KR20170085235A - Catalyst for producing glycerol carbonate from glycerol and carbon dioxide and preparation method of the same - Google Patents
Catalyst for producing glycerol carbonate from glycerol and carbon dioxide and preparation method of the same Download PDFInfo
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- KR20170085235A KR20170085235A KR1020160004592A KR20160004592A KR20170085235A KR 20170085235 A KR20170085235 A KR 20170085235A KR 1020160004592 A KR1020160004592 A KR 1020160004592A KR 20160004592 A KR20160004592 A KR 20160004592A KR 20170085235 A KR20170085235 A KR 20170085235A
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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
- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Abstract
The present invention relates to a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide and a process for their preparation. Specifically, the present invention relates to a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide, a metal oxide catalyst containing macropores of 100 to 3500 nm in size in the catalyst, and a lanthanum and zinc-based metal oxide catalyst and a method for producing the same.
The catalyst according to the present invention can exhibit excellent catalytic activity over a wide specific surface area by being manufactured to contain macropores therein, and it can be applied to the production process of glycerol carbonate, so that high purity glycerol carbonate can be produced at a high yield by using glycerol and carbon dioxide Can be manufactured.
Description
The present invention relates to a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide and a process for their preparation. Specifically, the present invention relates to a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide, a metal oxide catalyst containing macropores of 100 to 3500 nm in size in the catalyst, and a lanthanum and zinc-based metal oxide catalyst and a method for producing the same.
As fossil fuels such as petroleum, natural gas and coal are expected to be gradually depleted, biodiesel, which has similar properties to petroleum, is gaining popularity as a renewable and alternative energy source, and its usage is skyrocketing. However, in the production process of biodiesel, a waste liquid containing a high concentration of glycerol is produced as a by-product, which is incinerated in a simple manner. In this process, a great deal of cost is required and the economical efficiency of the biodiesel production process is deteriorating. In addition, a large amount of carbon dioxide is generated during the by-product incineration process, thereby causing secondary environmental pollution.
Accordingly, studies on the utilization of glycerol produced as a by-product in the biodiesel production process are under way. As a method, glycerol carbonate, epichlorohydrin, glycerol ether, 1,3-propanediol, glycolic acid Lt; RTI ID = 0.0 > of < / RTI > In particular, among the above-mentioned glycerol derivatives, glycerol carbonate exhibits properties such as biodegradability, hypoallergeness, high boiling point, nonvolatility and moisturizing property and can be applied as a main component in electrolyte, surfactant, medicine, It is known to be highly industrially available.
Studies on a method of converting glycerol to glycerol carbonate have been attracting attention and a method of transesterifying glycerol with a carbonate compound (Patent Document 1), a method of reacting glycerol with urea Document 2), and a method of reacting glycerol with carbon dioxide (Non-Patent Document 1) have been developed and reported.
Particularly, in the method of converting glycerol to glycerol carbonate, a method of reacting glycerol with carbon dioxide is in the spotlight in terms of using a low-cost and environmentally friendly raw material, and can be produced by using glycerol and carbon dioxide In recent years, there has been a growing interest in providing high economic efficiency and industrial efficiency.
Accordingly, studies have been actively conducted to develop a method of synthesizing glycerol carbonate by reacting glycerol with carbon dioxide. Up to now, various kinds of catalysts have been developed and applied. However, when the yield of glycerol carbonate is 10% (Non-patent document 2 and non-patent document 3).
Under these circumstances, the present inventors have developed a catalyst containing macropores inside a bimetallic oxide-based catalyst for the first time and applied it to a process for producing glycerol carbonate, thereby producing glycerol carbonate with high yield and selectivity from glycerol and carbon dioxide And the present invention has been completed.
It is an object of the present invention to provide a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide and a process for their preparation.
SUMMARY OF THE INVENTION The present invention is directed to a bimetallic oxide-based catalyst comprising macropores ranging from 100 to 3500 nm in size in a catalyst and a process for preparing the same. The present invention also provides a process for producing glycerol carbonate by reacting glycerol and carbon dioxide under the above catalyst to produce glycerol carbonate.
In order to achieve the above object, the first aspect of the present invention is a catalyst for producing glycerol carbonate for producing glycerol carbonate from glycerol and carbon dioxide, which is a binary metal oxide containing macropores of 100 to 3500 nm in size, Provides catalysts based on lanthanum dioxycarbonate (La 2 O 2 CO 3 ) and zinc oxide (ZnO).
A second aspect of the present invention is the method for producing a glycerol carbonate for producing a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide, glycol (ethylene glycol) lanthanum nitrate in (NO (La 3) 3) and zinc nitrate (Zn (NO 3 ) 2 ) is mixed and sintered.
The third aspect of the present invention relates to a method for producing glycerol carbonate comprising the step of reacting glycerol and carbon dioxide under a catalyst of lanthanum dioxide and zirconium oxide containing macropores of 100 to 3500 nm in size in a catalyst to produce glycerol carbonate ≪ / RTI >
Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.
The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The term " step "or" step of ~ " used throughout the specification does not mean "step for.
Throughout this specification, the term "combination thereof" included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.
Hereinafter, the catalyst for producing glycerol carbonate for producing glycerol carbonate from glycerol and carbon dioxide of the present invention and a method for producing the same will be described in detail.
The catalyst for producing glycerol carbonate for producing glycerol carbonate from glycerol and carbon dioxide of the present invention is a binary metal oxide containing macropores of 100 to 3500 nm in size and the binary metal oxide is lanthanum dioxycarbonate (La 2 O 2 CO 3 ) and zinc oxide (ZnO).
In one embodiment of the present invention, the molar ratio of lanthanum in the lanthanum dioxycarbonate and zinc in the zinc oxide may be from 1: 1 to 1: 8. Preferably, the molar ratio of lanthanum in the lanthanum dioxycarbonate and zinc in the zinc oxide may be from 1: 1 to 1: 6, more preferably from 1: 1 to 1: 4.
In one embodiment of the present invention, the catalyst is La 2 O 2 CO 3 And a ZnO-based metal oxide as a result of introduction of macropores into the interior of the catalyst, thereby providing a high selectivity of glycerol carbonate compared to a catalyst of the same composition in which macropores are not introduced. Thus, it is possible to produce high purity glycerol carbonate The yield of glycerol carbonate was 10% or more, indicating a remarkable yield improving effect (see Table 3).
The present invention also relates to a process for producing a catalyst for the production of glycerol carbonate from glycerol and carbon dioxide, comprising the steps of mixing lanthanum nitrate (La (NO 3 ) 3 ) and zinc nitrate (Zn (NO 3 ) 2 ) And firing the mixture.
The method for producing glycerol carbonate for producing glycerol carbonate from the above-mentioned glycerol and carbon dioxide is characterized in that by using ethylene glycol, the produced La 2 O 2 CO 3 And nonuniform macropores having a diameter of 100 to 3500 nm can be formed inside the ZnO-based metal oxide. The ethylene glycol is oxidized by nitric acid at a low temperature to form a complex mixture. In the subsequent firing process, a sufficient amount of gas is introduced and the temperature is increased to 550 ° C. During the process, ethylene glycol is removed, Large pore patterns can be placed.
In an embodiment of the present invention, an appropriate amount of methanol may be further mixed to provide uniformity of the sticky texture of zinc nitrate and the ethylene glycol in the lanthanum nitrate.
In one embodiment of the present invention, the molar ratio of the lanthanum nitrate to the zinc nitrate used in the production method may be 1: 1 to 1: 8.
In one embodiment of the present invention, the mixing process of ethylene glycol, lanthanum nitrate, and zinc nitrate may be performed while stirring at room temperature for 1 to 3 hours, and ethylene glycol and methanol may be further added can do.
In one embodiment of the present invention, the calcination may be performed at a temperature of 30 ° C to 550 ° C at a rate of 1 ° C / minute (min) and then at 550 ° C for 4 to 6 hours.
The present invention also provides a method for producing glycerol carbonate, which comprises reacting glycerol and carbon dioxide in the presence of lanthanum dioxide and a zinc oxide-based catalyst containing macropores of 100 to 3500 nm size in the catalyst to produce glycerol carbonate to provide.
In one embodiment of the present invention, the step is to convert glycerol to glycerol carbonate by reacting glycerol under a carbon dioxide atmosphere using the catalyst according to the present invention.
In an embodiment of the present invention, the amount of the catalyst used in the step may be 5 wt% based on the weight of glycerol, and the reaction may be performed while stirring in a carbon dioxide atmosphere. The reaction can be carried out at a temperature of 160 to 170 ° C for 2 to 12 hours and can be carried out at a reaction pressure of 7 MPa under vacuum conditions.
The method for producing glycerol carbonate of the present invention is characterized in that La 2 O 2 CO 3 containing macropores according to the present invention And a ZnO-based catalyst, thereby having high glycerol conversion, glycerol carbonate selectivity, and production yield.
As used herein, the term "glycerol conversion" means the total rate at which glycerol, the starting material, is converted to a reactant according to the reaction under the catalyst. That is, it means the total ratio of glycerol, which is a starting material, once converted and converted to a reactant.
As used herein, the term "glycerol carbonate selectivity" means the ratio of glycerol to glycerol carbonate converted from the total ratio of the glycerol to the reactant, that is, the glycerol conversion.
The term "glycerol carbonate production yield" used in the present invention means the yield of glycerol carbonate obtained according to the reaction under the above catalyst. As a result, the glycerol carbonate production yield is the same as the glycerol conversion x glycerol carbonate selectivity.
In one embodiment of the present invention, the production yield of the glycerol carbonate produced by the above method may be 10 to 15%.
Also, in one embodiment of the present invention, the selectivity of the glycerol carbonate in the step may be 40 to 60%, and the conversion of glycerol in the step may be 20 to 25%.
La 2 O 2 CO 3 containing macropores according to the present invention And a process for preparing glycerol carbonate from glycerol and carbon dioxide using a ZnO-based catalyst can be carried out as shown in the following reaction formula (1).
[Reaction Scheme 1]
La 2 O 2 CO 3 containing macropores according to the present invention And the activity of ZnO present in the ZnO-based catalyst to form zinc glycerolate, an intermediate of glycerol carbonate, and the formed zinc glycerolate is converted into La 2 O 2 CO 3 Can eventually be converted to glycerol carbonate through the reaction with carbon dioxide in the presence of < RTI ID = 0.0 > At this time, Zn in the ZnO acts as a Lewis-acid site and binds to a hydroxyl group located at the end of glycerol to induce the formation of an intermediate.
The catalyst for producing glycerol carbonate for producing glycerol carbonate from glycerol and carbon dioxide according to the present invention is a binary oxide based on La 2 O 2 CO 3 -ZnO and is manufactured to contain macropores in the interior thereof, Activity. Further, by applying the catalyst according to the present invention to the process of producing glycerol carbonate, it is possible to produce glycerol carbonate of high purity with high yield by using glycerol and carbon dioxide.
Figure 1 is a diagram that shows the X- ray diffraction pattern of La 2 O 2 CO 3 -ZnO-based catalyst, and that macropores are not introduced La 2 O 2 CO 3 -ZnO-based catalyst containing macropores according to the present invention.
FIG. 2 is an FE-SEM image of a catalyst having La / Zn ratio of 0.125 among La 2 O 2 CO 3 -ZnO based catalysts containing macropores according to the present invention.
FIG. 3 is a FE-SEM image of a La 2 O 2 CO 3 -ZnO-based catalyst having La / Zn ratio of 0.25, which contains macropores according to the present invention.
FIG. 4 is a FE-SEM image of a catalyst having La / Zn ratio of 1 among La 2 O 2 CO 3 -ZnO based catalysts containing macropores according to the present invention.
FIG. 5 is an FE-SEM image of La 2 O 2 CO 3 -ZnO based catalyst prepared in Comparative Example of the present invention in which macropores are not introduced.
6 is a diagram illustrating a nitrogen adsorption isothermal curve of La 2 O 2 CO 3 -ZnO-based catalyst, and that macropores are not introduced La 2 O 2 CO 3 -ZnO-based catalyst containing macropores according to the present invention.
FIG. 7 is a schematic diagram showing a reactor system used in the production of La 2 O 2 CO 3 -ZnO based catalysts containing macropores according to the present invention.
Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are intended to further illustrate the present invention, and the scope of the present invention is not limited to these examples.
Example 1: containing macropores La 2 O 2 CO 3 - ZnO Based catalyst
Lanthanum nitrate (La (NO 3 ) 3 ) and zinc nitrate (Zn (NO 3 ) 2 ) were added to 15 mL of ethylene glycol at different molar ratios as shown in the following Table 1 and stirred at room temperature for 2 hours. When the metal salt was completely dissolved, 10 mL of methanol was added and stirred. To maintain an appropriate concentration, a mixed solution of 15 mL of ethylene glycol and 10 mL of methanol was further added to the volume of a 50 mL volumetric flask. After the metal salt is transferred to the mixed solution in the crucible increases by 1 ℃ per minute in a furnace in the early 30 ℃ increased at least 8 hours and 40 minutes, followed by firing at 550 ℃ for 5 hours, La 2 O 2 CO 3 containing macropores -ZnO based catalysts were prepared.
Comparative Example : Depending on the typical catalyst preparation method La 2 O 2 CO 3 - ZnO Based catalyst
The lanthanum nitrate (La (NO 3 ) 3 ) and zinc nitrate (Zn (NO 3 ) 2 ) were mixed at the molar ratios shown in Table 1 and added to water in accordance with the molar concentration of the two metals to prepare a metal mixed aqueous solution Then, the metal mixed aqueous solution was added dropwise to 50 mL of water while stirring. Thereafter, 2 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 11. After the addition was completed, the mixture was aged at 60 캜 for 3 hours with stirring. The aged mixture was filtered and washed with deionized water to give a solid. The solids were dried in an oven maintained at 80 DEG C for 12 hours. The dried solid was then calcined at 500 ° C for 5 hours to prepare a La 2 O 2 CO 3 -ZnO based catalyst.
Example 2: Characterization of catalyst
2-1. Catalytic morphology analysis
The crystal phases of the catalysts prepared in Examples and Comparative Examples were examined with an energy-dispersive X-ray spectrometer (FE-SEM-EDX, JEOL, JSM-500F, Japan). The X-ray diffraction (XRD) pattern was measured with a Rigaku RAD-3C diffractometer (Rigaku) operating at a scanning rate of 2 ° (2θ) / min at 35 kV and 20 mA with Cu Kα radiation (λ = 1.5418 A) RAD-3C diffractometer, Japan).
As a result of the X-ray diffraction analysis, it can be seen that as the molar ratio of La / Zn is changed, and also depending on whether or not the macropores are included, the prepared catalyst exhibits distinct characteristic crystal peaks, (Fig. 1).
In addition, as shown in Fig. 1, in the case of La / Zn = 0.125 catalyst containing macropores, only the ZnO form was formed without La 2 O 2 CO 3 form appearing near 2θ values of 14, 23 and 30 , So the conversion to glycerol carbonate was determined to be a value that can not be calculated. In the case of La / Zn = 1 catalyst containing macropores, the intensity of ZnO was larger than that of La 2 O 2 CO 3 .
The surface morphology and pore size of the catalyst prepared in the above examples were observed using a field-emission scanning electron microscope (FE-SEM, JEOL JSM-600F, Japan).
As shown in FIG. 2 to FIG. 4, it can be seen that unstructured macropores were introduced into the catalyst prepared in the above example, and that the macropores had a diameter of 100 to 3500 nm. However, as shown in FIG. 5, it can be seen that the catalyst prepared in the above Comparative Example has the same composition and La / Zn ratio but does not contain macropores.
2-2. Surface Characterization of Catalysts
Nitrogen adsorption isotherms were measured using a specific surface area measuring device (Micromeritics ASAP 2010, USA) (FIG. 6), and the surface area of the catalyst prepared in the above example was measured through a BET (Brunauer-Emmett-Teller) method. As a result, as shown in the following Table 2, La / Zn = 0.125 and La / Zn = 0.125 in the La 2 O 2 CO 3 -ZnO based catalyst (macropores La / Zn) In the case of the catalyst having the ratio of Zn = 0.25, it can be seen that it has a larger BET surface area than the catalyst (La / Zn) in which the macropores prepared in the above Comparative Example are not introduced.
Example 3: Glycerol using the catalyst of the present invention Of carbonate Produce
The catalyst prepared in Example 1 and Comparative Example was used to react glycerol with carbon dioxide to prepare glycerol carbonate.
Into a reactor equipped with a condenser system and a vacuum pump (FIG. 7), 0.1 mol of glycerol, 20 mL of acetonitrile and 5 wt% of catalyst based on the weight of glycerol were charged and reacted under a carbon dioxide atmosphere. The reaction was carried out at 170 DEG C and 7 MPa (20 DEG C) for 12 hours. After completion of the reaction, the reaction mixture was filtered, and the catalyst was washed with acetone to recover the product on the surface of the catalyst. The filtrate and the washing solution were combined and concentrated under reduced pressure to obtain glycerol carbonate.
Example 4: glycerol Carbonate Yield, Glycerol Carbonate Analysis of selectivity and glycerol conversion
A standardized curve was prepared by using a gas chromatography (GC) measurement area ratio of tetraethylene glycol and glycerol carbonate used as an internal standard reagent and a GC measurement area ratio of tetraethylene glycol and glycerol, and then comparing the GC analysis results of the products produced by the reaction And selectivity to glycerol carbonate was calculated. The GC peaks of the byproducts formed in the reaction were confirmed to calculate the conversion of glycerol, and the yield of glycerol carbonate was calculated using the conversion and selectivity.
Table 3 shows the results of the analysis of glycerol carbonate yield, glycerol carbonate selectivity and glycerol conversion according to the method for producing glycerol carbonate of Example 3 above.
As shown in Table 3, the La 2 O 2 CO 3 -ZnO-based catalyst (macroporous -La / Zn) containing the macropores prepared in the above Example was not introduced with the macropores prepared in the above Comparative Example In particular, in the case of La / Zn = 1 ratio, the yield of the catalyst containing macropores is 14.4%, which is 5% higher than that of the catalyst containing no macropores. It can be confirmed that the yield is improved. In addition, La 2 O 2 CO 3 -ZnO based catalysts containing macropores exhibit somewhat lower glycerol conversion than catalysts that do not incorporate macropores, but have high glycerol carbonate selectivity of about 50-60% , It can be seen that La 2 O 2 CO 3 -ZnO-based catalysts containing macropores can be obtained with higher yields of higher purity glycerol carbonate than catalysts not introduced with macropores. That is, it can be seen that the catalyst according to the present invention can exhibit excellent catalytic activity over a wide specific surface area by including macropores in the interior thereof, and thus can exhibit an excellent conversion efficiency from glycerol to glycerol carbonate.
The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (7)
The catalyst is a bimetallic oxide containing macropores of 100 to 3500 nm in size,
The binary metal oxide is a catalyst based on lanthanum dioxycarbonate (La 2 O 2 CO 3 ) and zinc oxide (ZnO).
Ethylene glycol production process comprising the step of mixing and calcining the lanthanum nitrate (La (NO 3) 3) and zinc nitrate (Zn (NO 3) 2) to (ethylene glycol).
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| CN108129311A (en) * | 2018-01-15 | 2018-06-08 | 清华大学 | A kind of method from carbon dioxide and glycerine manufacture glycerol carbonate |
| CN111587372A (en) * | 2018-07-13 | 2020-08-25 | 富士电机株式会社 | Carbon dioxide gas sensor |
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| CN104437455A (en) | 2014-10-24 | 2015-03-25 | 华中科技大学 | Ester-exchange-reaction catalyst, as well as preparation method and application thereof |
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| CN108129311A (en) * | 2018-01-15 | 2018-06-08 | 清华大学 | A kind of method from carbon dioxide and glycerine manufacture glycerol carbonate |
| CN111587372A (en) * | 2018-07-13 | 2020-08-25 | 富士电机株式会社 | Carbon dioxide gas sensor |
| CN111587372B (en) * | 2018-07-13 | 2023-09-19 | 富士电机株式会社 | carbon dioxide gas sensor |
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