CN117326946B - Method for preparing ethyl acetate from ethanol - Google Patents
Method for preparing ethyl acetate from ethanol Download PDFInfo
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- CN117326946B CN117326946B CN202311628265.1A CN202311628265A CN117326946B CN 117326946 B CN117326946 B CN 117326946B CN 202311628265 A CN202311628265 A CN 202311628265A CN 117326946 B CN117326946 B CN 117326946B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 142
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000012530 fluid Substances 0.000 claims description 9
- 230000008016 vaporization Effects 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 alcoholysis Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
-
- 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
- B01J23/83—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
-
- 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
- B01J37/088—Decomposition of a metal salt
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of ethyl acetate production, in particular to a method for preparing ethyl acetate from ethanol; according to the method provided by the invention, the ethanol solution is gasified and then enters a fixed bed reactor loaded with the catalyst for gas phase catalytic dehydrogenation reaction, so that the ethyl acetate is prepared. The method provided by the invention has wider market prospect and is more suitable for popularization.
Description
Technical Field
The invention relates to the technical field of ethyl acetate production, in particular to a method for preparing ethyl acetate from ethanol.
Background
Ethyl acetate, also known as ethyl acetate, is an organic compound, an ester with a functional group-COOR (double bond between carbon and oxygen), and can undergo common reactions of common esters such as alcoholysis, ammonolysis, transesterification, reduction and the like, and is mainly used as a solvent, a food flavor and a cleaning and degreasing agent.
Ethyl acetate is used as an efficient green solvent, and with the development of global economy, the demand is increasing. The method for preparing ethyl acetate by directly catalyzing and dehydrogenating ethanol has the advantages of low cost, small equipment corrosion, no toxicity and the like, and is a main method for preparing ethyl acetate at present, but the existing method for preparing ethyl acetate by ethanol, such as the patent application number CN1062304, has the problem of low conversion rate of ethanol.
Accordingly, the present invention provides a method for preparing ethyl acetate from ethanol, which is used for solving the above-mentioned related technical problems.
Disclosure of Invention
The invention aims to provide a method for preparing ethyl acetate from ethanol, which has higher selectivity and yield, has obvious effect when being applied to the aspect of preparing ethyl acetate from ethanol, and has good stability in the process of preparing ethyl acetate from ethanol.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a method for preparing ethyl acetate from ethanol, which comprises the steps of vaporizing an ethanol solution, then introducing the vaporized ethanol solution into a fixed bed reactor loaded with a catalyst for gas-phase catalytic dehydrogenation reaction, and preparing the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material in proper amount of pure water for 20-30 min according to the solid-liquid ratio of 0.02-0.05 g/mL; after the ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion to 9.0-10.0, raising the temperature to 75-85 ℃, and carrying out heat preservation treatment for 120-130 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
putting hexadecyl trimethyl ammonium bromide into a proper amount of compound liquid according to the solid-liquid ratio of 0.12-0.14 g/mL, and adding ammonia water with the volume of 1.2% of the compound liquid; treating for 30-36 min at 36-40 ℃ under 120-140 r/min, then adding tetraethyl silicate with the same volume as ammonia water, treating for 26-28 h at 36-40 ℃ under 120-140 r/min, centrifuging and washing the obtained product, then placing the product in deionized water with the concentration of 3-4 times, treating for 12-14 h at 60-70 ℃, centrifuging and washing the obtained product again, placing the product in treatment fluid, treating for 4-6 h at 50-60 ℃, centrifuging, washing and drying the product to obtain the carrier;
placing the carrier into a proper amount of mixed solution according to the solid-liquid ratio of 0.22-0.26 g/mL, performing ultrasonic dispersion, then treating for 12-14 h at 36-40 ℃ and 310-360 r/min, after the reaction is finished, filtering by a vacuum pump, washing a filter cake with deionized water for 3-4 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain the catalyst.
The invention is further provided with: the compound material is prepared from copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.3-0.6: 0.5 to 0.8:1 are mixed and compounded.
The invention is further provided with: the compound liquid is prepared from ethanol and water according to the volume ratio of 0.4-0.8: 1 are mixed and compounded.
The invention is further provided with: the treatment fluid is prepared from hydrogen chloride and ethanol according to the volume ratio of 4-6: 1 are mixed and compounded.
The invention is further provided with: the calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
The invention is further provided with: the granularity of the catalyst is 40-120 meshes.
The invention is further provided with: the reaction temperature of the gas phase catalytic dehydrogenation reaction is 220-260 ℃ and the reaction pressure is 1.0-3.0 MPa.
The invention is further provided with: before vaporizing ethanol solution and introducing the vaporized ethanol solution into a fixed bed reactor loaded with catalyst for gas phase catalytic dehydrogenation reaction, introducing the catalyst into H 2 Heating to 280-290 ℃ at a speed of 4-5 ℃/min under the atmosphere, and reducing for 4-6 h at the temperature, H 2 The airspeed of the gas is 500 to 2000 hours -1 Then in H 2 Cooling to the reaction temperature of 220-260 ℃ under the atmosphere.
The invention is further provided with: the catalyst loading is 3-10 g, and the sample injection flow rate is 12mL/h.
Compared with the prior art, the invention has the beneficial effects that:
according to the method provided by the invention, the ethanol solution is gasified and then enters a fixed bed reactor loaded with the catalyst for gas phase catalytic dehydrogenation reaction, so that the ethyl acetate is prepared. The method provided by the invention has wider market prospect and is more suitable for popularization.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a statistical plot of ethanol conversion in accordance with the present invention;
FIG. 2 is a statistical plot of ethyl acetate selectivity of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one: the embodiment provides a method for preparing ethyl acetate from ethanol, which comprises the steps of vaporizing an ethanol solution, then introducing the vaporized ethanol solution into a fixed bed reactor loaded with a catalyst for gas-phase catalytic dehydrogenation reaction, and preparing the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material into a proper amount of pure water for 20 min according to a solid-liquid ratio of 0.02 g/mL; after the ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion to 9.0, heating to 75 ℃, and carrying out heat preservation treatment for 120 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
the hexadecyl trimethyl ammonium bromide is placed into a proper amount of compound liquid according to the solid-liquid ratio of 0.12g/mL, and then ammonia water with the volume of 1.2% of the compound liquid is added; treating for 30min at 36 ℃ under 120r/min, then adding tetraethyl silicate with the same volume as ammonia water, treating for 26h at 36 ℃ under 120r/min, centrifuging and washing the obtained product, then placing the product in deionized water which is 3 times of the product, treating for 12h at 60 ℃, centrifuging and washing the obtained product again, placing the product in a treatment solution, treating for 4h at 50 ℃, centrifuging, washing and drying the product to obtain a carrier;
placing the carrier in a proper amount of mixed solution according to the solid-liquid ratio of 0.22 g/mL, performing ultrasonic dispersion, then treating for 12 hours at 36 ℃ and 310r/min, filtering by a vacuum pump after the reaction is finished, washing a filter cake with deionized water for 3 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain the catalyst.
Wherein the compound material comprises copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.3:0.5:1 are mixed and compounded.
The compound liquid is prepared from ethanol and water according to the volume ratio of 0.4:1 are mixed and compounded.
The treatment fluid is prepared from hydrogen chloride and ethanol according to a volume ratio of 4:1 are mixed and compounded.
Calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
The particle size of the catalyst was 40 mesh.
The reaction temperature of the gas phase catalytic dehydrogenation reaction is 220 ℃ and the reaction pressure is 1.0MPa.
Before the ethanol solution is gasified and enters a fixed bed reactor loaded with a catalyst for gas phase catalytic dehydrogenation reaction, the catalyst is heated to 280 ℃ at a speed of 4 ℃/min under the H2 atmosphere, reduced for 4H at the temperature, the space velocity of H2 gas is 500H < -1 >, and then cooled to the reaction temperature of 220 ℃ under the H2 atmosphere.
The catalyst loading was 3g and the sample injection flow rate was 12mL/h.
Embodiment two: the embodiment provides a method for preparing ethyl acetate from ethanol, which comprises the steps of vaporizing an ethanol solution, then introducing the vaporized ethanol solution into a fixed bed reactor loaded with a catalyst for gas-phase catalytic dehydrogenation reaction, and preparing the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material into a proper amount of pure water for 22 min according to the solid-liquid ratio of 0.03 g/mL; after the ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion to 9.0, heating to 77 ℃, and carrying out heat preservation treatment for 122 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
cetyl trimethyl ammonium bromide is placed into a proper amount of compound liquid according to the solid-to-liquid ratio of 0.13 g/mL, and then ammonia water with the volume of 1.2% of the compound liquid is added; treating for 32min at 37 ℃ under 125r/min, then adding tetraethyl silicate with the same volume as ammonia water, treating for 27h at 37 ℃ under 122r/min, centrifuging and washing the obtained product, then placing the product in 4 times deionized water, treating for 13h at 62 ℃, centrifuging and washing the obtained product again, placing the product in a treatment solution, treating for 5h at 52 ℃, centrifuging, washing and drying the product to obtain a carrier;
placing the carrier in a proper amount of mixed solution according to the solid-liquid ratio of 0.23 g/mL, performing ultrasonic dispersion, then treating for 13h at 37 ℃ and 320r/min, filtering by a vacuum pump after the reaction is finished, washing a filter cake with deionized water for 4 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain the catalyst.
Wherein the compound material comprises copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.4:0.6:1 are mixed and compounded.
The compound liquid is prepared from ethanol and water according to the volume ratio of 0.5:1 are mixed and compounded.
The treatment fluid is prepared from hydrogen chloride and ethanol according to a volume ratio of 5:1 are mixed and compounded.
Calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
The particle size of the catalyst was 50 mesh.
The reaction temperature of the gas phase catalytic dehydrogenation reaction is 230 ℃ and the reaction pressure is 2.0MPa.
Before the ethanol solution is gasified and enters a fixed bed reactor loaded with a catalyst for gas phase catalytic dehydrogenation reaction, the catalyst is heated to 282 ℃ at 5 ℃/min under the H2 atmosphere, reduced for 5H at the temperature, the space velocity of H2 gas is 600H < -1 >, and then cooled to the reaction temperature of 230 ℃ under the H2 atmosphere.
The catalyst loading was 4g and the sample injection flow rate was 12mL/h.
Embodiment III: the embodiment provides a method for preparing ethyl acetate from ethanol, which comprises the steps of vaporizing an ethanol solution, then introducing the vaporized ethanol solution into a fixed bed reactor loaded with a catalyst for gas-phase catalytic dehydrogenation reaction, and preparing the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material into proper amount of pure water for 25min according to the solid-liquid ratio of 0.03 g/mL; after ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion liquid to 10.0, heating to 80 ℃, and carrying out heat preservation treatment for 125 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
cetyl trimethyl ammonium bromide is placed into a proper amount of compound liquid according to the solid-to-liquid ratio of 0.13 g/mL, and then ammonia water with the volume of 1.2% of the compound liquid is added; treating for 33min at 38deg.C and 130r/min, adding tetraethyl silicate equal in volume to ammonia water, treating for 27h at 38deg.C and 130r/min, centrifuging and washing the obtained product, placing in 4 times deionized water, treating for 13h at 65deg.C, centrifuging and washing the obtained product again, placing in treating liquid, treating for 5h at 55deg.C, centrifuging, washing, and drying to obtain carrier;
placing the carrier in a proper amount of mixed solution according to the solid-liquid ratio of 0.24 g/mL, performing ultrasonic dispersion, then treating for 13h at 38 ℃ and 330r/min, filtering by a vacuum pump after the reaction is finished, washing a filter cake with deionized water for 4 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain the catalyst.
Wherein the compound material comprises copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.4:0.6:1 are mixed and compounded.
The compound liquid is prepared from ethanol and water according to the volume ratio of 0.6:1 are mixed and compounded.
The treatment fluid is prepared from hydrogen chloride and ethanol according to a volume ratio of 5:1 are mixed and compounded.
Calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
The particle size of the catalyst was 80 mesh.
The reaction temperature of the gas phase catalytic dehydrogenation reaction is 240 ℃ and the reaction pressure is 2.0MPa.
Before the ethanol solution is gasified and enters a fixed bed reactor loaded with a catalyst for gas phase catalytic dehydrogenation reaction, the catalyst is heated to 285 ℃ at 5 ℃/min under the H2 atmosphere, reduced for 5H at the temperature, the space velocity of H2 gas is 1250H < -1 >, and then cooled to the reaction temperature of 240 ℃ under the H2 atmosphere.
The catalyst loading was 7g and the sample injection flow rate was 12mL/h.
Embodiment four: the embodiment provides a method for preparing ethyl acetate from ethanol, which comprises the steps of vaporizing an ethanol solution, then introducing the vaporized ethanol solution into a fixed bed reactor loaded with a catalyst for gas-phase catalytic dehydrogenation reaction, and preparing the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material into a proper amount of pure water for 27min according to the solid-liquid ratio of 0.04 g/mL; after the ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion to 10.0, heating to 82 ℃, and carrying out heat preservation treatment for 127 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
cetyl trimethyl ammonium bromide is placed into a proper amount of compound liquid according to the solid-to-liquid ratio of 0.13 g/mL, and then ammonia water with the volume of 1.2% of the compound liquid is added; treating at 39deg.C and 135r/min for 35min, adding tetraethyl silicate equal in volume to ammonia water, treating at 39deg.C and 135r/min for 27h, centrifuging and washing the obtained product, placing in 4 times deionized water, treating at 67 deg.C for 13h, centrifuging and washing the obtained product again, placing in treating solution, treating at 57 deg.C for 5h, centrifuging, washing, and drying to obtain carrier;
placing the carrier in a proper amount of mixed solution according to the solid-liquid ratio of 0.25 g/mL, performing ultrasonic dispersion, then treating for 13h at 39 ℃ and 350r/min, filtering by a vacuum pump after the reaction is finished, washing a filter cake with deionized water for 4 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain the catalyst.
Wherein the compound material comprises copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.5:0.7:1 are mixed and compounded.
The compound liquid is prepared from ethanol and water according to the volume ratio of 0.7:1 are mixed and compounded.
The treatment fluid is prepared from hydrogen chloride and ethanol according to a volume ratio of 5:1 are mixed and compounded.
Calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
The particle size of the catalyst was 110 mesh.
The reaction temperature of the gas phase catalytic dehydrogenation reaction is 250 ℃ and the reaction pressure is 2.0MPa.
Before the ethanol solution is gasified and enters a fixed bed reactor loaded with a catalyst for gas phase catalytic dehydrogenation reaction, the catalyst is heated to 288 ℃ at 5 ℃/min under the H2 atmosphere, reduced for 5H at the temperature, the space velocity of H2 gas is 1800H < -1 >, and then cooled to the reaction temperature of 250 ℃ under the H2 atmosphere.
The catalyst loading was 9g and the sample injection flow rate was 12mL/h.
Fifth embodiment: the embodiment provides a method for preparing ethyl acetate from ethanol, which comprises the steps of vaporizing an ethanol solution, then introducing the vaporized ethanol solution into a fixed bed reactor loaded with a catalyst for gas-phase catalytic dehydrogenation reaction, and preparing the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material into a proper amount of pure water for 30min according to a solid-liquid ratio of 0.05 g/mL; after ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion liquid to 10.0, heating to 85 ℃, and carrying out heat preservation treatment for 130 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
cetyl trimethyl ammonium bromide is placed into a proper amount of compound liquid according to the solid-to-liquid ratio of 0.14 g/mL, and then ammonia water with the volume of 1.2% of the compound liquid is added; treating at 40deg.C for 36min at 140r/min, adding tetraethyl silicate equal in volume to ammonia water, treating at 40deg.C for 28 hr at 140r/min, centrifuging and washing the obtained product, standing in 4 times deionized water, treating at 70deg.C for 14 hr, centrifuging and washing the obtained product again, standing in treating liquid, treating at 60deg.C for 6 hr, centrifuging, washing, and drying to obtain carrier;
placing the carrier in a proper amount of mixed solution according to the solid-liquid ratio of 0.26 g/mL, performing ultrasonic dispersion, then treating for 14 hours at 40 ℃ and 360r/min, filtering by a vacuum pump after the reaction is finished, washing a filter cake with deionized water for 4 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain the catalyst.
Wherein the compound material comprises copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.6:0.8:1 are mixed and compounded.
The compound liquid is prepared from ethanol and water according to the volume ratio of 0.8:1 are mixed and compounded.
The treatment fluid is prepared from hydrogen chloride and ethanol according to a volume ratio of 6:1 are mixed and compounded.
Calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
The particle size of the catalyst was 120 mesh.
The reaction temperature of the gas phase catalytic dehydrogenation reaction is 260 ℃ and the reaction pressure is 3.0MPa.
Before the ethanol solution is gasified and enters a fixed bed reactor loaded with a catalyst for gas phase catalytic dehydrogenation reaction, the catalyst is heated to 290 ℃ at 5 ℃/min under the H2 atmosphere, reduced for 6H at the temperature, the space velocity of H2 gas is 2000H < -1 >, and then cooled to the reaction temperature of 2260 ℃ under the H2 atmosphere.
The catalyst loading was 10g and the sample injection flow rate was 12mL/h.
Test 1, conversion and selectivity test and analysis of the results: ethyl acetate was prepared from ethanol according to the methods of examples one to five, respectively (as example 1 group, example 2 group, example 3 group, example 4 group, and example 5 group, respectively). The products were analyzed by gas chromatography (internal standard method) and the test results are shown in Table 1.
As can be seen from table 1 and fig. 1 to 2, the methods of examples 1 to 5 can significantly improve the ethanol conversion rate and the ethyl acetate selectivity; while the difference in ethanol conversion and ethyl acetate selectivity between the groups of examples 1-5 is not significant. The results show that the methods of examples 1-5 have higher selectivity and yield, and have obvious effects when applied to the preparation of ethyl acetate from ethanol.
Test run 2, continuous reaction run and result analysis: continuous experiments were performed using the methods of examples one to five, respectively, and differences in ethanol conversion and ethyl acetate selectivity after initial 20, h, and reaction 250, h were recorded. The relevant data are recorded in table 2.
As can be seen from Table 2, the catalysts of the methods of examples 1 to 5 did not show significant differences in the conversion of ethanol and the selectivity of ethyl acetate in the production of ethyl acetate from ethanol after 250 hours; the above results indicate that the catalysts of the methods of examples 1-5 exhibit good stability in the process of preparing ethyl acetate from ethanol.
According to the method provided by the invention, the ethanol solution is gasified and then enters a fixed bed reactor loaded with the catalyst to carry out gas-phase catalytic dehydrogenation reaction, so that the ethyl acetate is prepared. Therefore, the method provided by the invention has wider market prospect and is more suitable for popularization.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (6)
1. A method for preparing ethyl acetate from ethanol is characterized in that ethanol solution is vaporized and then enters a fixed bed reactor loaded with a catalyst for gas phase catalytic dehydrogenation reaction to prepare the ethyl acetate;
the preparation method of the catalyst comprises the following steps:
ultrasonically dispersing the compound material in proper amount of pure water for 20-30 min according to the solid-liquid ratio of 0.02-0.05 g/mL; after the ultrasonic dispersion is finished, regulating the pH value of the obtained dispersion to 9.0-10.0, raising the temperature to 75-85 ℃, and carrying out heat preservation treatment for 120-130 min at the temperature;
after the heat preservation is finished, a mixed solution is obtained;
putting hexadecyl trimethyl ammonium bromide into a proper amount of compound liquid according to the solid-liquid ratio of 0.12-0.14 g/mL, and adding ammonia water with the volume of 1.2% of the compound liquid; treating for 30-36 min at 36-40 ℃ under 120-140 r/min, then adding tetraethyl silicate with the same volume as ammonia water, treating for 26-28 h at 36-40 ℃ under 120-140 r/min, centrifuging and washing the obtained product, then placing the product in deionized water with the concentration of 3-4 times, treating for 12-14 h at 60-70 ℃, centrifuging and washing the obtained product again, placing the product in treatment fluid, treating for 4-6 h at 50-60 ℃, centrifuging, washing and drying the product to obtain the carrier;
placing the carrier into a proper amount of mixed solution according to the solid-liquid ratio of 0.22-0.26 g/mL, performing ultrasonic dispersion, then treating for 12-14 h at 36-40 ℃ and 310-360 r/min, after the reaction is finished, filtering by a vacuum pump, washing a filter cake with deionized water for 3-4 times, and drying the filter cake to constant weight at 80 ℃;
calcining the dried filter cake in a tube furnace, cooling to room temperature, and grinding to obtain a catalyst;
the compound material is prepared from copper nitrate trihydrate, zinc nitrate hexahydrate and cerium nitrate hexahydrate according to the mass ratio of 0.3-0.6: 0.5 to 0.8:1, mixing and compounding;
the compound liquid is prepared from ethanol and water according to the volume ratio of 0.4-0.8: 1, mixing and compounding;
the treatment fluid is prepared from hydrogen chloride and ethanol according to the volume ratio of 4-6: 1 are mixed and compounded.
2. A process for the preparation of ethyl acetate from ethanol as claimed in claim 1, wherein: the calcination is divided into two stages, respectively as follows:
the first stage: heating to 500 ℃ at the speed of 10 ℃/min, and preserving heat and calcining for 3 hours;
and a second stage: cooling to 450 ℃ at a speed of 5 ℃/min, and preserving heat and calcining for 1h.
3. A process for the preparation of ethyl acetate from ethanol as claimed in claim 1, wherein: the granularity of the catalyst is 40-120 meshes.
4. A process for the preparation of ethyl acetate from ethanol as claimed in claim 1, wherein: the reaction temperature of the gas phase catalytic dehydrogenation reaction is 220-260 ℃ and the reaction pressure is 1.0-3.0 MPa.
5. A process for the preparation of ethyl acetate from ethanol as claimed in claim 1, wherein: before vaporizing ethanol solution and introducing the vaporized ethanol solution into a fixed bed reactor loaded with catalyst for gas phase catalytic dehydrogenation reaction, introducing the catalyst into H 2 Heating to 280-290 ℃ at a speed of 4-5 ℃/min under the atmosphere, and reducing for 4-6 h at the temperature, H 2 The airspeed of the gas is 500 to 2000 hours -1 Then in H 2 Cooling to the reaction temperature of 220-260 ℃ under the atmosphere.
6. A process for the preparation of ethyl acetate from ethanol as claimed in claim 1, wherein: the catalyst loading is 3-10 g, and the sample injection flow rate is 12mL/h.
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| GB1546004A (en) * | 1976-04-16 | 1979-05-16 | Mitsubishi Gas Chemical Co | Process for producing methyl formate |
| US4319037A (en) * | 1976-04-16 | 1982-03-09 | Mitsubishi Gas Chemical Company, Inc. | Process for producing methyl formate |
| US4565803A (en) * | 1983-12-16 | 1986-01-21 | Shell Oil Company | Methanol synthesis catalyst |
| EP0171804A2 (en) * | 1984-08-16 | 1986-02-19 | Union Carbide Corporation | Production of acetate esters from alcohols using rhodium complex catalysts |
| US6809217B1 (en) * | 1998-10-01 | 2004-10-26 | Davy Process Technology Limited | Process for the preparation of ethyl acetate |
| CN111774070A (en) * | 2020-07-13 | 2020-10-16 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing dehydrogenation of methanol, preparation method and application thereof |
| CN116162023A (en) * | 2021-11-24 | 2023-05-26 | 中国科学院大连化学物理研究所 | Method for preparing ethyl acetate by alcohol dehydrogenation condensation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1546004A (en) * | 1976-04-16 | 1979-05-16 | Mitsubishi Gas Chemical Co | Process for producing methyl formate |
| US4319037A (en) * | 1976-04-16 | 1982-03-09 | Mitsubishi Gas Chemical Company, Inc. | Process for producing methyl formate |
| US4565803A (en) * | 1983-12-16 | 1986-01-21 | Shell Oil Company | Methanol synthesis catalyst |
| EP0171804A2 (en) * | 1984-08-16 | 1986-02-19 | Union Carbide Corporation | Production of acetate esters from alcohols using rhodium complex catalysts |
| US6809217B1 (en) * | 1998-10-01 | 2004-10-26 | Davy Process Technology Limited | Process for the preparation of ethyl acetate |
| CN111774070A (en) * | 2020-07-13 | 2020-10-16 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing dehydrogenation of methanol, preparation method and application thereof |
| CN116162023A (en) * | 2021-11-24 | 2023-05-26 | 中国科学院大连化学物理研究所 | Method for preparing ethyl acetate by alcohol dehydrogenation condensation |
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