and then roasted for 6 hours at 500 ℃ to obtain a catalyst, and the prepared metal oxide and molecular sieve composite catalyst is H-Beta (43) -Zn1Ce5O2(0.5:10) and XRD thereof is shown in FIG. 1, indicating that H-Beta (43) is uniformly dispersed in the oxide Zn1Ce5O2The above.
Example 4
1g of Zn prepared in example 1 above was taken1Ce5O2And 0.1g of the H-Beta (43) molecular sieve prepared in the above example 2, and the mixture is mechanically mixed uniformly, ground for 0.5 to 1 hour, and then roasted for 6 hours at 500 ℃ to obtain the metal oxide and molecular sieve composite catalyst, wherein the prepared metal oxide and molecular sieve composite catalyst is H-Beta (43) -Zn1Ce5O2(1:10) (wherein 1:10 is H-Beta (43) molecular sieve and Zn1Ce5O2Mass ratio of (b), the XRD thereof is shown in FIG. 1, indicating that H-Beta (43) is uniformly dispersed in the oxide Zn1Ce5O2The above.
Example 5
1g of Zn prepared in example 1 above was taken1Ce5O2And 0.2g of the H-Beta (43) molecular sieve prepared in the above example 2, and the mixture is mechanically mixed uniformly, ground for 0.5 to 1 hour, and then roasted for 6 hours at 500 ℃ to obtain the metal oxide and molecular sieve composite catalyst, wherein the prepared metal oxide and molecular sieve composite catalyst is H-Beta (43) -Zn1Ce5O2(2:10) (wherein 2:10 is H-Beta (43) molecular sieve and Zn1Ce5O2Mass ratio of (b), the XRD thereof is shown in FIG. 1, indicating that H-Beta (43) is uniformly dispersed in the oxide Zn1Ce5O2The above.
Example 6
1g of Zn prepared in example 1 above was taken1Ce5O2And 0.3g of the H-Beta (43) molecular sieve prepared in example 2 above were mechanically mixed well and groundRoasting for 6 hours at 500 ℃ after 0.5-1 hour to obtain the metal oxide and molecular sieve composite catalyst, wherein the prepared metal oxide and molecular sieve composite catalyst is H-Beta (43) -Zn1Ce5O2(3:10) (wherein 3:10 is H-Beta (43) molecular sieve and Zn1Ce5O2Mass ratio of (b), the XRD thereof is shown in FIG. 1, indicating that H-Beta (43) is uniformly dispersed in the oxide Zn1Ce5O2The above.
2. Application of zinc cerium oxide and zeolite molecular sieve composite catalyst in reaction for preparing propylene by directly converting bioethanol by one-step method
All reaction examples were carried out in a continuous flow fixed bed reaction apparatus equipped with a gas mass flow meter and an on-line product analysis chromatograph. On-line product analysis using Shimadzu GC-2014C gas chromatography, a ten-way valve sampling was used to achieve full product analysis, with the FID detector analyzing hydrocarbons and oxygenates; TCD detector for analyzing CO and CO2And the like.
Example 7
Catalyst Zn in example 11Ce5O2The catalytic evaluation test of (2) was carried out in a continuous flow fixed bed reaction apparatus under the following specific reaction conditions: the catalyst dosage is 0.2g, before reaction, the catalyst is firstly purged and activated for 1h in nitrogen atmosphere of 30ml/min at 460 ℃ for pretreatment, and the heating rate is 5 ℃/min. The application of the pretreated catalyst in the reaction for preparing propylene by a bioethanol one-step method is realized, the reaction temperature is 460 ℃, and the ethanol volume space velocity is 700h-1The ethanol partial pressure is 35KPa, the reaction gas is the mixture of ethanol and water with the molar ratio of 1:2.5, and the total flow rate is 13.5 ml/min. The reaction results are shown in FIG. 2.
Example 8
The catalytic evaluation experiment of the catalyst H-Beta (43) in example 2 was carried out in a continuous flow fixed bed reaction apparatus under the following specific reaction conditions: the catalyst dosage is 0.1g, before reaction, the catalyst is firstly purged and activated for 1h in nitrogen atmosphere of 30ml/min at 460 ℃ for pretreatment, and the heating rate is 5 ℃/min. After the catalyst is pretreated, the catalyst is applied to the reaction for preparing propylene by an ethanol one-step method, and the reaction is carried outThe temperature is 460 ℃, and the volume space velocity of the ethanol is 700h-1The ethanol partial pressure is 35KPa, the reaction gas is the mixture of ethanol and water with the molar ratio of 1:2.5, and the total flow rate is 13.5 ml/min. The reaction results are shown in FIG. 2.
Example 9
Catalyst HBeta (43) -Zn in example 31Ce5O2The catalytic evaluation experiment (0.5:10) was carried out in a continuous flow fixed bed reaction apparatus under the following specific reaction conditions: the catalyst dosage is 0.2g, before reaction, the catalyst is firstly purged and activated for 1h in nitrogen atmosphere of 30ml/min at 460 ℃ for pretreatment, and the heating rate is 5 ℃/min. After the catalyst is pretreated, the catalyst is applied to the reaction for preparing propylene by an ethanol one-step method, the reaction temperature is 460 ℃, and the volume space velocity of the ethanol is 700h-1the ethanol partial pressure is 35KPa, the reaction gas is the mixture of ethanol and water with the molar ratio of 1:2.5, and the total flow rate is 13.5 ml/min. The reaction results are shown in FIG. 2.
example 10
Catalyst HBeta (43) -Zn in example 41Ce5O2The catalytic evaluation experiment (1:10) was carried out in a continuous flow fixed bed reaction apparatus under the following specific reaction conditions: the catalyst dosage is 0.2g, before reaction, the catalyst is firstly purged and activated for 1h in nitrogen atmosphere of 30ml/min at 460 ℃ for pretreatment, and the heating rate is 5 ℃/min. After the catalyst is pretreated, the catalyst is applied to the reaction for preparing propylene by an ethanol one-step method, the reaction temperature is 460 ℃, and the volume space velocity of the ethanol is 700h-1The ethanol partial pressure is 35KPa, the reaction gas is the mixture of ethanol and water with the molar ratio of 1:2.5, and the total flow rate is 13.5 ml/min. The reaction results are shown in FIG. 2.
Example 11
catalyst HBeta (43) -Zn in example 51Ce5O2The catalytic evaluation test (2:10) was carried out in a continuous flow fixed bed reaction apparatus under the following specific reaction conditions: the catalyst dosage is 0.2g, before reaction, the catalyst is firstly purged and activated for 1h in nitrogen atmosphere of 30ml/min at 460 ℃ for pretreatment, and the heating rate is 5 ℃/min. After the catalyst is pretreated, the catalyst is applied to the reaction for preparing propylene by an ethanol one-step method, the reaction temperature is 460 ℃,The volume space velocity of the ethanol is 700h-1the ethanol partial pressure is 35KPa, the reaction gas is the mixture of ethanol and water with the molar ratio of 1:2.5, and the total flow rate is 13.5 ml/min. The reaction results are shown in FIG. 2.
Example 12
Catalyst HBeta (43) -Zn in example 61Ce5O2The catalytic evaluation test (3:10) was carried out in a continuous flow fixed bed reaction apparatus under the following specific reaction conditions: the catalyst dosage is 0.2g, before reaction, the catalyst is firstly purged and activated for 1h in nitrogen atmosphere of 30ml/min at 460 ℃ for pretreatment, and the heating rate is 5 ℃/min. After the catalyst is pretreated, the catalyst is applied to the reaction for preparing propylene by an ethanol one-step method, the reaction temperature is 460 ℃, and the volume space velocity of the ethanol is 700h-1The ethanol partial pressure is 35KPa, the reaction gas is the mixture of ethanol and water with the molar ratio of 1:2.5, and the total flow rate is 13.5 ml/min. The reaction results are shown in FIG. 2.
As can be seen from FIG. 2, the best catalyst HBeta (43) -Zn is obtained after 10h of reaction1Ce5O2(1:10) the excellent catalytic performance of 100% ethanol conversion and 53% propylene selectivity is achieved. The raw materials required by the catalyst preparation are environment-friendly, cheap and easily available, the preparation method is simple and convenient, the catalytic performance is excellent, in addition, the reactant ethanol source is renewable biomass, the catalyst is expected to replace a petroleum route one-step method to produce a large amount of chemical propylene, and the process has a good application prospect.

Claims (10)

1. A preparation method of a metal oxide and microporous zeolite molecular sieve composite catalyst for producing propylene is characterized by preparing a metal oxide by using metal salt as a precursor, and compounding the metal oxide and a microporous zeolite molecular sieve according to a mass ratio of 1: 0.1-5 to prepare the metal oxide-microporous zeolite molecular sieve composite catalyst.
2. The method according to claim 1, wherein the metal oxide is zinc cerium oxide, and the metal salt precursor comprises a metal zinc salt precursor and a metal cerium salt precursor; the microporous zeolite molecular sieve has a CHA, MFI, FAU or BEA type molecular sieve structure.
3. The method according to claim 1, wherein the metal zinc salt precursor is zinc sulfate, zinc nitrate, zinc chloride or zinc acetate, and the metal cerium salt precursor is cerium nitrate, cerium chloride or cerium acetate.
4. The method according to claim 1, wherein the zinc cerium oxide is prepared by a coprecipitation method, an impregnation method, or a sol-gel method.
5. The method of claim 1, wherein the microporous zeolitic molecular sieve comprises a pretreatment process comprising: calcination, strong acid heat treatment, or hydrothermal treatment.
6. The method according to claim 1, wherein the composite catalyst is prepared by a mechanical mixing method, a precipitation-deposition method, or a sol-gel method.
7. The preparation method of claim 1, wherein the preparation method of the composite catalyst comprises the following steps:
(1) Preparation of zinc cerium oxide
Dropwise adding 3-8M ammonia water into a mixed salt solution of zinc salt and cerium salt under the stirring condition until the pH value is 8-10 to obtain a mixed hydroxide suspension, stirring at 25-80 ℃ for 10-24 h, performing suction filtration and washing, drying at 80-110 ℃ for 20-24 h, and roasting at 400-600 ℃ for 5-8 h to obtain zinc cerium oxide;
Wherein the molar ratio of the metal zinc, the metal cerium and the water in the mixed salt solution is 1: 0.5-10: 6;
(2) Pretreatment of microporous zeolite molecular sieves
Roasting the microporous zeolite molecular sieve with Si/Al of 10-20 at 600-700 ℃ for 10-14 h to obtain a pretreated microporous zeolite molecular sieve, wherein the Si/Al of the pretreated microporous zeolite molecular sieve is 30-90;
(3) Preparation of composite catalyst
Mixing the zinc cerium oxide obtained in the step (1) and the microporous zeolite molecular sieve pretreated in the step (2) according to the ratio of 1: (0.1-5), grinding for 0.5-1 h, and roasting at 400-600 ℃ for 4-6 h.
8. The use of the metal oxide and microporous zeolite molecular sieve composite catalyst as claimed in claim 1 in the reaction of producing propylene directly from bioethanol by one-step process.
9. The use of claim 8, wherein ethanol and water enter the reactor simultaneously, wherein the molar ratio of water to ethanol is 0 to 5: 1; the reaction temperature is 350-550 ℃, the ethanol partial pressure is 10-50 KPa, and the ethanol volume space velocity is 200-2000 h-1。
10. The application of claim 8, wherein the catalyst further comprises a pretreatment process, the pretreatment atmosphere is one of nitrogen, argon or helium, the flow rate of the atmosphere is 20-50 ml/min, the pretreatment temperature is 300-500 ℃, the pretreatment time is 0.5-3 h, and the temperature rise rate is 1-10 ℃/min.
CN201910877256.3A 2019-09-17 2019-09-17 Preparation method and application of composite catalyst for directly producing propylene by bioethanol one-step method Pending CN110560155A (en)

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