CN113797914A - Catalyst for synthesizing ethylene carbonate, preparation method and application thereof - Google Patents
Catalyst for synthesizing ethylene carbonate, preparation method and application thereof Download PDFInfo
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- CN113797914A CN113797914A CN202111143676.2A CN202111143676A CN113797914A CN 113797914 A CN113797914 A CN 113797914A CN 202111143676 A CN202111143676 A CN 202111143676A CN 113797914 A CN113797914 A CN 113797914A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 90
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000004202 carbamide Substances 0.000 claims abstract description 81
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 238000000975 co-precipitation Methods 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000012716 precipitator Substances 0.000 claims abstract description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 20
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 29
- 239000012065 filter cake Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229910021281 Co3O4In Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004364 calculation method Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- 229910007564 Zn—Co Inorganic materials 0.000 description 6
- 229910007612 Zn—La Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003562 morphometric effect Effects 0.000 description 3
- 238000013425 morphometry Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- PLHJDBGFXBMTGZ-WEVVVXLNSA-N furazolidone Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)OCC1 PLHJDBGFXBMTGZ-WEVVVXLNSA-N 0.000 description 1
- 229960001625 furazolidone Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- B01J23/83—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 rare earths or actinides
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C07D317/38—Ethylene carbonate
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to the field of preparation of ethylene carbonate, and provides a catalyst for synthesizing ethylene carbonate, a preparation method and application thereof. The catalyst is a composite oxide catalyst which consists of one or two of Zn, La and Co and is used for the reaction of synthesizing ethylene carbonate from urea and ethylene glycol. The catalyst is prepared by mixing an aqueous solution of zinc nitrate, an aqueous solution of lanthanum nitrate and an aqueous solution of cobalt nitrate in proportion, adding the mixture into an aqueous solution of a precipitator urea, controlling the pH of the solution, and carrying out coprecipitation reaction. The preparation process of the catalyst is simple and easy to implement, and the cost is low; the catalyst has high activity, high ethylene carbonate yield, mild reaction conditions, good stability and easy separation and regeneration.
Description
Technical Field
The invention relates to the field of preparation of ethylene carbonate, and particularly relates to a catalyst for synthesizing ethylene carbonate, a preparation method and application thereof.
Background
Ethylene carbonate is an important organic synthesis intermediate, is an important raw material for preparing dimethyl carbonate, furazolidone, lubricating oil and lubricating grease, and can replace ethylene oxide to be used for a dioxygenation reaction; the organic solvent is also an organic solvent with excellent performance, and can be used as a solvent of various polymers, a solvent of acid gas, a spinning silk-drawing liquid and water glass series sizing agent; the product is also an auxiliary agent with excellent performance, and can be used as a plastic foaming agent, an additive of concrete, a stabilizer of synthetic lubricating oil and a fiber finishing agent; is one of indispensable components of the electrolyte of the high-efficiency lithium ion battery.
The preparation method of the ethylene carbonate mainly comprises a phosgene method, an ester exchange method, an ethylene oxide method and a urea method. The phosgene method is to prepare ethylene carbonate by taking phosgene and ethylene glycol as raw materials to react. Phosgene is eliminated because of its high toxicity and explosive property. The ester exchange method is to prepare ethylene carbonate by taking dimethyl carbonate or diethyl carbonate and ethanol as raw materials through ester exchange reaction. Because the raw material dimethyl carbonate or diethyl carbonate is high in price and the reaction yield is low, the production cost is high, and the raw material dimethyl carbonate or diethyl carbonate is rarely used industrially. The ethylene oxide method is the main method for producing ethylene carbonate industrially at present, and ethylene oxide and CO are used2The ethylene carbonate is prepared from raw materials through an addition reaction, but the method has the characteristics of huge potential safety hazard and high cost in the production process due to the wide explosion limit (3-100%) and high price of ethylene oxide. The urea method is a new method for preparing ethylene carbonate in recent years, and the ethylene carbonate is prepared by reacting urea and ethylene glycol as raw materials.The method has the characteristics of cheap and easily obtained raw materials of urea and ethylene glycol, mild reaction conditions, low production cost, environment-friendly and safe process and the like, and the published literature data shows that organic tin compounds, metal oxides, alkali and inorganic salts have certain catalytic action on the reaction of urea and ethylene glycol for preparing the ethylene carbonate. Wherein the metal oxide catalyst is selected from Zn/Cu oxide, Zn/Fe oxide, Zn/Mg oxide, Zn/A1 oxide, especially Zn (NO)3)2·6H2The ZnO catalyst prepared by mixing O and urea has a good catalytic effect on the reaction of urea and ethylene glycol to prepare ethylene carbonate, and the yield of ethylene carbonate can reach 63.32-93.6% (based on urea). In order to further increase the yield of ethylene carbonate, making the urea process more attractive for the preparation of ethylene carbonate, it is necessary to develop a more efficient catalyst.
Disclosure of Invention
The invention provides a catalyst for synthesizing ethylene carbonate, a preparation method and application thereof, aiming at further improving the yield of the ethylene carbonate prepared by the existing urea method.
In order to realize the purpose, the invention is realized by the following technical scheme:
one aspect of the present invention provides a catalyst for synthesizing ethylene carbonate, which is a composite oxide composed of Zn and one or two of La and Co. When the catalyst is a composite oxide consisting of Zn and La or Co elements, the Zn, La and Co elements are ZnO and La respectively2O3、Co3O4Calculated by the presence of the morphology of ZnO and La2O3Or Co3O4The mass ratio of (A) to (B) is 1-99: 99-1; when the catalyst is a composite oxide consisting of three elements of Zn, La and Co, the elements of Zn, La and Co are ZnO and La respectively2O3、Co3O4Calculated by the presence of the morphology of ZnO and La2O3-Co3O4The mass ratio of the sum is 1-99: 99 to 1, wherein La2O3And Co3O4The mass ratio of (A) to (B) is 1-99: 99-1.
Another aspect of the present invention provides a preparation method of the catalyst for synthesizing ethylene carbonate, including the following steps:
step 1: adding Zn (NO)3)2·6H2O、La(NO3)3·6H2O and Co (NO)3)2·6H2Dissolving O in water to prepare an aqueous solution of zinc nitrate, an aqueous solution of lanthanum nitrate and an aqueous solution of cobalt nitrate respectively, preparing an aqueous solution of urea as a precipitator, and preparing an aqueous solution of sodium hydroxide as a pH value regulator;
step 2: mixing an aqueous solution of zinc nitrate, an aqueous solution of lanthanum nitrate and an aqueous solution of cobalt nitrate according to the set composition of the catalyst, adding the mixed aqueous solutions into an aqueous solution of urea to perform a coprecipitation reaction, dropwise adding an aqueous solution of sodium hydroxide, and controlling the pH value of the coprecipitation reaction;
and step 3: aging after complete precipitation, filtering, and washing the filter cake with deionized water until no Na remains in the eluate+Until detecting;
and 4, step 4: and drying the filter cake, and calcining in an air atmosphere to obtain the composite oxide catalyst.
Furthermore, the concentration of the zinc nitrate aqueous solution is 5-50 wt%, the concentration of the lanthanum nitrate aqueous solution is 5-45 wt%, the concentration of the cobalt nitrate aqueous solution is 5-50 wt%, the concentration of the urea aqueous solution is 20-50 wt%, and the concentration of the sodium hydroxide aqueous solution is 1-10 wt%. The concentrations of the aqueous solutions of the zinc nitrate, the lanthanum nitrate and the cobalt nitrate are lower than the saturated concentrations of the nitrates at 25 ℃, so that the uniform mixing of the components in the preparation of the mixed solution is facilitated, and the phenomenon that the precipitation of the nitrates due to supersaturation affects the uniform distribution of the active components and further causes the uneven distribution of the active components in the coprecipitation is avoided. The concentration of the precipitator urea aqueous solution is set to be 20-50 wt%, which is beneficial to complete precipitation of metal ions. The pH value regulator of sodium hydroxide with the concentration of 1-10 wt% is prepared in the invention, which is beneficial to controlling the uniformity of precipitated particles.
Further, the temperature of the coprecipitation reaction in the step 2 is 25-60 ℃, and the pH value of the reaction is 8-13. The temperature is too low, the molecular kinetic energy of the solute is small, and the crystal with uniformly distributed active components is not favorably obtained; but the temperature is too high, the molecular kinetic energy of the solute is increased too fast, and the formation of stable crystals is not facilitated, the coprecipitation reaction temperature is set to be 25-60 ℃, and the crystals with uniformly distributed active components and stable structures are obtained.
Further, the aging time in the step 3 is 4-48 hours. The aging time is 4-48 hours, which is beneficial to obtaining crystals with moderate particle size and uniform distribution.
Further, in the step 4, the drying temperature is 80-120 ℃, and the drying time is 4-48 hours. The drying temperature is too low to facilitate the water evaporation in the macropores and micropores of the crystal, and the water evaporation in the macropores and micropores of the crystal is too fast due to too high temperature, so that the strength of the crystal is reduced or the structure is damaged. The drying temperature is set to 80-120 ℃, so that the water in macropores and micropores in the crystal can be evaporated, and the strength of the crystal cannot be reduced or the structure cannot be damaged.
Further, in the step 4, the calcining temperature is 450-1000 ℃, and the calcining time is 4-48 hours. The invention sets the calcination temperature at 450-1000 ℃ to be beneficial to obtaining the composite metal oxide catalyst with higher strength. When the temperature exceeds 1000 ℃, part of active metal can be sintered, and the activity of the catalyst is reduced; temperatures below 450 c can affect the strength of the catalyst. The calcination time is 4-48 hours, which is beneficial to obtaining the composite metal oxide catalyst with sufficient oxidation.
Another aspect of the present invention provides an application of the above composite oxide catalyst in preparation of ethylene carbonate by reaction of ethylene glycol and urea, specifically: adding a composite oxide catalyst with 0.5-10% of the mass of urea into a mixture of ethylene glycol and urea with a molar ratio of 1-5: 1, maintaining the reaction pressure at-0.01-0.09 MPa, the reaction temperature at 120-170 ℃ and the reaction time at 1-5 hours, and obtaining the ethylene carbonate product with high yield.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation process of the catalyst is simple and easy to implement, and the cost is low;
(2) the catalyst has high activity, mild reaction conditions and high yield of the ethylene carbonate;
(3) the catalyst of the invention has good stability, more times of repeated use and easy separation and regeneration.
Detailed Description
The following examples are given in the detailed description and the specific operation on the premise of the technical solutions of the present invention, but do not limit the protection scope of the patent of the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations should fall within the protection scope of the present invention.
Example 1
Zn (NO) according to the set catalyst composition3)2·6H2O and La (NO)3)3·6H2Dissolving O in water respectively to prepare 5 wt% of zinc nitrate and 45 wt% of lanthanum nitrate aqueous solution, preparing 20 wt% of urea aqueous solution as a precipitator, and preparing 1 wt% of sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution and lanthanum nitrate aqueous solution into a precipitator urea aqueous solution at 25 ℃ for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value in the coprecipitation process to be kept within 8. Aging for 48 hours after complete precipitation, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. Drying the obtained filter cake at 80 ℃ for 48 hours, and calcining the filter cake at 450 ℃ in air atmosphere for 48 hours to obtain the filter cake containing ZnO and La2O3The mass ratio of morphology calculation is 1: 99 of a Zn-La composite oxide catalyst.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 1:1, the adding amount of the Zn-La composite oxide catalyst is 10 percent of the mass of the urea, the reaction pressure is-0.01 MPa, the reaction temperature is 170 ℃, and the reaction time is 1 hour. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. Through analysis and calculation, the urea conversion rate is 99.5%, and the ethylene carbonate yield is 80.6%.
Example 2
Zn (NO) according to the set catalyst composition3)2·6H2O and La (NO)3)3·6H2Dissolving O in water respectively to prepare 25 wt% of zinc nitrate and 20 wt% of lanthanum nitrate aqueous solution, preparing 35 wt% of urea aqueous solution as a precipitator, and preparing 5 wt% of sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution and lanthanum nitrate aqueous solution into a precipitator urea aqueous solution at 40 ℃ for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value in the coprecipitation process to be kept within 13. Aging for 20 hours after complete precipitation, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. Drying the obtained filter cake at 120 deg.C for 4 hr, and calcining at 1000 deg.C in air atmosphere for 4 hr to obtain the final product containing ZnO and La2O3The mass ratio of morphology calculation is 6: 4, a Zn-La composite oxide catalyst.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 2.5:1, the adding amount of the Zn-La composite oxide catalyst is 5 percent of the mass of the urea, the reaction pressure is-0.05 MPa, the reaction temperature is 155 ℃, and the reaction time is 3 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. Through analysis and calculation, the urea conversion rate is 100%, and the ethylene carbonate yield is 92.5%.
Example 3
Zn (NO) according to the set catalyst composition3)2·6H2O and La (NO)3)3·6H2Dissolving O in water respectively to prepare 50 wt% zinc nitrate and 5 wt% lanthanum nitrate aqueous solution, preparing 50 wt% urea aqueous solution as a precipitator, and preparing 10 wt% sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution and lanthanum nitrate aqueous solution into a precipitator urea aqueous solution at 60 DEG CAnd (3) carrying out coprecipitation reaction, and dropwise adding a sodium hydroxide aqueous solution serving as a pH value regulator to control the pH value in the coprecipitation process to be kept within 10. Aging for 22 hours after the precipitation is completed, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. The obtained filter cake is dried at 100 ℃ for 24 hours and then calcined at 800 ℃ in an air atmosphere for 20 hours to obtain the product containing ZnO and La2O3The mass ratio of morphology calculation is 99: 1, a Zn-La composite oxide catalyst.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 2.0:1, the adding amount of the Zn-La composite oxide catalyst is 3.5 percent of the mass of the urea, the reaction pressure is-0.06 MPa, the reaction temperature is 150 ℃, and the reaction time is 2.5 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. The analysis calculation shows that the urea conversion rate is 100 percent and the ethylene carbonate yield is 93.8 percent.
Example 4
Zn (NO) according to the set catalyst composition3)2·6H2O and Co (NO)3)2·6H2Dissolving O in water to prepare 10 wt% of zinc nitrate and 25 wt% of cobalt nitrate aqueous solution, simultaneously preparing 30 wt% of urea aqueous solution as a precipitator, and preparing 1 wt% of sodium hydroxide aqueous solution as a PH value regulator.
Adding the prepared zinc nitrate aqueous solution and cobalt nitrate aqueous solution into a precipitator urea aqueous solution at 40 ℃ for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value in the coprecipitation process to be kept within 10. Aging for 24 hours after complete precipitation, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. The obtained filter cake is dried at 80 ℃ for 24 hours and then calcined at 600 ℃ in air atmosphere for 34 hours to obtain the ZnO and Co3O4The mass ratio of morphology calculation is 3: 7 is a Zn-Co composite oxide catalyst.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 5:1, the adding amount of the Zn-Co composite oxide catalyst is 0.5 percent of the mass of the urea, the reaction pressure is-0.09 MPa, the reaction temperature is 120 ℃, and the reaction time is 5 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. Through analysis and calculation, the urea conversion rate is 99.0%, and the ethylene carbonate yield is 85.3%.
Example 5
Zn (NO) according to the set catalyst composition3)2·6H2O and Co (NO)3)2·6H2Dissolving O in water to prepare 5 wt% of zinc nitrate and 50 wt% of cobalt nitrate aqueous solution, simultaneously preparing 30 wt% of urea aqueous solution as a precipitator, and preparing 5 wt% of sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution and cobalt nitrate aqueous solution into a precipitator urea aqueous solution at 25 ℃ for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value in the coprecipitation process to be kept within 11. Aging for 20 hours after complete precipitation, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. The obtained filter cake is dried at 80 ℃ for 21 hours and then calcined at 500 ℃ in air atmosphere for 19 hours to obtain the ZnO and Co3O4The mass ratio of morphology calculation is 1: 99 of a Zn-Co composite oxide catalyst.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 1.5:1, the adding amount of the Zn-Co composite oxide catalyst is 2 percent of the mass of the urea, the reaction pressure is-0.07 MPa, the reaction temperature is 145 ℃, and the reaction time is 3 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. The analysis calculation shows that the urea conversion rate is 100 percent and the ethylene carbonate yield is 72.5 percent.
Example 6
Zn (NO) according to the set catalyst composition3)2·6H2O and Co (NO)3)2·6H2Dissolving O in water to prepare 50 wt% zinc nitrate and 5 wt% cobalt nitrate aqueous solution, and preparing concentrated solutionUrea aqueous solution with the concentration of 40 wt% is used as a precipitator, and sodium hydroxide aqueous solution with the concentration of 10 wt% is prepared to be used as a PH value regulator.
Adding the prepared zinc nitrate aqueous solution and cobalt nitrate aqueous solution into a precipitator urea aqueous solution at 60 ℃ for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value in the coprecipitation process to be kept within 8. Aging for 6 hours after complete precipitation, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. Drying the obtained filter cake at 90 ℃ for 12 hours, and calcining the filter cake at 450 ℃ in air atmosphere for 48 hours to obtain the ZnO and Co3O4The mass ratio of morphology calculation is 99: 1, a Zn-Co composite oxide catalyst.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 2.5:1, the addition amount of the Zn-Co composite oxide catalyst is 5 percent of the mass of the urea, the reaction pressure is-0.02 MPa, the reaction temperature is 165 ℃, and the reaction time is 3 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. Through analysis and calculation, the urea conversion rate is 99.8%, and the ethylene carbonate yield is 92.1%.
Example 7
Zn (NO) according to the set catalyst composition3)2·6H2O、La(NO3)3·6H2O and Co (NO)3)2·6H2Dissolving O in water respectively to prepare 20 wt% of zinc nitrate, 20 wt% of lanthanum nitrate and 15 wt% of cobalt nitrate aqueous solution, preparing 30 wt% of urea aqueous solution as a precipitator and preparing 5 wt% of sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution, lanthanum nitrate aqueous solution and cobalt nitrate aqueous solution into a precipitator urea aqueous solution at 45 ℃ according to the composition requirement set by a catalyst for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value of the coprecipitation process to be kept within 9. Aging for 8 hours after the precipitation is completed, then filtering, and washing a filter cake by deionized water until the filter cake is washed outNo residual Na in the solution+Until the detection. Drying the obtained filter cake at 100 deg.C for 10 hr, and calcining at 700 deg.C in air atmosphere for 20 hr to obtain the final product containing ZnO and La2O3And Co3O4A Zn-La-Co composite oxide catalyst in a morphometric calculated mass ratio of 7:2: 1.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 2.5:1, the adding amount of the Zn-La-Co composite oxide catalyst is 7 percent of the mass of the urea, the reaction pressure is-0.06 MPa, the reaction temperature is 155 ℃, and the reaction time is 3 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. The analysis calculation shows that the urea conversion rate is 100 percent and the ethylene carbonate yield is 95.7 percent.
Example 8
Zn (NO) according to the set catalyst composition3)2·6H2O、La(NO3)3·6H2O and Co (NO)3)2·6H2Dissolving O in water respectively to prepare 5 wt% of zinc nitrate, 45 wt% of lanthanum nitrate and 5 wt% of cobalt nitrate aqueous solution, preparing 50 wt% of urea aqueous solution as a precipitator and preparing 10 wt% of sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution, lanthanum nitrate aqueous solution and cobalt nitrate aqueous solution into a precipitator urea aqueous solution at 25 ℃ according to the composition requirement set by a catalyst for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value of the coprecipitation process to be kept within 8. Aging for 44 hours after the precipitation is completed, then filtering, and washing the filter cake by deionized water until no Na residue exists in the eluate+Until the detection. Drying the obtained filter cake at 100 deg.C for 8 hr, and calcining at 600 deg.C in air atmosphere for 24 hr to obtain the final product containing ZnO and La2O3And Co3O4A Zn-La-Co composite oxide catalyst with a morphometric calculated mass ratio of 1:98: 1.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 2.5:1, the adding amount of the Zn-La-Co composite oxide catalyst is 5 percent of the mass of the urea, the reaction pressure is-0.05 MPa, the reaction temperature is 155 ℃, and the reaction time is 3 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. The analysis calculation shows that the urea conversion rate is 100 percent and the ethylene carbonate yield is 85.6 percent.
Example 9
Zn (NO) according to the set catalyst composition3)2·6H2O、La(NO3)3·6H2O and Co (NO)3)2·6H2Dissolving O in water respectively to prepare 5 wt% of zinc nitrate, 10 wt% of lanthanum nitrate and 50 wt% of cobalt nitrate aqueous solution, preparing 20 wt% of urea aqueous solution as a precipitator and preparing 8 wt% of sodium hydroxide aqueous solution as a pH value regulator.
Adding the prepared zinc nitrate aqueous solution, lanthanum nitrate aqueous solution and cobalt nitrate aqueous solution into a precipitator urea aqueous solution at 40 ℃ according to the composition requirement set by a catalyst for coprecipitation reaction, and dropwise adding a pH value regulator sodium hydroxide aqueous solution to control the pH value of the coprecipitation process to be kept within 10. Aging for 12 hours after complete precipitation, then performing suction filtration, and washing a filter cake by deionized water until no Na residue exists in an eluate+Until the detection. Drying the obtained filter cake at 90 deg.C for 18 hr, and calcining at 550 deg.C in air atmosphere for 20 hr to obtain the final product containing ZnO and La2O3And Co3O4A Zn-La-Co composite oxide catalyst with a morphometric calculated mass ratio of 1:1: 98.
The reaction of urea and ethylene glycol is carried out in a three-neck flask under the following reaction conditions: the molar ratio of the ethylene glycol to the urea is 2.5:1, the adding amount of the Zn-La-Co composite oxide catalyst is 8 percent of the mass of the urea, the reaction pressure is-0.05 MPa, the reaction temperature is 155 ℃, and the reaction time is 2.5 hours. After a small amount of reaction solution sample was centrifuged, the product composition was analyzed by gas chromatography using the supernatant. Through analysis and calculation, the urea conversion rate is 95%, and the ethylene carbonate yield is 80.5%.
Example 10
A Zn-La-Co composite oxide catalyst was prepared and a synthesis reaction of ethylene carbonate was carried out under the conditions of example 7. The reaction with the addition of fresh Zn-La-Co composite oxide catalyst is the first reaction. After the first reaction is finished and the sample is taken, the liquid in the three-neck flask is distilled out, the catalyst is remained in the three-neck flask, and then only the ethylene glycol and the urea are added into the three-neck flask to carry out the second reaction. After the second reaction is finished and the sample is taken, the liquid in the three-neck flask is distilled out, the catalyst is left in the three-neck flask, and then only the ethylene glycol and the urea are added into the three-neck flask to carry out the third reaction. The operation is carried out until the tenth reaction is finished. The results of the ten reactions are given in the following table:
| number of reaction times | Urea conversion (%) | Ethylene carbonate yield (%) |
| For the first time | 100 | 95.6 |
| For the second time | 100 | 95.1 |
| The third time | 100 | 94.6 |
| Fourth time | 100 | 94.0 |
| Fifth time | 100 | 93.3 |
| The sixth time | 100 | 92.8 |
| The seventh time | 100 | 91.2 |
| The eighth time | 100 | 90.5 |
| The ninth time | 99.8 | 87.8 |
| The tenth time | 99.1 | 83.7 |
Claims (9)
1. The catalyst for synthesizing the ethylene carbonate is characterized in that the catalyst is a composite oxide consisting of one or two of Zn, La and Co.
2. The catalyst for synthesizing ethylene carbonate according to claim 1, wherein when the catalyst is a composite oxide composed of Zn and La or Co, the Zn, La and Co elements are ZnO and La, respectively2O3、Co3O4Calculated by the presence of the morphology of ZnO and La2O3Or Co3O4In a mass ratio of 1-99: 99-1; when the catalyst is a composite oxide consisting of three elements of Zn, La and Co, the elements of Zn, La and Co are ZnO and La respectively2O3、Co3O4Calculated by the presence of the morphology of ZnO and La2O3-Co3O4The mass ratio of the sum is 1-99: 99 to 1, wherein La2O3And Co3O4The mass ratio of (A) to (B) is 1-99: 99-1.
3. A method for preparing a catalyst for synthesizing ethylene carbonate according to claim 1 or 2, comprising the steps of:
step 1: adding Zn (NO)3)2·6H2O、La(NO3)3·6H2O and Co (NO)3)2·6H2Dissolving O in water to prepare an aqueous solution of zinc nitrate, an aqueous solution of lanthanum nitrate and an aqueous solution of cobalt nitrate respectively, preparing an aqueous solution of urea as a precipitator, and preparing an aqueous solution of sodium hydroxide as a pH value regulator;
step 2: mixing an aqueous solution of zinc nitrate, an aqueous solution of lanthanum nitrate and an aqueous solution of cobalt nitrate according to the set composition of the catalyst, adding the mixed aqueous solutions into an aqueous solution of urea to perform a coprecipitation reaction, dropwise adding an aqueous solution of sodium hydroxide, and controlling the pH value of the coprecipitation reaction;
and step 3: aging after complete precipitation, filtering, and washing the filter cake with deionized water until no Na remains in the eluate+Until detecting;
and 4, step 4: and drying the filter cake, and calcining in an air atmosphere to obtain the composite oxide catalyst.
4. The method according to claim 3, wherein the concentration of the aqueous solution of zinc nitrate is 5 to 50 wt%, the concentration of the aqueous solution of lanthanum nitrate is 5 to 45 wt%, the concentration of the aqueous solution of cobalt nitrate is 5 to 50 wt%, the concentration of the aqueous solution of urea is 20 to 50 wt%, and the concentration of the aqueous solution of sodium hydroxide is 1 to 10 wt%.
5. The method for preparing the catalyst for synthesizing ethylene carbonate according to claim 3, wherein the temperature of the coprecipitation reaction in the step 2 is 25 to 60 ℃, and the pH value of the reaction is 8 to 13.
6. The method for preparing a catalyst for synthesizing ethylene carbonate according to claim 3, wherein the aging time in the step 3 is 4-48 hours.
7. The method for preparing a catalyst for synthesizing ethylene carbonate according to claim 3, wherein the drying temperature in the step 4 is 80-120 ℃ and the drying time is 4-48 hours.
8. The method for preparing a catalyst for synthesizing ethylene carbonate according to claim 3, wherein the calcination temperature in the step 4 is 450-1000 ℃ and the calcination time is 4-48 hours.
9. The application of the catalyst for synthesizing ethylene carbonate according to claim 1 or 2, wherein when ethylene glycol and urea are reacted to prepare ethylene carbonate, a composite oxide catalyst with 0.5-10% of the mass of urea is added into a mixture of ethylene glycol and urea with a molar ratio of 1-5: 1, the reaction pressure is maintained at-0.01-0.09 MPa, the reaction temperature is 120-170 ℃, and the reaction time is 1-5 hours, so that an ethylene carbonate product can be obtained with high yield.
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