CN103230795A - Copper-based catalyst for preparing ethanol from acetic acid ester in hydrogenation manner and application of copper-based catalyst - Google Patents
Copper-based catalyst for preparing ethanol from acetic acid ester in hydrogenation manner and application of copper-based catalyst Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of ethanol from acetic acid ester in a hydrogenation manner, and particularly relates to a copper-based catalyst for preparing ethanol from acetic acid ester in a hydrogenation manner. The invention aims at solving the technical problem that a preparation method of a high-activity and high-selectivity ethanol catalyst prepared from the acetic acid ester in the hydrogenation manner is provided. The adopted technical scheme is that an active component of the catalyst is copper oxide; the ratio of copper to metal additive is 1:(0.8-3); and the catalyst is prepared from a precipitator by a coprecipitation method and applied to catalytic hydrogenation of the acetic acid ester. The copper-based catalyst is widely applied to the technical field of preparation of the ethanol from the acetic acid ester in the hydrogenation manner.
Description
Technical field
The present invention relates to acetic acid esters preparation of ethanol by hydrogenating technical field, is a kind of copper-based catalysts catalysis acetic acid esters preparation of ethanol by hydrogenating specifically.
Background technology
Ethanol is commonly called as alcohol, and its skeleton symbol is CH
3CH
2OH.Ethanol is important chemical material and fuel, and it is of many uses.It can be used as the solvent of organic synthesis, various washing agent, extractant etc.; The manufacturing raw material that can be used for agricultural chemicals, medicine, washing agent etc.; Equally, it also is a kind of clean energy resource, be again a kind of good gasoline oxygenation agent and octane number blend component, can partly substitute petroleum fuel, effectively reduce CO content in the tail gas, reduce environmental pollution, be called as 21 century " green energy resource ", according to estimates, 60% of ethanol production will be as vehicle fuel in the world wide.Yet, about the technology of preparing of ethanol, mainly adopt chemical synthesis route and biological fermentation process at present.In the chemical synthesis, traditional technologies such as ethylene hydration method, because the few oily many coals of China, its development has been subjected to very big restriction; Along with world food is in short supply, alcohol production has to turn to the developing direction of non-cereal crops as raw material.At present, the acetic acid synthesis from methanol carbonylation technology is ripe, acetic acid market is tending towards saturated, development is raw material with acetic acid, through intermediate product ethyl acetate hydrogenation preparing ethanol, can give full play to the advantage of rich coal resources in China, can possess and the advantage of traditional grain fermentation with the petroleum path competition.Simultaneously, can alleviate the predicament that present domestic acetic acid industry is in the serious surplus of production capacity, market continued downturn, develop its downstream industry chain.Therefore, exploitation acetic acid esters hydrogenation preparing ethanol is an important topic, and the effective catalyst that development is used for acetic acid esters hydrogenation preparing ethanol is the technological difficulties of this problem.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, a kind of preparation method of acetic acid esters hydrogenation preparing alcohol catalysis agent of high-activity high-selectivity is provided, specifically be to use acetic acid esters to pass through copper-based catalysts, direct hydrogenation preparing ethanol under mild reaction conditions, catalytic effect is greatly improved, the ethanol yield has industrial application value up to 95%.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of copper-based catalysts of acetic acid esters preparation of ethanol by hydrogenating, this activity of such catalysts component is cupric oxide, and wherein copper is 1:0.8-3 with the amount of substance ratio of metal promoter, and adopts following method to make:
Copper nitrate and metal promoter nitrate are 1:0.8-3 according to the amount of substance ratio, be dissolved in water and be mixed with the solution A that copper ion concentration is 0.5-1.0 mol/L, in solution A, dropwise add the precipitating reagent that concentration is 0.5-1.0 mol/L then, constantly stir simultaneously, drop to the pH value and stop to add precipitating reagent for 8-9, and at room temperature leave standstill, aging 10-24 hour, suction filtration, after getting filter cake and spending deionised water and be 6-8 to pH, at 100-120 ℃ of dry 8-12 hour, be cooled to room temperature, heating rate with 2-5 ℃/min is raised to 300-550 ℃ again, calcined 2-6 hour, and naturally cooled to room temperature, namely obtain copper-based catalysts.
Described metal promoter is one or more the mixture in aluminum nitrate, zinc nitrate, barium nitrate and the manganese nitrate.
Described precipitating reagent is sodium carbonate, NaOH or ammoniacal liquor.
A kind of method of copper-based catalysts catalysis acetic acid esters preparation of ethanol by hydrogenating: catalyst was reduced in hydrogen atmosphere 3-6 hour, reduction temperature 300-350 ℃, hydrogen flow rate 50-100 mL/min, the reduction back cools the temperature to 200-280 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of described hydrogen and acetic acid esters is 70-100:1, and the control reaction condition is: air speed 0.5-3 hr
-1, reaction temperature is 200-280 ℃, reaction pressure is 1.0-8.0 MPa, finishes catalytic hydrogenation reaction.
Described acetic acid esters is methyl acetate or ethyl acetate.
The beneficial effect that the present invention compared with prior art has is: the present invention is mixed metal salt with copper nitrate and auxiliary agent nitrate, adopts coprecipitation to prepare copper-based catalysts; Catalyst preparation process is simple, the catalyst activity height, and catalyst performance stabilised, the life-span is long, and is reusable.Acetic acid esters conversion ratio height can arrive more than 95%, and ethanol is selectively good, can reach 98%.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Copper nitrate and aluminum nitrate mixing are made into the solution A that copper ion concentration is 1.0mol/L, natrium carbonicum calcinatum is made into the solution B that concentration is 0.5mol/L, copper nitrate wherein: aluminum nitrate=1:0.8(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 9 stops, leave standstill, aging 24 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 120 ℃ of baking ovens dry 8 hours, cool to room temperature was raised to 450 ℃ with 2 ℃/min from room temperature again, and behind the calcining 4h, taking-up is kept dry, and namely gets catalyst.
In the stainless steel tubulose reactor of diameter 25mm, the prepared Cu-Al catalyst of 10 mL 20-40 orders of packing into, the bed 8 mL 20-40 order quartz sands of respectively packing into up and down.Before reaction, with the pure hydrogen of 50 mL/min, be heated to 300 ℃ final temperature with 1 ℃/min speed and reduce this catalyst, after reducing 3 hours, temperature drops to 230 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation.
Reaction temperature, reaction pressure and the acetic acid esters inlet amount of the reactor of catalyst is equipped with in adjusting, with the evaporation of this reaction feed liquid and under 230 ℃ temperature, enter this reactor with hydrogen and carry out hydrogenation reaction, reaction condition is: the volume ratio of hydrogen and acetic acid esters is 100:1, air speed 3 hr
-1, reaction pressure is 1.0 MPa, product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 80%, and ethanol selectively is 88%; The methyl acetate conversion ratio is 75%, and methyl alcohol, ethanol selectively are 80%.
Embodiment 2
Copper nitrate and zinc nitrate mixing are made into the solution A that copper ion concentration is 0.5mol/L, natrium carbonicum calcinatum is made into the solution B that concentration is 1.0mol/L, copper nitrate wherein: zinc nitrate=1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 8 stops, leave standstill, aging 10 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 100 ℃ of baking ovens dry 12 hours, cool to room temperature was raised to 550 ℃ with 5 ℃/min from room temperature again, and behind the calcining 2h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 6 hours, 300 ℃ of reduction temperatures, hydrogen flow rate 50 mL/min, the reduction back cools the temperature to 200 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 70:1, and the control reaction condition is: air speed 0.5 hr
-1, reaction temperature is 280 ℃, and reaction pressure is 8.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 60%, and ethanol selectively is 55%; The methyl acetate conversion ratio is 54%, and methyl alcohol, ethanol selectively are 50%.
Embodiment 3
Copper nitrate, barium nitrate mixing are made into the solution A that copper ion concentration is 0.8mol/L, natrium carbonicum calcinatum is made into the solution B that concentration is 0.8mol/L, copper nitrate wherein: barium nitrate=1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 9 stops, leave standstill, aging 20 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 110 ℃ of baking ovens dry 10 hours, cool to room temperature was raised to 450 ℃ with 3 ℃/min from room temperature again, and behind the calcining 4h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 4 hours, 320 ℃ of reduction temperatures, hydrogen flow rate 80 mL/min, the reduction back cools the temperature to 250 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 90:1, and the control reaction condition is: air speed 2 hr
-1, reaction temperature is 220 ℃, and reaction pressure is 6.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 85%, and ethanol selectively is 80%; The methyl acetate conversion ratio is 76%, and methyl alcohol, ethanol selectively are 80%.
Embodiment 4
Copper nitrate, aluminum nitrate and zinc nitrate mixing are made into the solution A that copper ion concentration is 0.6mol/L, natrium carbonicum calcinatum is made into the solution B that concentration is 0.6mol/L, copper nitrate wherein: aluminum nitrate: zinc nitrate=1:1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 9 stops, leave standstill, aging 15 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 120 ℃ of baking ovens dry 12 hours, cool to room temperature was raised to 300 ℃ with 4 ℃/min from room temperature again, and behind the calcining 5h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 5 hours, 340 ℃ of reduction temperatures, hydrogen flow rate 60 mL/min, the reduction back cools the temperature to 260 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 75:1, and the control reaction condition is: air speed 2.5 hr
-1, reaction temperature is 260 ℃, and reaction pressure is 5.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 74%, and ethanol selectively is 95%; The methyl acetate conversion ratio is 65%, and methyl alcohol, ethanol selectively are 89%.
Embodiment 5
Copper nitrate, aluminum nitrate and zinc nitrate mixing are made into the solution A that copper ion concentration is 0.9mol/L, 28% ammoniacal liquor is precipitating reagent, copper nitrate wherein: aluminum nitrate: zinc nitrate=1:1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add ammoniacal liquor, constantly stir, dropping to the pH value and be 8 stops, leave standstill, aging 17 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 105 ℃ of baking ovens dry 8 hours, cool to room temperature was raised to 500 ℃ with 2 ℃/min from room temperature again, and behind the calcining 4h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 5 hours, 310 ℃ of reduction temperatures, hydrogen flow rate 80 mL/min, the reduction back cools the temperature to 270 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 85:1, and the control reaction condition is: air speed 1 hr
-1, reaction temperature is 230 ℃, and reaction pressure is 4.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 66%, and ethanol selectively is 97%; The methyl acetate conversion ratio is 62%, and methyl alcohol, ethanol selectively are 90%.
Embodiment 6
Copper nitrate, aluminum nitrate and zinc nitrate mixing are made into the solution A that copper ion concentration is 0.6mol/L, NaOH is made into the solution B that concentration is 0.6mol/L, copper nitrate wherein: aluminum nitrate: zinc nitrate=1:1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add ammoniacal liquor, constantly stir, dropping to the pH value and be 8 stops, leave standstill, aging 20 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 120 ℃ of baking ovens dry 8 hours, cool to room temperature was raised to 450 ℃ with 2 ℃/min from room temperature again, and behind the calcining 4h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 4 hours, 310 ℃ of reduction temperatures, hydrogen flow rate 95 mL/min, the reduction back cools the temperature to 260 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 88:1, and the control reaction condition is: air speed 1.2 hr
-1, reaction temperature is 255 ℃, and reaction pressure is 3.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 86%, and ethanol selectively is 97%; The methyl acetate conversion ratio is 84%, and methyl alcohol, ethanol selectively are 95%.
Embodiment 7
Copper nitrate, zinc nitrate and barium nitrate mixing are made into the solution A that copper ion concentration is 0.7mol/L, natrium carbonicum calcinatum is made into the solution B that concentration is 0.7mol/L, copper nitrate wherein: zinc nitrate: barium nitrate=1:1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 8 stops, leave standstill, aging 17 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 120 ℃ of baking ovens dry 8 hours, cool to room temperature was raised to 450 ℃ with 2 ℃/min from room temperature again, and behind the calcining 4h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 5 hours, 240 ℃ of reduction temperatures, hydrogen flow rate 99 mL/min, the reduction back cools the temperature to 245 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 78:1, and the control reaction condition is: air speed 2.2 hr
-1, reaction temperature is 260 ℃, and reaction pressure is 7.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 89%, and ethanol selectively is 95%; The methyl acetate conversion ratio is 87%, and methyl alcohol, ethanol selectively are 90%.
Embodiment 8
Copper nitrate, zinc nitrate and barium nitrate mixing are made into the solution A that copper ion concentration is 0.7mol/L, NaOH is made into the solution B that concentration is 0.7mol/L, copper nitrate wherein: zinc nitrate: barium nitrate=1:1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 9 stops, leave standstill, aging 14 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 120 ℃ of baking ovens dry 8 hours, cool to room temperature was raised to 450 ℃ with 3 ℃/min from room temperature again, and behind the calcining 4h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 4 hours, 335 ℃ of reduction temperatures, hydrogen flow rate 65 mL/min, the reduction back cools the temperature to 270 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 90:1, and the control reaction condition is: air speed 0.8 hr
-1, reaction temperature is 230 ℃, and reaction pressure is 6.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 99%, and ethanol selectively is 99%; The methyl acetate conversion ratio is 97%, and methyl alcohol, ethanol selectively are 97%.
Embodiment 9
Copper nitrate, aluminum nitrate, zinc nitrate and manganese nitrate mixing are made into the solution A that copper ion concentration is 0.8mol/L, sodium carbonate is made into the solution B that concentration is 0.8mol/L, copper nitrate wherein: aluminum nitrate: zinc nitrate: manganese nitrate=1:1:1:1(amount of substance than), under 60 ℃ of water bath with thermostatic control conditions, in solution A, dropwise add solution B, constantly stir, dropping to the pH value and be 9 stops, leave standstill, aging 16 hours, filter, filter cake spend deionised water to pH be 6-8.With gained filter cake in 120 ℃ of baking ovens dry 8 hours, cool to room temperature was raised to 450 ℃ with 4 ℃/min from room temperature again, and behind the calcining 5h, taking-up is kept dry, and namely gets catalyst.
Catalyst was reduced in hydrogen atmosphere 5 hours, 315 ℃ of reduction temperatures, hydrogen flow rate 55 mL/min, the reduction back cools the temperature to 260 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of hydrogen and acetic acid esters is 85:1, and the control reaction condition is: air speed 2 hr
-1, reaction temperature is 240 ℃, and reaction pressure is 4.0 MPa, and product separates through cooling off laggard promoting the circulation of qi liquid, collects the gas, liquid product and analyzes.The ethyl acetate conversion ratio is 91%, and ethanol selectively is 99%; The methyl acetate conversion ratio is 90%, and methyl alcohol, ethanol selectively are 97%.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Therefore, no matter from that, above-mentioned embodiment of the present invention all can only be thought can not limit invention to explanation of the present invention, claims have been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, in the implication suitable with claims of the present invention and any variation in the scope, all should think to be included in the scope of claims.
Claims (5)
1. the copper-based catalysts of an acetic acid esters preparation of ethanol by hydrogenating, it is characterized in that: this activity of such catalysts component is cupric oxide, wherein the amount of substance of copper and metal promoter is than being 1:0.8-3, and adopts following method to make:
Copper nitrate and metal promoter nitrate are 1:0.8-3 according to the amount of substance ratio, be dissolved in water and be mixed with the solution A that copper ion concentration is 0.5-1.0 mol/L, in solution A, dropwise add the precipitating reagent that concentration is 0.5-1.0 mol/L then, constantly stir simultaneously, drop to the pH value and stop to add precipitating reagent for 8-9, and at room temperature leave standstill, aging 10-24 hour, suction filtration, after getting filter cake and spending deionised water and be 6-8 to pH, at 100-120 ℃ of dry 8-12 hour, be cooled to room temperature, heating rate with 2-5 ℃/min is raised to 300-550 ℃ again, calcined 2-6 hour, and naturally cooled to room temperature, namely obtain copper-based catalysts.
2. the copper-based catalysts of a kind of acetic acid esters preparation of ethanol by hydrogenating according to claim 1 is characterized in that described metal promoter is one or more the mixture in aluminum nitrate, zinc nitrate, barium nitrate and the manganese nitrate.
3. the copper-based catalysts of a kind of acetic acid esters preparation of ethanol by hydrogenating according to claim 1 is characterized in that described precipitating reagent is sodium carbonate, NaOH or ammoniacal liquor.
4. the method for the described copper-based catalysts catalysis of claim 1 an acetic acid esters preparation of ethanol by hydrogenating is characterized in that:
Catalyst was reduced in hydrogen atmosphere 3-6 hour, reduction temperature 300-350 ℃, hydrogen flow rate 50-100 mL/min, the reduction back cools the temperature to 200-280 ℃ under hydrogen atmosphere, beginning acetic acid esters hydrogenation reaction, the acetic acid esters gasification is mixed with hydrogen in the feeding reactor, and the volume ratio of described hydrogen and acetic acid esters is 70-100:1, and the control reaction condition is: air speed 0.5-3 hr
-1, reaction temperature is 200-280 ℃, reaction pressure is 1.0-8.0 MPa, finishes catalytic hydrogenation reaction.
5. the method for a kind of copper-based catalysts catalysis acetic acid esters preparation of ethanol by hydrogenating according to claim 4 is characterized in that described acetic acid esters is methyl acetate or ethyl acetate.
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| CN103980089A (en) * | 2014-05-05 | 2014-08-13 | 大连理工大学 | Method for preparing ethyl alcohol and isopropyl alcohol |
| CN104437509A (en) * | 2014-10-29 | 2015-03-25 | 西安凯立化工有限公司 | Preparation method of catalyst for preparing ethyl alcohol through acetate hydrogenation |
| CN105944723A (en) * | 2016-05-21 | 2016-09-21 | 中山市绿浪助剂有限公司 | Preparation method of catalyst for preparation of low carbon alcohol by synthesis gas |
| CN115845869A (en) * | 2022-11-24 | 2023-03-28 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethanol by methyl acetate hydrogenation, preparation method and application thereof |
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Application publication date: 20130807 |