CN110575828A - Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof - Google Patents
Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof Download PDFInfo
- Publication number
- CN110575828A CN110575828A CN201810586233.2A CN201810586233A CN110575828A CN 110575828 A CN110575828 A CN 110575828A CN 201810586233 A CN201810586233 A CN 201810586233A CN 110575828 A CN110575828 A CN 110575828A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ethanol
- nitrate
- acetaldehyde
- butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
- B01J21/08—Silica
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/14—Silica and magnesia
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- 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
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2076—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)- moiety is eliminated
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/14—Silica and magnesia
-
- 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
-
- 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
- C07C2523/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
Abstract
The application discloses a catalyst for producing 1, 3-butadiene by reacting ethanol and acetaldehyde, which comprises a carrier containing silicon dioxide and an active component loaded on the carrier and containing zirconium dioxide; the active component is loaded on the carrier by impregnation of a precursor of the active component. The catalyst shows excellent activity, selectivity and stability in the reaction of synthesizing 1, 3-butadiene from ethanol and acetaldehyde. The catalyst provided by the invention overcomes the defects of low efficiency, rapid inactivation and high production cost of the existing catalyst, and has the advantages of simple preparation process, cheap and easily-obtained raw materials, and large-scale industrial production.
Description
Technical Field
The application relates to a high-efficiency catalyst and a preparation method thereof, which can be used for catalyzing ethanol and acetaldehyde to react and synthesize 1, 3-butadiene and belongs to the field of catalytic synthesis.
background
1, 3-butadiene is an important organic chemical raw material and has very wide application, and the production mainly depends on a petroleum refining process. With the increasing exhaustion of petroleum resources, it is of great importance to find other raw material resources or develop new production paths.
Ethanol can be converted to 1, 3-butadiene over a suitable catalyst. In recent years, the yield of ethanol produced by a biological fermentation process is gradually increased, and in addition, the successful research and development of a coal-to-ethanol technology can further improve the production capacity of ethanol. Therefore, the ethanol is used for replacing the traditional petroleum route to produce high-value olefin, and the method has practical significance.
The process of converting ethanol into 1, 3-butadiene may be divided into a one-step process and a two-step process according to the difference of catalysts and reaction processes. Compared with a one-step method, the butadiene selectivity of the two-step method is high, the catalyst is long in stabilization time, and the method has industrial application value. The reaction of ethanol/acetaldehyde to produce 1, 3-butadiene is the core process of the two-step process, and the development of a high-efficiency catalyst is the key to the smooth proceeding of the reaction and is the focus of research. The cost of raw materials of the early tantalum oxide/silicon dioxide industrialized catalyst is high, and the economical efficiency is difficult to guarantee (US 2421361). Whereas the classical magnesia/silica catalysts which work better for the one-step process have a less than ideal catalytic effect for this reaction (ACS sustamable chem. eng.2017,5,722). Research shows that the zirconium oxide/silicon oxide catalyst also has good catalytic performance in the reaction of synthesizing 1, 3-butadiene from ethanol/acetaldehyde, and has cost advantage compared with a tantalum oxide catalyst, thereby attracting the attention of researchers. However, the existing catalyst uses ethyl silicate as a silicon source, the preparation cost is still high, and a large amount of nitric acid is needed in the process of preparing the catalyst by adopting a sol-gel method, so that the catalyst has obvious influence on equipment and environment (RSC adv, 2015,5, 103982). Therefore, the synthesis of highly efficient zirconia/silica catalysts by mild preparation methods using cheaper synthesis raw materials is an important goal to be achieved by researchers in the field.
Disclosure of Invention
In accordance with one aspect of the present application, a catalyst for the reaction of ethanol and acetaldehyde to form 1, 3-butadiene is provided. The catalyst shows excellent activity, selectivity and stability in the reaction of synthesizing 1, 3-butadiene from ethanol and acetaldehyde. The catalyst provided by the invention overcomes the defects of low efficiency, rapid inactivation and high production cost of the existing catalyst, and has the advantages of simple preparation process, cheap and easily-obtained raw materials, and large-scale industrial production.
The catalyst for producing 1, 3-butadiene by the reaction of ethanol and acetaldehyde is characterized by comprising a carrier containing silicon dioxide and an active component loaded on the carrier and containing zirconium dioxide; the active component is loaded on the carrier by impregnation of a precursor of the active component.
Optionally, the content of the zirconium dioxide in the catalyst is 1-10 wt%.
Optionally, the upper limit of the amount of zirconium dioxide in the catalyst is selected from 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt% or 5 wt%; the lower limit is selected from 4 wt%, 3 wt%, 2 wt% or 1 wt%.
Optionally, the content of the zirconium dioxide in the catalyst is 2-5 wt%.
optionally, the silica is porous silica.
Optionally, the porous silica is selected from at least one of coarse silica gel, fine silica gel, beer silica gel, mesoporous silica, pure silicalite, and titanium silicalite.
Optionally, the catalyst active component further comprises an auxiliary agent containing a metal oxide; the content of the auxiliary agent in the catalyst is 0.2-0.8 wt%.
Optionally, the upper limit of the content of the promoter in the catalyst is selected from 0.8 wt%,
Optionally, the metal oxide is selected from at least one of copper oxide, zinc oxide, chromium oxide, magnesium oxide, and silver oxide.
As an embodiment, the catalyst is applied to a two-step method for preparing 1, 3-butadiene catalytic reaction; is used for catalyzing the reaction of ethanol and acetaldehyde to generate 1, 3-butadiene.
in one embodiment, the catalyst is an acid-base bifunctional catalyst.
As an embodiment, the ethanol and the acetaldehyde react to generate the 1, 3-butadiene catalyst, zirconium dioxide is used as a main active component, other metal oxides can be doped to be used as an auxiliary agent, and porous silicon dioxide is used as a carrier;
Wherein the mass content of the zirconium dioxide in the catalyst is 1-10%.
Optionally, the content of the zirconium dioxide in the catalyst is 2% to 5% by mass.
Optionally, the auxiliary agent is one or more of copper, zinc, chromium, magnesium and silver metal oxides, and the mass content of the auxiliary agent in the catalyst is 0-1%.
Optionally, the mass content of the auxiliary agent in the catalyst is 0.2-0.8%.
the porous silica is coarse silica gel, fine silica gel, beer silica gel, mesoporous silica, pure silicalite, or titanium silicalite.
According to one aspect of the application, the method for preparing the catalyst is provided, the catalyst prepared by the impregnation method is stable in performance and high in catalysis efficiency, and large-scale industrial production can be realized.
The method comprises the following steps:
a) obtaining a solution containing a zirconium dioxide precursor;
b) Adding a carrier into the solution obtained in the step a), reacting to obtain a solid product, and drying and roasting to obtain the catalyst.
Alternatively, step a) is to obtain a solution containing zirconium dioxide and the promoter precursor.
Optionally, the auxiliary agent precursor is selected from at least one of nitrate of copper, nitrate of zinc, nitrate of chromium, nitrate of magnesium and nitrate of silver.
Optionally, the zirconia precursor in step a) is selected from at least one of zirconium nitrate, zirconyl nitrate, zirconium chloride, and zirconium oxychloride.
Alternatively, the reaction in step b) is carried out under conditions such that the solution is stirred at a temperature below 90 ℃ until it is evaporated to dryness.
Optionally, the reaction in step b) is carried out under the conditions of stirring for 2-30 hours at a temperature lower than 50 ℃, and then stirring is carried out at 50-90 ℃ until the solution is evaporated to dryness.
Optionally, the upper limit of the temperature of the reaction below 50 ℃ in step b) is selected from 50 ℃, 40 ℃, 30 ℃, 35 ℃, 30 ℃ or 25 ℃; the lower limit is selected from 20 deg.C, 15 deg.C, 10 deg.C, 5 deg.C or 0 deg.C.
Optionally, the reaction in step b) is at room temperature below 50 ℃.
Optionally, the upper limit of stirring for 2 to 30 hours in step b) is selected from 30 hours, 28 hours, 26 hours, 24 hours, 20 hours, 18 hours, 16 hours, 14 hours or 12 hours; the lower limit is selected from 12 hours, 10 hours, 8 hours, 6 hours, 4 hours, or 2 hours.
Optionally, the stirring at 50-90 ℃ in the step b) is carried out until the upper limit of 50-90 ℃ in the evaporation of the solution to dryness is selected from 90 ℃, 85 ℃, 80 ℃, 75 ℃ or 70 ℃; the lower limit is selected from 70 deg.C, 65 deg.C, 60 deg.C, 55 deg.C or 50 deg.C.
Optionally, the solvent of the solution in step a) is water and/or ethanol.
As an embodiment, the method for preparing the above catalyst is performed by using an impregnation method through the following steps:
a) Dissolving precursors of zirconium dioxide and an auxiliary agent in a solvent;
b) Adding the carrier into a zirconium dioxide precursor solution, stirring for 2-30 hours at the temperature lower than 50 ℃, and then continuously stirring at the temperature of 50-90 ℃ until the solution is evaporated to dryness;
c) And further drying and roasting the obtained solid to obtain the catalyst.
Optionally, the zirconia precursor is zirconium nitrate, zirconyl nitrate, zirconium chloride, and zirconium oxychloride.
Optionally, the precursor of the auxiliary agent is nitrate of copper, zinc, chromium, magnesium and silver.
optionally, the solvent is water, ethanol or a mixture of the two.
In the application, "room temperature" means 20 to 30 ℃.
According to another aspect of the application, a method for producing 1, 3-butadiene by reacting ethanol and acetaldehyde is provided, wherein in the presence of a catalyst, a raw material containing ethanol and acetaldehyde is introduced into a reactor and reacts at 300-500 ℃ for 2-4 h to obtain the 1, 3-butadiene;
The catalyst is selected from at least one of the catalysts described above, and catalysts prepared according to the methods described above.
Optionally, the molar ratio of ethanol to acetaldehyde in the raw material is 2-3: 1.
Optionally, the reactor is at least one fixed bed reactor.
the beneficial effects that this application can produce include:
1) The application provides a high-efficiency catalyst for catalyzing ethanol and acetaldehyde to react and synthesize 1, 3-butadiene, and the catalyst is simple in composition and low in price and easy to obtain raw materials.
2) The application provides a preparation method of the catalyst, which is simple in preparation process, strong in operability and capable of carrying out large-scale industrial production.
drawings
FIG. 1 is a graph showing the catalytic effect of the sample prepared in example 1 of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and solvents in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
EXAMPLE 1 preparation of the catalyst
dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, and evaporating the obtained powder at 650 ℃ in airCalcination in an atmosphere for 6h gave a zirconia/silica catalyst, noted as sample 1#。
EXAMPLE 2 preparation of the catalyst
Dissolving 0.375g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.8g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder in air atmosphere at 650 ℃ for 6h to obtain a zirconia/silica catalyst, and recording as a sample 2#。
EXAMPLE 3 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate in 20mL of deionized water, adding 1.96g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, which is recorded as sample 3#。
EXAMPLE 4 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of fine-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, and recording as sample 4#。
EXAMPLE 5 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of beer silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, and recording as a sample 5#。
EXAMPLE 6 preparation of the catalyst
dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of mesoporous silica powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, and recording as a sample 6#。
EXAMPLE 7 preparation of the catalyst
0.075g of zirconyl nitrate was dissolved in 20mL of absolute ethanolIn (1.96) g of pure silicalite powder was added, stirred at room temperature for 12h, then stirred continuously at 60 ℃ until the solution evaporated to dryness, and the resulting powder was calcined at 650 ℃ in an air atmosphere for 6h to give the zirconia/silica catalyst, noted as sample 7#。
EXAMPLE 8 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of titanium silicalite molecular sieve powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, and marking as a sample 8#。
EXAMPLE 9 preparation of the catalyst
Dissolving 0.105g of zirconium oxychloride in 20mL of absolute ethanol, adding 1.96g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in air atmosphere for 6h to obtain a zirconium oxide/silicon dioxide catalyst, and recording as a sample 9#。
EXAMPLE 10 preparation of catalyst
dissolving 0.075g of zirconyl nitrate and 0.036g of zinc nitrate hexahydrate in 20mL of absolute ethanol, adding 1.95g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconium oxide/silicon dioxide catalyst, which is marked as sample 10#。
EXAMPLE 11 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate and 0.031g of copper nitrate trihydrate in 20mL of anhydrous ethanol, adding 1.95g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconium oxide/silicon dioxide catalyst, which is marked as sample 11#。
EXAMPLE 12 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate and 0.064g of magnesium nitrate hexahydrate in 20mL of anhydrous ethanol, adding 1.95g of coarse-pore silica gel powder, stirring at room temperature for 12h, then continuously stirring at 60 ℃ until the solution is evaporated to dryness, and roasting the obtained powder at 650 ℃ in an air atmosphereAfter 6h, a zirconia/silica catalyst was obtained, designated as sample 12#。
EXAMPLE 13 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of coarse-pore silica gel powder, stirring at room temperature for 2h, then continuously stirring at 90 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, and marking as a sample 13#。
EXAMPLE 14 preparation of the catalyst
Dissolving 0.075g of zirconyl nitrate in 20mL of absolute ethanol, adding 1.96g of coarse-pore silica gel powder, stirring at room temperature for 30h, then continuously stirring at 50 ℃ until the solution is evaporated to dryness, roasting the obtained powder at 650 ℃ in an air atmosphere for 6h to obtain a zirconia/silica catalyst, which is recorded as sample 14#。
EXAMPLE 15 use of the catalyst
Taking 0.35g of sample 1 which is pressed into tablets and sieved by a 20-40 mesh sieve#The mixture is put into a fixed bed reactor, pretreated for 60min at 450 ℃ in nitrogen atmosphere, then the temperature is reduced to 350 ℃, raw materials of ethanol and acetaldehyde (the molar ratio of ethanol to acetaldehyde is 2.5/1) are introduced to start reaction, the flow rate of the raw materials is 0.012mL/min, the flow rate of nitrogen is 20mL/min, and analysis is carried out after 30min of reaction.
Product analysis was performed on-line using Agilent gas chromatography 7890, FID detector, HP-PLOT Q capillary column.
The reaction results are shown in FIG. 1. Results of reaction for 3 h: ethanol/acetaldehyde conversion was 51% and 1, 3-butadiene selectivity was 72%.
EXAMPLE 16 use of the catalyst
Taking 0.35g of sample 6 which is pressed into tablets and sieved by a 20-40 mesh sieve#The mixture is put into a fixed bed reactor, pretreated for 60min at 450 ℃ in nitrogen atmosphere, then the temperature is reduced to 350 ℃, raw materials of ethanol and acetaldehyde (the molar ratio of ethanol to acetaldehyde is 2.5/1) are introduced to start reaction, the flow rate of the raw materials is 0.012mL/min, the flow rate of nitrogen is 20mL/min, and analysis is carried out after 30min of reaction.
Product analysis was performed on-line using Agilent gas chromatography 7890, FID detector, HP-PLOT Q capillary column.
Results of reaction for 3 h: the ethanol/acetaldehyde conversion was 56% and the 1, 3-butadiene selectivity was 73.4%.
EXAMPLE 17 use of the catalyst
Taking 0.35g of sample 11 which is pressed into tablets and sieved by a 20-40 mesh sieve#The mixture is put into a fixed bed reactor, pretreated for 60min at 450 ℃ in nitrogen atmosphere, then the temperature is reduced to 350 ℃, raw materials of ethanol and acetaldehyde (the molar ratio of ethanol to acetaldehyde is 2.5/1) are introduced to start reaction, the flow rate of the raw materials is 0.012mL/min, the flow rate of nitrogen is 20mL/min, and analysis is carried out after 30min of reaction.
Product analysis was performed on-line using Agilent gas chromatography 7890, FID detector, HP-PLOT Q capillary column.
Results of reaction for 3 h: ethanol and acetaldehyde conversion was 51%, and 1, 3-butadiene selectivity was 66%.
The reaction results of the other samples were tested, and the reaction results of 3 hours were compared with those of sample 11#Similarly.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A catalyst for producing 1, 3-butadiene by reacting ethanol and acetaldehyde is characterized by comprising a carrier containing silicon dioxide and an active component containing zirconium dioxide loaded on the carrier; the active component is loaded on the carrier by impregnation of a precursor of the active component.
2. The catalyst according to claim 1, wherein the zirconia is present in the catalyst in an amount of 1 to 10 wt.%;
Preferably, the content of the zirconium dioxide in the catalyst is 2-5 wt%;
Preferably, the silica is porous silica;
preferably, the porous silica is selected from at least one of coarse silica gel, fine silica gel, beer silica gel, mesoporous silica, pure silicalite, and titanium silicalite.
3. The catalyst according to claim 1, wherein the catalytically active component further comprises a promoter comprising a metal oxide; the content of the auxiliary agent in the catalyst is 0-1 wt%;
Preferably, the content of the auxiliary agent in the catalyst is 0.2-0.8 wt%;
preferably, the metal oxide is selected from at least one of copper oxide, zinc oxide, chromium oxide, magnesium oxide, and silver oxide.
4. A process for preparing the catalyst of any one of claims 1 to 3, comprising the steps of:
a) Obtaining a solution containing a zirconium dioxide precursor;
b) Adding a carrier into the solution obtained in the step a), reacting to obtain a solid product, and drying and roasting to obtain the catalyst.
5. The method according to claim 4, wherein step a) is carried out to obtain a solution containing zirconium dioxide and a precursor of the auxiliary agent;
Preferably, the auxiliary agent precursor is selected from at least one of nitrate of copper, nitrate of zinc, nitrate of chromium, nitrate of magnesium and nitrate of silver.
6. The method according to claim 4, wherein the zirconia precursor in step a) is selected from at least one of zirconium nitrate, zirconyl nitrate, zirconium chloride and zirconium oxychloride.
7. the method of claim 4, wherein the reaction in step b) is carried out under conditions of stirring at a temperature below 90 ℃ until the solution is evaporated to dryness.
8. The method according to claim 4, wherein the reaction in step b) is carried out under the conditions of stirring at a temperature lower than 50 ℃ for 2-30 hours and then stirring at 50-90 ℃ until the solution is evaporated to dryness.
9. The method according to claim 4, wherein the solvent of the solution in step a) is water and/or ethanol.
10. A method for generating 1, 3-butadiene through the reaction of ethanol and acetaldehyde is characterized in that under the condition of existence of a catalyst, raw materials containing ethanol and acetaldehyde are introduced into a reactor and react for 2-4 hours at the temperature of 300-500 ℃ to obtain the 1, 3-butadiene;
The catalyst is selected from at least one of the catalyst of any one of claims 1 to 3, the catalyst prepared according to the process of any one of claims 4 to 9;
Preferably, the reactor is at least one fixed bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810586233.2A CN110575828A (en) | 2018-06-08 | 2018-06-08 | Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810586233.2A CN110575828A (en) | 2018-06-08 | 2018-06-08 | Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110575828A true CN110575828A (en) | 2019-12-17 |
Family
ID=68809033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810586233.2A Pending CN110575828A (en) | 2018-06-08 | 2018-06-08 | Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110575828A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842905A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Carrier and catalyst, and preparation method and application thereof |
| CN114452997A (en) * | 2022-01-25 | 2022-05-10 | 浙江工业大学 | Nitrogen-doped supported oxide catalyst and preparation method and application thereof |
| CN114618464A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Mesoporous catalyst and preparation method thereof, and application of mesoporous catalyst in reaction of ethanol and acetaldehyde to generate 1, 3-butadiene |
| CN115364844A (en) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | Regenerated deoxidation catalyst and preparation method and application thereof |
| US11642657B2 (en) | 2021-09-13 | 2023-05-09 | Petróleo Brasileiro S.A.—Petrobras | Method for preparing a catalyst for one-step production of butadiene from ethanol, catalyst and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110117953A (en) * | 2010-04-22 | 2011-10-28 | 금호석유화학 주식회사 | Nano-silica based catalysts for the production of 1,3-butadiene and production method of 1,3-butadiene thereof |
| CN105073689A (en) * | 2013-03-27 | 2015-11-18 | 旭化成化学株式会社 | Butadiene production method |
| CN105263621A (en) * | 2013-05-07 | 2016-01-20 | 西索斯公司 | Process for the production of 1,3-butadiene |
| CN106861752A (en) * | 2017-01-09 | 2017-06-20 | 北京化工大学 | Solid catalyst and its preparation and application for ethanol synthesis butadiene |
| US20170349503A1 (en) * | 2016-06-07 | 2017-12-07 | Fina Technology, Inc. | Metal oxide catalyst systems for conversion of ethanol to butadiene |
-
2018
- 2018-06-08 CN CN201810586233.2A patent/CN110575828A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110117953A (en) * | 2010-04-22 | 2011-10-28 | 금호석유화학 주식회사 | Nano-silica based catalysts for the production of 1,3-butadiene and production method of 1,3-butadiene thereof |
| CN105073689A (en) * | 2013-03-27 | 2015-11-18 | 旭化成化学株式会社 | Butadiene production method |
| CN105263621A (en) * | 2013-05-07 | 2016-01-20 | 西索斯公司 | Process for the production of 1,3-butadiene |
| US20170349503A1 (en) * | 2016-06-07 | 2017-12-07 | Fina Technology, Inc. | Metal oxide catalyst systems for conversion of ethanol to butadiene |
| CN106861752A (en) * | 2017-01-09 | 2017-06-20 | 北京化工大学 | Solid catalyst and its preparation and application for ethanol synthesis butadiene |
Non-Patent Citations (3)
| Title |
|---|
| MEIXIANG GAO等: "1,3-Butadiene Production from Bioethanol and Acetaldehyde over Zirconium Oxide Supported on Series Silica Catalysts", 《CATALYSIS SURVEYS FROM ASIA》 * |
| 李翔等: "ZrO2/SiO2催化乙醇乙醛制备1,3-丁二烯", 《化工进展》 * |
| 韩正: "乙醇合成1,3-丁二烯改性ZrO2/SiO2催化剂的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842905A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Carrier and catalyst, and preparation method and application thereof |
| CN113842905B (en) * | 2020-06-28 | 2023-08-29 | 中国石油化工股份有限公司 | Carrier and catalyst, and preparation method and application thereof |
| CN114618464A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Mesoporous catalyst and preparation method thereof, and application of mesoporous catalyst in reaction of ethanol and acetaldehyde to generate 1, 3-butadiene |
| CN114618464B (en) * | 2020-12-10 | 2024-01-09 | 中国科学院大连化学物理研究所 | Mesoporous catalyst and preparation method thereof and application thereof in reaction of ethanol and acetaldehyde to generate 1, 3-butadiene |
| CN115364844A (en) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | Regenerated deoxidation catalyst and preparation method and application thereof |
| US11642657B2 (en) | 2021-09-13 | 2023-05-09 | Petróleo Brasileiro S.A.—Petrobras | Method for preparing a catalyst for one-step production of butadiene from ethanol, catalyst and use thereof |
| CN114452997A (en) * | 2022-01-25 | 2022-05-10 | 浙江工业大学 | Nitrogen-doped supported oxide catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110575828A (en) | Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof | |
| Liu et al. | Functionalized MIL-101 with imidazolium-based ionic liquids for the cycloaddition of CO2 and epoxides under mild condition | |
| US6521808B1 (en) | Preparation and use of a catalyst for the oxidative dehydrogenation of lower alkanes | |
| Zhang et al. | Direct synthesis of V-containing all-silica beta-zeolite for efficient one-pot, one-step conversion of carbohydrates into 2, 5-diformylfuran | |
| Chieregato et al. | Structure–Reactivity Correlations in Vanadium‐Containing Catalysts for One‐Pot Glycerol Oxidehydration to Acrylic Acid | |
| CN102652130A (en) | Process for producing olefin oxide | |
| Kiatphuengporn et al. | Roles of acidic sites in alumina catalysts for efficient d-xylose conversion to lactic acid | |
| CN103288691B (en) | A kind of method of dimethyl thioether oxidation | |
| Yao et al. | Highly efficient catalytic oxidation of cyclohexane over cobalt-doped mesoporous titania with anatase crystalline structure | |
| CN107739297B (en) | Method for preparing methanol, formaldehyde and CO by directly and selectively oxidizing methane | |
| JP6718017B2 (en) | Method for producing 1,3-cyclohexanedimethanol | |
| Feng et al. | Zn 1, 3, 5-benzenetricarboxylate as an efficient catalyst for the synthesis of cyclic carbonates from CO 2 | |
| Choudhary et al. | Epoxidation of styrene by anhydrous H 2 O 2 over TS-1 and γ-Al 2 O 3 catalysts: Effect of reaction water, poisoning of acid sites and presence of base in the reaction mixture | |
| CN106955690B (en) | Solid alkaline catalyst for preparing butanol by catalyzing ethanol and preparation method thereof | |
| Astrakova et al. | Effect of bases on catalytic properties of cobalt-nitrogen-carbon composites in oxidative esterification of benzyl alcohol with methanol | |
| CN112295556A (en) | Supported catalyst and preparation method thereof | |
| Wu et al. | Direct oxidation of methane to methanol using CuMoO 4 | |
| CN112275270A (en) | Supported catalyst and preparation method thereof | |
| Kravchenko et al. | Olefin epoxidation over metal-organic frameworks modified with transition metals | |
| CN112479222A (en) | Hierarchical pore pure silicon zeolite molecular sieve and preparation method thereof | |
| Corma et al. | From MOFs to zeolites: zirconium sites for epoxide rearrangement | |
| Wang et al. | Synthesis of porous confined ionic liquid phosphotungstate based on MIL-101 and its solvent-free catalytic oxidation of cyclohexene to adipic acid | |
| CN114618464B (en) | Mesoporous catalyst and preparation method thereof and application thereof in reaction of ethanol and acetaldehyde to generate 1, 3-butadiene | |
| JPS62148437A (en) | Production of oxygen-containing organic compound | |
| CN116987265B (en) | Metal halide coupled triazinyl porous organic framework, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191217 |
|
| RJ01 | Rejection of invention patent application after publication |