CN111250099B - A kind of preparation method and application of composite metal oxide catalyst - Google Patents
A kind of preparation method and application of composite metal oxide catalyst Download PDFInfo
- Publication number
- CN111250099B CN111250099B CN202010241192.0A CN202010241192A CN111250099B CN 111250099 B CN111250099 B CN 111250099B CN 202010241192 A CN202010241192 A CN 202010241192A CN 111250099 B CN111250099 B CN 111250099B
- Authority
- CN
- China
- Prior art keywords
- source
- inorganic
- composite metal
- zinc
- magnesium
- 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.)
- Active
Links
Images
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
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical catalysis, and discloses a preparation method of a composite metal oxide catalyst, which comprises the following steps: dissolving water-soluble inorganic zinc source, inorganic calcium source, inorganic magnesium source and inorganic iron source in water, adding an alkali source, and adjusting the pH of the solution to 8-12 to obtain a reaction solution; heating the reaction liquid to 50-100 ℃, reacting for 4-8 h, cooling, aging for 6-24 h, filtering, washing and drying to obtain a ZnCaMgFe hydrotalcite material; and calcining the ZnCaMgFe hydrotalcite-like material at 350-550 ℃ to obtain the composite metal oxide catalyst. The invention also provides application of the composite metal oxide catalyst obtained by the preparation method of the catalyst in preparing propylene glycol ether by catalyzing alcohol and propylene oxide. The catalyst has the advantages of high activity, high selectivity, easy recovery, low energy consumption, easy separation and the like.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a preparation method and application of a composite metal oxide catalyst.
Background
Propylene glycol ether, especially Propylene Glycol Methyl Ether (PGME), has two functional groups with strong dissolving capacity in its chemical structure, ether bond and hydroxyl group, and is hydrophobic and hydrophilic, so that propylene glycol methyl ether may be used as universal solvent with excellent performance. Propylene glycol methyl ether has a molecular structure and physical and chemical properties similar to those of glycol ether, and is considered to be an alternative to glycol ether. Methanol and propylene oxide are used as raw materials to synthesize propylene glycol methyl ether industrially, but due to the steric effect of propylene oxide, the ring opening positions of propylene oxide are different under the conditions of acid and alkali, and then the propylene oxide and alcohols undergo addition reaction, so that 1-methoxy-2-propanol is generated by the alkali, and 2-methoxy-1-propanol is generated by the acid. Meanwhile, the toxicity of the product I is higher than that of the product II, so that people pay more and more attention to the synthesis of propylene glycol ether by alkali catalysis.
At present, the traditional strong-alkaline catalysts such as sodium (potassium) alkoxide, sodium hydroxide, tertiary amine and the like are mostly adopted for synthesizing propylene glycol methyl ether industrially, the alkalinity is uniform, the catalytic efficiency is high, but the catalysts have the defects of strong corrosivity, large generation amount of three wastes, difficulty in recycling the catalysts and the like, and are gradually eliminated.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method and application of a composite metal oxide catalyst.
The invention provides a preparation method of a composite metal oxide catalyst, which comprises the following steps:
dissolving water-soluble inorganic zinc source, inorganic calcium source, inorganic magnesium source and inorganic iron source in water, adding an alkali source, and adjusting the pH of the solution to 8-12 to obtain a reaction solution;
heating the reaction liquid to 50-100 ℃, reacting for 4-8 h, cooling, aging for 6-24 h, filtering, washing and drying to obtain a ZnCaMgFe hydrotalcite material;
and calcining the ZnCaMgFe hydrotalcite-like material at 350-550 ℃ to obtain the composite metal oxide catalyst.
The invention also provides application of the composite metal oxide obtained by the preparation method of the composite metal oxide catalyst in preparing propylene glycol ether by catalyzing alcohol and propylene oxide.
The invention provides a preparation method of a composite metal oxide catalyst, wherein the obtained composite metal oxide catalyst is an oxide containing ZnCaMgFe hydrotalcite, and the hydrotalcite laminate has the characteristics of adjustable controllability on chemical composition, internal space composition, internal grain size and distribution, anion type and quantity between laminates and the like. Ca. The Mg element oxide is alkaline, the addition of Zn element can adjust the acidity and alkalinity of the catalyst, the catalytic performance of the catalyst is improved by adjusting the acidity and alkalinity, and the catalyst has the advantages of few byproducts, high activity, high selectivity, low energy consumption and the like. The addition of Fe element makes the composite metal oxide catalyst have magnetism, and is convenient to separate. In addition, the composite metal oxide catalyst has simple preparation process and low production cost, and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of a composite metal oxide obtained in example 2 of the present invention.
FIG. 2 is a graph showing the magnetic properties of the composite metal oxide obtained in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a composite metal oxide catalyst, which comprises the following steps:
dissolving water-soluble inorganic zinc source, inorganic calcium source, inorganic magnesium source and inorganic iron source in water, adding an alkali source, and adjusting the pH of the solution to 8-12 to obtain a reaction solution;
heating the reaction liquid to 50-100 ℃, reacting for 4-8 h, cooling, aging for 6-24 h, filtering, washing and drying to obtain a ZnCaMgFe hydrotalcite material;
and calcining the ZnCaMgFe hydrotalcite-like material at 350-550 ℃ to obtain the composite metal oxide catalyst.
Specifically, the inorganic zinc source is at least one of zinc sulfate, zinc nitrate and zinc chloride and their respective hydrates, preferably, the inorganic zinc source is at least one of zinc sulfate, zinc nitrate and zinc chlorideThe inorganic zinc source is zinc nitrate or hydrate thereof; the inorganic calcium source is at least one of calcium nitrate, calcium chloride and respective hydrates thereof; preferably, the inorganic calcium source is calcium nitrate or a hydrate thereof; the inorganic magnesium source is at least one of magnesium sulfate, magnesium nitrate, magnesium chloride and respective hydrates thereof, preferably, the inorganic magnesium source is magnesium nitrate or a hydrate thereof; the inorganic iron source is at least one of ferric nitrate and ferric chloride and hydrates thereof, and preferably, the inorganic iron source is ferric nitrate or hydrates thereof. In order to ensure that the ions are fully mixed, the total molar concentration of zinc, calcium, magnesium and iron in the reaction solution is 0.5-2M. In order to ensure that the ZnCaMgFe hydrotalcite like material is formed, divalent metal and trivalent metal n [ M ] are contained in the reaction liquid2+]/n[M3+]The range ratio is 1-4: 1, namely the ratio of the total amount of zinc, calcium and magnesium to the amount of iron is 1-4: 1. preferably, to ensure higher conversion and selectivity of alcoholysis ring opening of propylene oxide, the divalent metal is mixed with the trivalent metal n [ M ]2+]/n[M3+]The range ratio is controlled to be 2-3: 1. more preferably, the molar ratio of Zn, Ca, Mg and Fe in the inorganic zinc source, inorganic calcium source, inorganic magnesium source and inorganic iron source is (0.2-0.5): (0.8-1): (0.8-1): 1.
more specifically, dissolving a water-soluble inorganic zinc source, an inorganic calcium source, an inorganic magnesium source and an inorganic iron source in water, adding an alkali source, heating to 50-80 ℃, stirring and refluxing for 5-12 h, cooling, aging for 6-12 h, filtering, washing, and drying at 80-100 ℃ for 10-20 h to obtain the ZnCaMgFe hydrotalcite material.
In order to ensure that the hydrotalcite is fully converted into the metal oxide at high temperature, the calcination temperature is controlled to be above 400 ℃, the calcination time is not less than 2 hours, and more preferably, in order to ensure that the hydrotalcite is converted into the spinel as little as possible, more active sites are reserved, the calcination temperature is controlled to be 450-550 ℃, and the calcination time is 2-4 hours.
Preferably, the alkali source is NaOH, urea, NaOH and NaCO3At least one buffer solution, preferably, the alkali source is NaOH and NaCO3And (4) a buffer solution. More preferably, an alkali source is added to adjust the pH of the solution to 10-11.
The invention also provides application of the composite metal oxide obtained by the preparation method of the composite metal oxide catalyst in preparing propylene glycol ether by catalyzing alcohol and propylene oxide.
Specifically, propylene oxide and alcohol are fed into a reactor to contact with the composite metal oxide, and the mixture is heated to 80-160 ℃ in a closed environment to obtain propylene glycol ether. Wherein the mass ratio of the composite metal oxide catalyst to the reactant is 1: 10 to 1000. Preferably, the molar ratio of propylene oxide to alcohol is 1: 1-10, wherein the mass ratio of the composite metal oxide catalyst to the reactants is 1: 50-500, and the reaction time is 0.5-12 h. The pressure is usually between 0.1 and 1 MPa. More preferably, the molar ratio of propylene oxide to alcohol is 1: 3-5, wherein the mass ratio of the composite metal oxide catalyst to the reactants is 1: 50 to 150. The alcohol is C1～C8Any one of alcohols. The fixed bed evaluated the life of the composite metal oxide, and hardly decreased in 500 hours. In addition, compared with the existing solid catalyst, the composite metal oxide catalyst has the advantages of greatly improving the conversion rate of propylene oxide and the selectivity of propylene glycol ether, having good magnetism, being capable of being repeatedly used and having low cost.
The preparation method and application of the composite metal oxide catalyst are illustrated by specific examples below. The raw materials in the following examples can be directly prepared according to the existing methods, and of course, the raw materials in other examples can also be directly purchased from the market, and are not limited thereto.
Example 1:
composite metal (Zn)0.35Ca1Mg1Fe1) Synthesis of oxides:
the weighed molar ratio was 0.35: 1: 1: 1 nitrate of Zn, Ca, Mg and Fe is added into a 500mL three-necked bottle, 100mL deionized water is added and stirred for dissolving for 2 hours, and then 0.1M NaOH/Na is added dropwise2CO3After the pH value of the buffer salt solution is adjusted to 10-11, heating to 60 ℃, continuously stirring for 6h, standing at room temperature for aging for 12h, filtering, washing and drying to obtain brick red Zn0.35Ca1Mg1Fe1A hydrotalcite-like material; zn is added0.35Ca1Mg1Fe1Calcining the hydrotalcite-like material in a tube furnace at 450 ℃ for 2h in the air atmosphere to obtain the composite metal (Zn)0.35Ca1Mg1Fe1) And cooling the oxide, and taking out for later use.
1.07 wt% of the reactant of the composite metal (Zn)0.35Ca1Mg1Fe1) Oxides, in a molar ratio of 3: 1, adding methanol and propylene oxide into a high-pressure reaction kettle simultaneously, heating to 120 ℃, and reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 72.43%, and the selectivity of propylene glycol monomethyl ether was calculated to be 90.71%.
Example 2:
composite metal (Zn)0.43Ca1Mg1Fe1) Synthesis of oxides:
the weighed molar ratio was 0.43: 1: 1: 1 nitrate of Zn, Ca, Mg and Fe is added into a 500mL three-necked bottle, 100mL deionized water is added and stirred for dissolving for 2 hours, and then 0.1M NaOH/Na is added dropwise2CO3After the pH value of the buffer salt solution is adjusted to 10-11, heating to 60 ℃, continuously stirring for 6h, standing at room temperature for aging for 12h, filtering, washing and drying to obtain brick red Zn0.43Ca1Mg1Fe1A hydrotalcite-like material; zn is added0.43Ca1Mg1Fe1Calcining the hydrotalcite-like material in a tube furnace at 450 ℃ for 2h in the air atmosphere to obtain the composite metal (Zn)0.43Ca1Mg1Fe1) And cooling the oxide, and taking out for later use.
1.07 wt% of the reactant of the composite metal (Zn)0.43Ca1Mg1Fe1) Oxides, in a molar ratio of 3: 1, adding methanol and propylene oxide into a high-pressure reaction kettle simultaneously, heating to 120 ℃, and reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 81.30% and the selectivity of propylene glycol monomethyl ether was calculated to be 94.63%.
Example 3:
composite metal (Zn)0.5Ca1Mg1Fe1) Synthesis of oxides:
the weighed molar ratio was 0.5: 1: 1: 1 nitrate of Zn, Ca, Mg and Fe is added into a 500mL three-necked bottle, 100mL deionized water is added and stirred for dissolving for 2 hours, and then 0.1M NaOH/Na is added dropwise2CO3After the pH value of the buffer salt solution is adjusted to 10-11, heating to 60 ℃, continuously stirring for 6h, standing at room temperature for aging for 12h, filtering, washing and drying to obtain brick red Zn0.5Ca1Mg1Fe1A hydrotalcite-like material; zn is added0.5Ca1Mg1Fe1Calcining the hydrotalcite-like material in a tube furnace at 450 ℃ for 2h in the air atmosphere to obtain the composite metal (Zn)0.5Ca1Mg1Fe1) And cooling the oxide, and taking out for later use.
1.07 wt% of the reactant of the composite metal (Zn)0.5Ca1Mg1Fe1) Oxides, in a molar ratio of 3: 1, adding methanol and propylene oxide into a high-pressure reaction kettle simultaneously, heating to 120 ℃, and reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 50.76%, and the selectivity of propylene glycol monomethyl ether was calculated to be 92.82%.
Example 4:
methanol, propylene oxide and the composite metal (Zn) obtained in example 20.43Ca1Mg1Fe1) And (3) uniformly mixing the oxides, feeding the mixture into a high-pressure reaction kettle, and heating the mixture to 120 ℃, wherein the molar ratio of the propylene oxide to the alcohol is 1: 3, composite metal (Zn)0.43Ca1Mg1Fe1) The mass of the oxide was 1.07 wt% of the reactants, and the reaction was carried out for 6 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 91.08%, and the selectivity of propylene glycol monomethyl ether was calculated to be 91.73%.
Example 5:
methanol, propylene oxide and the composite metal (Zn) obtained in example 20.43Ca1Mg1Fe1) And (3) uniformly mixing the oxides, feeding the mixture into a high-pressure reaction kettle, and heating the mixture to 140 ℃, wherein the molar ratio of the propylene oxide to the alcohol is 1: 3, composite metal (Zn)0.43Ca1Mg1Fe1) The mass of the oxide was 1.07 wt% of the reactants, and the reaction was carried out for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 93.32%, and the selectivity of propylene glycol monomethyl ether was calculated to be 89.09%.
Example 6:
methanol, propylene oxide and the composite metal (Zn) obtained in example 20.43Ca1Mg1Fe1) And (3) uniformly mixing the oxides, feeding the mixture into a high-pressure reaction kettle, and heating the mixture to 120 ℃, wherein the molar ratio of the propylene oxide to the alcohol is 1: 1, composite metal (Zn)0.43Ca1Mg1Fe1) The mass of the oxide was 1.07 wt% of the reactants, and the reaction was carried out for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 18.30% and the selectivity of propylene glycol monomethyl ether was calculated to be 94.07%.
Example 7:
methanol, propylene oxide and the composite metal (Zn) obtained in example 20.43Ca1Mg1Fe1) The oxides are evenly mixed and then are sent into a high-pressure reaction kettle to be heated to 120 ℃, wherein the mol ratio of the propylene oxide to the alcohol is 1:5, and the composite metal (Zn) is0.43Ca1Mg1Fe1) The mass of the oxide was 1.07 wt% of the reactants, and the reaction was carried out for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 81.64%, and the selectivity of propylene glycol monomethyl ether was calculated to be 93.52%.
Example 8:
methanol, propylene oxide and the composite metal (Zn) obtained in example 20.43Ca1Mg1Fe1) And (3) uniformly mixing the oxides, feeding the mixture into a high-pressure reaction kettle, and heating the mixture to 120 ℃, wherein the molar ratio of the propylene oxide to the alcohol is 1: 7, composite metal (Zn)0.43Ca1Mg1Fe1) The mass of the oxide was 1.07 wt% of the reactants, and the reaction was carried out for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 63.00% and the selectivity of propylene glycol monomethyl ether was calculated to be 93.68%.
Comparative example 1:
composite metal (Ca)0.5Mg1.5Fe1) Synthesis of oxides:
the weighed molar ratio was 0.5: 1.5: 1 nitrate of Ca, Mg and Fe is added into a 500mL three-necked bottle, 100mL deionized water is added and stirred for dissolving for 2 hours, and then 0.1M NaOH/Na is added dropwise2CO3After the pH value of the buffer salt solution is adjusted to 10-11, heating to 60 ℃, continuously stirring for 6h, standing at room temperature for aging for 12h, filtering, washing and drying to obtain Ca0.5Mg1.5Fe1A hydrotalcite-like material; adding Ca0.5Mg1.5Fe1Calcining the hydrotalcite-like material in a tubular furnace at 450 ℃ for 2h in the air atmosphere to obtain the composite metal (Ca)0.5Mg1.5Fe1) And cooling the oxide, and taking out for later use.
1.07 wt% of the reactant of composite metal (Ca)0.5Mg1.5Fe1) Oxides, in a molar ratio of 3: 1, adding methanol and propylene oxide into a high-pressure reaction kettle simultaneously, heating to 120 ℃, and reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 25.06% and the selectivity of propylene glycol monomethyl ether was calculated to be 80.33%.
Comparative example 2:
composite metal (Ca)1Mg1Fe1) Synthesis of oxides:
weighing the mixture according to a molar ratio of 1: 1: 1 nitrate of Ca, Mg and Fe is added into a 500mL three-necked bottle, 100mL deionized water is added and stirred for dissolving for 2 hours, and then 0.1M NaOH/Na is added dropwise2CO3After the pH value of the buffer salt solution is adjusted to 10-11, heating to 60 ℃, continuously stirring for 6h, standing at room temperature for aging for 12h, filtering, washing and drying to obtain brick red Ca1Mg1Fe1Hydrotalcite-like compounds; adding Ca1Mg1Fe1Calcining hydrotalcite-like compound in a tubular furnace at 450 ℃ for 2h in the air atmosphere to obtain composite metal (Ca)1Mg1Fe1) And cooling the oxide, and taking out for later use.
1.07 wt% of the reactant of composite metal (Ca)1Mg1Fe1) Oxides, in a molar ratio of 3: 1, adding methanol and propylene oxide into a high-pressure reaction kettle simultaneously, heating to 120 ℃, and reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 60.40%, and the selectivity of propylene glycol monomethyl ether was calculated to be 96.15%.
Comparative example 3:
composite metal (Ca)2Mg2Fe1) Synthesis of oxides:
the weighing molar ratio is 2: 2: 1 nitrate of Ca, Mg and Fe is added into a 500mL three-necked bottle, 100mL deionized water is added and stirred for dissolving for 2 hours, and then 0.1M NaOH/Na is added dropwise2CO3After the pH value of the buffer salt solution is adjusted to 10-11, heating to 60 ℃, continuously stirring for 6h, standing at room temperature for aging for 12h, filtering, washing and drying to obtain brick red Ca2Mg2Fe1Hydrotalcite-like compounds; adding Ca2Mg2Fe1Pyrolyzing hydrotalcite-like compound at 450 ℃ for 2h in air atmosphere in a tubular furnace to obtain composite metal (Ca)2Mg2Fe1) And cooling the oxide, and taking out for later use.
1.07 wt% of the reactant of composite metal (Ca)2Mg2Fe1) Oxides, in a molar ratio of 3: 1, adding methanol and propylene oxide into a high-pressure reaction kettle simultaneously, heating to 120 ℃, and reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 57.02%, and the selectivity of propylene glycol monomethyl ether was calculated to be 90.84%.
Comparative example 4:
under the condition of no catalyst, uniformly mixing methanol and propylene oxide, feeding the mixture into a high-pressure reaction kettle, heating to 120 ℃, wherein the molar ratio of the propylene oxide to the alcohol is 1: 3, reacting for 4 hours. The composition of the obtained liquid phase mixture was measured by gas chromatography of the obtained mixture, and the conversion of propylene oxide was calculated to be 14.21% and the selectivity of propylene glycol monomethyl ether was calculated to be 86.18%.
As can be seen from examples and comparative example 1, the presence of the mixed metal oxide serves to improve the conversion and selectivity; proper Ca, Mg and Fe molar ratio is favorable for the conversion rate of the propylene oxide; the addition of a part-way lewis acid can suitably improve the conversion rate of propylene oxide, but both peracid and overbase are not favorable for the conversion of propylene oxide. The catalyst has strong magnetism and is easy to recover, and has important significance in catalyzing alcohol and propylene oxide to prepare propylene glycol ether.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The application of a composite metal oxide catalyst in catalyzing alcohol and propylene oxide to prepare propylene glycol ether comprises the following steps:
dissolving water-soluble inorganic zinc source, inorganic calcium source, inorganic magnesium source and inorganic iron source in water, adding an alkali source, and adjusting the pH of the solution to 8-12 to obtain a reaction solution;
heating the reaction liquid to 50-100 ℃, reacting for 4-8 h, cooling, aging for 6-24 h, filtering, washing and drying to obtain a ZnCaMgFe hydrotalcite material;
calcining the ZnCaMgFe hydrotalcite-like material at 350-550 ℃ to obtain the composite metal oxide catalyst,
wherein the total molar concentration of zinc, calcium, magnesium and iron in the reaction liquid is 0.5-2M, and the molar ratio of zinc, calcium, magnesium and iron in the reaction liquid is (0.2-0.5): (0.8-1): (0.8-1): 1.
2. the use of claim 1, wherein the inorganic zinc source is at least one of zinc sulfate, zinc nitrate, and zinc chloride, and their respective hydrates, and the inorganic calcium source is at least one of calcium nitrate and calcium chloride, and their respective hydrates; the inorganic magnesium source is at least one of magnesium sulfate, magnesium nitrate, magnesium chloride and respective hydrates thereof, and the inorganic iron source is at least one of ferric nitrate, ferric chloride and hydrates thereof.
3. The use according to claim 1 or 2, wherein the inorganic zinc source is zinc nitrate or a hydrate thereof, the inorganic calcium source is calcium nitrate or a hydrate thereof, the inorganic magnesium source is magnesium nitrate or a hydrate thereof, and the inorganic iron source is iron nitrate or a hydrate thereof.
4. Use according to claim 1, wherein the ZnCaMgFe-based hydrotalcite material is calcined at 400 to 550 ℃ for 2 to 4 hours.
5. Use according to claim 1, wherein the alkali source is NaOH, urea, NaOH and NaCO3At least one of a buffer.
6. Use according to claim 1, wherein the alcohol is C1～C8Any one of alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010241192.0A CN111250099B (en) | 2020-03-31 | 2020-03-31 | A kind of preparation method and application of composite metal oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010241192.0A CN111250099B (en) | 2020-03-31 | 2020-03-31 | A kind of preparation method and application of composite metal oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111250099A CN111250099A (en) | 2020-06-09 |
| CN111250099B true CN111250099B (en) | 2021-05-07 |
Family
ID=70944592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010241192.0A Active CN111250099B (en) | 2020-03-31 | 2020-03-31 | A kind of preparation method and application of composite metal oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111250099B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318595A (en) * | 2000-04-17 | 2001-10-24 | 北京化工大学 | Composite oganic-inorganic selective ultraviolet blocking material and its preparation |
| CN1443745A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Solid alkali catalyst for synthesizing propanediol ether |
| CN1443743A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for preparing propanediol ether |
| CN1546227A (en) * | 2003-12-11 | 2004-11-17 | 中国科学院山西煤炭化学研究所 | A kind of solid catalyst for synthesizing propylene glycol ether and its preparation method and application |
| CN1762578A (en) * | 2005-09-28 | 2006-04-26 | 茂名学院 | Supported solid alkali catalyst for synthesis of propylene glycol |
| CN100999448A (en) * | 2007-01-05 | 2007-07-18 | 华东师范大学 | Synthesis method of propylene glycol ether |
| CN101613259A (en) * | 2008-06-27 | 2009-12-30 | 江苏瑞佳化学有限公司 | The preparation method of electronic grade propylene glycol monomethyl ether |
| CN102266763A (en) * | 2010-06-04 | 2011-12-07 | 南京工程学院 | Solid alkaline catalyst for synthesis of 1-methoxy-2-propanol, and preparation method thereof |
| CN103406119A (en) * | 2013-08-19 | 2013-11-27 | 太原工业学院 | Bio-diesel catalyst Ca-Mg-Zn-Al-O and preparation method thereof |
| CN103785450A (en) * | 2014-01-28 | 2014-05-14 | 富德（北京）能源化工有限公司 | Bifunctional catalyst for olefins oxidative dehydrogenation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2343124B1 (en) * | 2001-11-08 | 2021-01-06 | Mitsubishi Chemical Corporation | METHOD FOR PREPARATION of a COMPOSITE OXIDE CATALYST |
| JP5867831B2 (en) * | 2011-01-27 | 2016-02-24 | 国立研究開発法人物質・材料研究機構 | Method for producing anion-exchange layered double hydroxide and method for replacing carbonate ion of layered double hydroxide containing carbonate ion |
| CN103785347A (en) * | 2012-10-30 | 2014-05-14 | 北京低碳清洁能源研究所 | Composite oxide adsorbent for adsorption of medium/high temperature CO2 |
| CN103721735B (en) * | 2013-12-31 | 2016-04-27 | 富德（北京）能源化工有限公司 | For catalyst precursor and the catalyst of selective oxidation dehydrogenation |
-
2020
- 2020-03-31 CN CN202010241192.0A patent/CN111250099B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318595A (en) * | 2000-04-17 | 2001-10-24 | 北京化工大学 | Composite oganic-inorganic selective ultraviolet blocking material and its preparation |
| CN1443745A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Solid alkali catalyst for synthesizing propanediol ether |
| CN1443743A (en) * | 2002-03-13 | 2003-09-24 | 中国石油化工股份有限公司 | Method for preparing propanediol ether |
| CN1546227A (en) * | 2003-12-11 | 2004-11-17 | 中国科学院山西煤炭化学研究所 | A kind of solid catalyst for synthesizing propylene glycol ether and its preparation method and application |
| CN1762578A (en) * | 2005-09-28 | 2006-04-26 | 茂名学院 | Supported solid alkali catalyst for synthesis of propylene glycol |
| CN100999448A (en) * | 2007-01-05 | 2007-07-18 | 华东师范大学 | Synthesis method of propylene glycol ether |
| CN101613259A (en) * | 2008-06-27 | 2009-12-30 | 江苏瑞佳化学有限公司 | The preparation method of electronic grade propylene glycol monomethyl ether |
| CN102266763A (en) * | 2010-06-04 | 2011-12-07 | 南京工程学院 | Solid alkaline catalyst for synthesis of 1-methoxy-2-propanol, and preparation method thereof |
| CN103406119A (en) * | 2013-08-19 | 2013-11-27 | 太原工业学院 | Bio-diesel catalyst Ca-Mg-Zn-Al-O and preparation method thereof |
| CN103785450A (en) * | 2014-01-28 | 2014-05-14 | 富德（北京）能源化工有限公司 | Bifunctional catalyst for olefins oxidative dehydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111250099A (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6304830B2 (en) | Catalyst for butadiene production by oxidative dehydrogenation of butene used in fluidized bed reactor, and production method and use thereof | |
| EP0938446B1 (en) | Method of hydrocarbon reforming and catalyst and catalyst precursor therefor | |
| CN101507917A (en) | Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof | |
| CN112823879B (en) | Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol | |
| CN110624529A (en) | Preparation and use methods of hydroxide intercalation calcium magnesium aluminum hydrotalcite solid base catalyst | |
| WO2014072802A2 (en) | Synthesis of dimethyl carbonate and related compounds | |
| GB2064352A (en) | Preparation of copper-zinc aluminium catalyst compositions | |
| CN101367041A (en) | Preparation of a solid base catalyst and its application in aldol condensation reaction | |
| CN111054425B (en) | hydrotalcite/MCM-41 mesoporous silicon composite solid base catalyst and in-situ preparation method and application thereof | |
| CN111250099B (en) | A kind of preparation method and application of composite metal oxide catalyst | |
| US4232171A (en) | Process for producing methyl formate | |
| CN105944731B (en) | A kind of composite oxide catalysts of urea and phenol synthesis salicylamide and preparation method and application | |
| CN113398912A (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
| CN114749168A (en) | High-activity zirconium dioxide/zinc oxide catalyst and preparation method and application thereof | |
| CN102675059A (en) | Method for combining ethylene glycol monoethyl ether with ternary composite metal oxide as catalyst | |
| CN111655369B (en) | Method for preparing metal complex catalyst and metal complex catalyst prepared by the same | |
| CN109433202B (en) | A ruthenium-based catalyst supported on the surface of barium tantalate and its application in ammonia synthesis | |
| CN112206762A (en) | A kind of preparation method of Na-γ-Al2O3 catalyst and application of catalytic synthesis of anisole | |
| CN115999637B (en) | A hydrophobic nanorod catalyst and its preparation method and application | |
| CN114588904B (en) | Cu-based metal oxide catalyst, preparation method thereof and synthesis method of 2,3-butanediol using the same | |
| JP2003010684A (en) | Catalyst for manufacturing hydrogen and hydrogen manufacturing method | |
| CN116768226B (en) | Catalyst for synthesizing DPG and preparation method and application thereof | |
| CN114832839B (en) | Persulfate-assisted synthesis of iron-based solid superacid catalyst and its preparation and application | |
| KR102216767B1 (en) | Method for preparing metal complex catalyst and metal complex catalyst prepared thereof | |
| JP2010069453A (en) | Catalyst for reforming dimethyl ether |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |