CN103920502B - The Catalysts and its preparation method of ethyl acetate gas phase hydrogenation ethanol and application under a kind of temperate condition - Google Patents
The Catalysts and its preparation method of ethyl acetate gas phase hydrogenation ethanol and application under a kind of temperate condition Download PDFInfo
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- CN103920502B CN103920502B CN201410151456.8A CN201410151456A CN103920502B CN 103920502 B CN103920502 B CN 103920502B CN 201410151456 A CN201410151456 A CN 201410151456A CN 103920502 B CN103920502 B CN 103920502B
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Abstract
The invention discloses Catalysts and its preparation method and the application of ethyl acetate gas phase hydrogenation ethanol under a kind of temperate condition, described catalyst take Cu as main active component, with at least one in Zn or Sn for co-catalyst, with Al
2o
3for carrier, and at least one element added respectively in alkali metal and transition metal is as auxiliary agent.Catalyst stability of the present invention is good, high to the conversion ratio of ethyl acetate, ethanol selective good, and in measured condition and range, ethyl acetate conversion ratio reaches more than 98%, ethanol selective close to 100%, and can maintain higher air speed.The manufacture craft of catalyst is simple, with low cost simultaneously, little to ambient influnence, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to Catalysts and its preparation method and the application of ethyl acetate gas phase hydrogenation ethanol under a kind of temperate condition.
Background technology
Ethanol, is commonly called as alcohol, and chemical formula is C
2h
5oH or EtOH.Ethanol is of many uses, can be used as solvent, industrial chemicals, disinfectant and fuel etc.Ethanol can dissolve many inorganic matters, can dissolve many organic matters again, is a kind of innoxious solvent of excellent performance.Ethanol can be used to produce acetaldehyde, ether, ethyl acetate, ethamine, dyestuff, coating and washing agent etc.Volume fraction be 70 ~ 75% ethanol be often used as medical disinfectant.Meanwhile, ethanol can call in gasoline as vehicle fuel, to improve the Performance and quality of oil product.
The technology of preparing of ethanol, the method for current comparative maturity has biomass ferment method and ethylene hydration method.Be a kind of more novel method with ethyl acetate preparation of ethanol through hydrogenation, the method is with the coal of cheapness for raw material fundamentally, and does not use the ethene of grain in short supply and high price.Also once description was had in the past by carboxylate preparation of ethanol through hydrogenation, such as, at CN102423710A, CN1230458A, CN86105765A, DE-A-3401896, DE-A-3443277, EP-A-95408, DE-A-3217492, have in USP4346240, BE892958, EP-A-36939 and USP4405819 and describe.
CN102423710A discloses a kind of Catalysts and its preparation method of acetate preparation of ethanol through hydrogenation, and this catalyst take Cu as active component, with SiO
2for carrier, with transition metal or/and at least one in alkali metal is auxiliary agent.The content requirement of catalyst to active component is low, only needs active component Cu content more than 15%.Under optimum process condition, the selective of ethanol reaches 99%, and space-time yield is 1.55g/ (g catalyst h
-1).
CN1230458A discloses a kind of method of synthesis gas two step synthesis ethanol, namely the method for ethanol is prepared with carbon monoxide, it relates to a kind of method preparing ethanol from acetaldehyde, ethyl acetate, acetic acid or its mixture gas phase hydrogenation, its hydrogen source is in synthesis gas, used catalyst main component is CuO, and carrier is Al
2o
3, auxiliary agent be a kind of alkali metal oxide if CaO, MgO, BaO or transition metal oxide are as FeO, CoO, WO, MoO, ZnO, or the combination of above-mentioned oxide.Catalyst chemical forms, key component CuO:10-17W%, carrier A l
2o
3: 1-55W%, auxiliary agent: 1-55W%.Catalyst adopts infusion process or coprecipitation preparation, catalyst baking temperature 10-200 DEG C, sintering temperature 300-600 DEG C, roasting time 1-10 hour.
CN86105765A discloses the method by carboxylate Hydrogenation alcohol, under the catalyst containing copper and at least one magnesium, lanthanide series metal or actinide metals exists, make carboxylate Hydrogenation for alcohol under high temperature, normal pressure or high pressure, the space-time yield of the method is 1.54g/ (g catalyst h
-1).But group of the lanthanides or actinide metals expensive, cost is high, is unfavorable for suitability for industrialized production.
DE-A-3443277 disclose when with carbon dioxide to improve reduction-state cupric oxide and Zinc oxide catalytic activity aliphatic (acid) ester hydrogenolysis.
DE892958 discloses the hydrogenolysis alcohol by carboxylate, and its method under the absolute pressure of the temperature of 75 ~ 300 DEG C and 0.1 ~ double centner/square centimeter, the ester/hydrogen mixture of gaseous state is contacted.
USP4405819 discloses carboxylic ester hydrogenation catalyst.They are metal and the metal oxide of transition elements, these transition metal be I B element as copper, II B element is as zinc, and VI B element is as chromium, and VII B element is as manganese, and VIII element is as iron.And as required load on bentonite, Fo Latu, active carbon, aluminium oxide etc.But be best with copper chromite.
Other aforementioned patents disclose non-copper catalyst, as rhodium (DE-A-3401896), a kind of carrier, rhodium and tin, germanium and/or lead (EP-A-95408), rhodium and a kind of noble metal (DE-A-3217492) are placed in VIII race's metal (USP4346240) and VIII race's metal of the alkali metal containing component on carrier, are placed in the alkali metal on high-area carbon and free radical anion (EP-A-36936).
Summary of the invention
The object of the present invention is to provide a kind of method of ethyl acetate preparation of ethanol through hydrogenation, namely under having the Cu-series catalyst of reduction activation to exist, under certain reaction temperature and reaction pressure, make ethyl acetate hydrogenation generate ethanol.
For achieving the above object, the technical solution used in the present invention is as follows: a kind of method of ethyl acetate preparation of ethanol through hydrogenation, the method is under having the Cu-series catalyst of reduction activation to exist, at the reaction pressure of the reaction temperatures of 160 ~ 280 DEG C, 1.0 ~ 5.0MPa, hydrogen ethyl acetate mol ratio 20 ~ 50 and ethyl acetate quality liquid hourly space velocity (LHSV) 0.5 ~ 2h
-1condition under make ethyl acetate hydrogenation generate ethanol.
Described Cu-series catalyst take Cu as main active component, with at least one in Zn or Sn for co-catalyst, with Al
2o
3for carrier, and at least one element added respectively in alkali metal and transition metal is as auxiliary agent.
As preferably, major catalyst of the present invention is at least one in Zn or Sn, described alkali metal be in Na, Mg, K at least one, described transition metal is at least one in Ir, Bi, Os, Mn, and described carrier derives from Al (NO
3)
39H
2o.In described catalyst, the usage ratio of each composition is: main active component content is 50 ~ 300% of vehicle weight, and cocatalyst content is 5 ~ 20% of vehicle weight, and auxiliary agent content is 0.2 ~ 2% of vehicle weight.
The preparation method of described Cu-series catalyst comprises the following steps:
(1) copper salt, promoter metal salt, promoter metal salt and the slaine that will be converted into carrier are mixed with mixed aqueous solution;
(2) under the condition of 60 DEG C, by the mixed aqueous solution of step (1) described slaine and precipitant mix, and constantly stir, controlling solution terminal pH is 7 ~ 8;
(3) continue stirring 1 ~ 2 hour after feeding in raw material, then leave standstill aging 2 ~ 4 hours at 80 DEG C;
(4) solution is filtered, collect filter cake, and spend deionized water;
(5) by the filter cake after washing at 100 ~ 120 DEG C of temperature dry 12 ~ 24 hours;
(6) by the roasting in air atmosphere of dried filter cake, rise to 400 ~ 600 DEG C with the speed of 5 DEG C/min, and keep 4 ~ 8 hours under outlet temperature;
(7) filter cake after roasting reduces 8 ~ 12 hours in the mixed atmosphere of hydrogen and nitrogen, and reduction temperature is 220 ~ 320 DEG C, and the gas hourly space velocity of mist gets 4000 ~ 8000h
-1.
Compared with prior art, the invention has the advantages that: the method for a kind of ethyl acetate of the present invention catalytic hydrogenation ethanol has high ethyl acetate conversion ratio and high ethanol selectivity, and the good stability of catalyst.In measured condition and range, ethyl acetate maximum conversion reaches more than 98%, ethanol selective close to 100%, and can maintain higher air speed.The manufacture craft of catalyst of the present invention is simple, with low cost simultaneously, little to ambient influnence, is applicable to suitability for industrialized production.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, the present invention is described with once specific embodiment further, but the present invention is limited to absolutely not these examples.
Embodiment 1
Take Cu (NO
3)
23H
2o28 gram, Zn (NO
3)
26H
2o5 gram, Al (NO
3)
36H
2o15 gram, H
2irCl
6xH
2o0.1 gram, Bi (NO
3)
35H
2o0.5 gram is dissolved in 250ml deionized water; Take anhydrous Na
2cO
330 grams are dissolved in 250ml deionized water.Two solution are flow to sample under 60 DEG C of conditions, and control pH is 7 ~ 8, reinforced complete, continue stirring after 1 hour, at 80 DEG C, leave standstill aging 3 hours; Feed liquid is filtered while hot, then spends deionized water 3 times, suction filtration; Catalyst in an oven in 110 DEG C of dryings 12 hours, then proceed in Muffle furnace carry out in air atmosphere roasting (5 DEG C/min is warming up to 400 DEG C, afterwards at 400 DEG C keep 4 hours); Compression molding is placed in reaction tube, is the nitrogen of 10% and the mist of hydrogen with hydrogen volume mark, 250 DEG C, normal pressure, air speed 5000h
-1reduce 8 hours under condition, obtain catalyst A.
Be used for by above-mentioned catalyst in the reaction of ethyl acetate gas-phase catalytic hydrogenation ethanol, device adopts fixed bed reactors, tube inner diameter 10mm, long 80cm.At the constant temperature zone filling 4g catalyst of reactor, upper and lower side loads the quartz sand of same particle size and isolates with silica wool.Reaction tube adopts syllogic diamond heating, and reaction tube built-in thermoelectric is even.
Ethyl acetate is vaporized in reactor upper end and is mixed with hydrogen, and gaseous mixture passes through beds, temperature 200 DEG C, and pressure 2.5Mpa, hydrogen ethyl acetate mol ratio 20 and ethyl acetate quality liquid hourly space velocity (LHSV) 1.0h
-1condition under with catalyst exposure, product is drawn by reactor bottom, and after condenser and gas-liquid separator, liquid product is by gas-chromatography off-line analysis, and gas-phase product is by gas-chromatography on-line analysis.The conversion ratio 90% of ethyl acetate, selective 99% of ethanol.
Embodiment 2
Take Cu (NO
3)
23H
2o28 gram, SnC
2o
46 grams, Al (NO
3)
36H
2o15 gram, H
2irCl
6xH
2o0.1 gram is dissolved in 250ml deionized water; Take anhydrous Na
2cO
330 grams are dissolved in 250ml deionized water.Metal salt solution is instilled in precipitating reagent under 60 DEG C of conditions, and to control terminal pH be 7 ~ 8, fed in raw material complete, continue stirring after 1 hour, at 80 DEG C, leave standstill aging 3 hours; Feed liquid is filtered while hot, then spends deionized water 3 times, suction filtration; Catalyst in an oven in 110 DEG C of dryings 12 hours, then proceed in Muffle furnace carry out in air atmosphere roasting (5 DEG C/min is warming up to 350 DEG C, afterwards at 350 DEG C keep 4 hours); Compression molding is placed in reaction tube, is the nitrogen of 10% and the mist of hydrogen with hydrogen volume mark, 270 DEG C, normal pressure, air speed 3000h
-1reduce 8 hours under condition, obtain catalyst B.
Be used for by this example catalyst B in the reaction of ethyl acetate gas-phase catalytic hydrogenation ethanol, reaction unit and PROCESS FOR TREATMENT and analytical method are with example 1.Unlike reaction temperature 240 DEG C, reaction pressure 3Mpa, hydrogen ethyl acetate mol ratio 30, ethyl acetate quality liquid hourly space velocity (LHSV) 1.5h
-1.Ethyl acetate conversion ratio 78%, ethanol selectivity 95%.
Embodiment 3
Take Cu (NO
3)
23H
2o28 gram, Zn (NO
3)
26H
2o5 gram, Al (NO
3)
36H
2o15 gram, Bi (NO
3)
35H
2o0.5 gram, K
2osCl
60.1g is dissolved in 250ml deionized water; Take NaOH8 gram to be dissolved in 250ml deionized water.Precipitating reagent is added in metal salt solution under 60 DEG C of conditions, and to control final pH be 7 ~ 8, fed in raw material complete, continue stirring after 1 hour, at 80 DEG C, leave standstill aging 3 hours; Feed liquid is filtered while hot, then spends deionized water 3 times, suction filtration; Catalyst in an oven in 110 DEG C of dryings 12 hours, then proceed in Muffle furnace carry out in air atmosphere roasting (5 DEG C/min is warming up to 400 DEG C, afterwards at 400 DEG C keep 4 hours); Compression molding is placed in reaction tube, is the nitrogen of 10% and the mist of hydrogen with hydrogen volume mark, 270 DEG C, normal pressure, air speed 6000h
-1reduce 8 hours under condition, obtain catalyst C.
Be used for by this example catalyst C in the reaction of ethyl acetate gas-phase catalytic hydrogenation ethanol, reaction unit and PROCESS FOR TREATMENT and analytical method are with example 1.Unlike reaction temperature 260 DEG C, reaction pressure 3.0Mpa, hydrogen ethyl acetate mol ratio 50, ethyl acetate quality liquid hourly space velocity (LHSV) 0.8h
-1.Ethyl acetate conversion ratio 97%, ethanol selectivity 99%.
Embodiment 4
Take Cu (NO
3)
23H
2o28 gram, Zn (NO
3)
26H
2o5 gram, Al (NO
3)
36H
2o15 gram, Bi (NO
3)
35H
2o0.5 gram, Mn (NO
3)
20.5 gram is dissolved in 250ml deionized water.Above-mentioned metal salt solution being instilled under 60 DEG C of conditions mass fraction is in the ammoniacal liquor of 28%, and control pH is 7 ~ 8, has fed in raw material complete, continues stirring after 1 hour, at 80 DEG C, leaves standstill aging 3 hours; Feed liquid is filtered while hot, then spends deionized water 3 times, suction filtration; Catalyst in an oven in 110 DEG C of dryings 12 hours, then proceed in Muffle furnace carry out in air atmosphere roasting (5 DEG C/min is warming up to 400 DEG C, afterwards at 400 DEG C keep 4 hours); Compression molding is placed in reaction tube, is the nitrogen of 10% and the mist of hydrogen with hydrogen volume mark, 250 DEG C, normal pressure, air speed 5000h
-1reduce 8 hours under condition, obtain catalyst D.
Be used for by this example catalyst D in the reaction of ethyl acetate gas-phase catalytic hydrogenation ethanol, reaction unit and PROCESS FOR TREATMENT and analytical method are with example 1.Unlike reaction temperature 220 DEG C, reaction pressure 3Mpa, hydrogen ethyl acetate mol ratio 40, ethyl acetate quality liquid hourly space velocity (LHSV) 1.0h
-1.Ethyl acetate conversion ratio 90%, ethanol selectivity 94%.
Embodiment 5
Take Al (NO
3)
36H
2o15 gram is dissolved in 50ml deionized water, takes anhydrous Na
2cO
330 grams are dissolved in 250ml deionized water.By Al (NO
3)
3the Na that solution and 50ml join
2cO
3solution is under 60 DEG C of conditions and flow to sample, and control pH is 7 ~ 8, reinforced complete, continues stirring after 1 hour, will containing Cu (NO
3)
23H
2o28 gram, Zn (NO
3)
26H
2o5 gram, Bi (NO
3)
35H
2o0.5 gram, H
2irCl
6xH
2the Na that the 200ml metal salt solution of O0.1 gram and 200ml join
2cO
3solution is parallel-flow precipitation in this mother liquor, and same control temperature is 60 DEG C, and pH is 7 ~ 8, after reinforced, at 80 DEG C, leaves standstill aging 3 hours; Feed liquid is filtered while hot, then spends deionized water 3 times, suction filtration; Catalyst in an oven in 110 DEG C of dryings 12 hours, then proceed in Muffle furnace carry out in air atmosphere roasting (5 DEG C/min is warming up to 400 DEG C, afterwards at 400 DEG C keep 4 hours); Compression molding is placed in reaction tube, is the nitrogen of 10% and the mist of hydrogen with hydrogen volume mark, 250 DEG C, normal pressure, air speed 5000h
-1reduce 8 hours under condition, obtain catalyst E.
Be used for by this example catalyst E in the reaction of ethyl acetate gas-phase catalytic hydrogenation ethanol, reaction unit and PROCESS FOR TREATMENT and analytical method are with example 1.Unlike reaction temperature 250 DEG C, reaction pressure 4Mpa, hydrogen ethyl acetate mol ratio 40, ethyl acetate quality liquid hourly space velocity (LHSV) 1.5h
-1.Ethyl acetate conversion ratio 97%, ethanol selectivity 99%.
Claims (3)
1. a preparation method for Cu-series catalyst, this Cu-series catalyst take Cu as main active component, with at least one in Zn or Sn for co-catalyst, with Al
2o
3for carrier, and at least one element added respectively in alkali metal and transition metal is as auxiliary agent, it is characterized in that, this Cu-series catalyst is used for ethyl acetate preparation of ethanol through hydrogenation, in this Cu-series catalyst, the usage ratio of each composition is: main active component content is 50 ~ 300% of vehicle weight, cocatalyst content is 5 ~ 20% of vehicle weight, and auxiliary agent content is 0.2 ~ 2% of vehicle weight;
Comprise the steps:
(1) copper salt, promoter metal salt, promoter metal salt and the slaine that will be converted into carrier are mixed with mixed aqueous solution; Auxiliary agent transition metal salt is H
2irCl
6xH
2o, Bi (NO
3)
35H
2o, K
2osCl
6or Mn (NO
3)
2;
(2) under the condition of 60 DEG C, by the mixed aqueous solution of step (1) described slaine and precipitant mix, and constantly stir, controlling solution terminal pH is 7 ~ 8;
(3) continue stirring 1 ~ 2 hour after feeding in raw material, then leave standstill aging 2 ~ 4 hours at 80 DEG C;
(4) solution is filtered, collect filter cake, and spend deionized water;
(5) by the filter cake after washing at 100 ~ 120 DEG C of temperature dry 12 ~ 24 hours;
(6) by the roasting in air atmosphere of dried filter cake, rise to 400 ~ 600 DEG C with the speed of 5 DEG C/min, and keep 4 ~ 8 hours under outlet temperature;
(7), after the filter cake compression molding after roasting, reduce 8 ~ 12 hours in the mixed atmosphere of hydrogen and nitrogen, reduction temperature is 220 ~ 320 DEG C, and the gas hourly space velocity of mist gets 4000 ~ 8000h
-1.
2. preparation method as claimed in claim 1, is characterized in that the copper salt described in step 1 is Cu (NO
3)
23H
2o, promoter metal salt is Zn (NO
3)
26H
2o or SnC
2o
4, additive alkali slaine is NaNO
3, Mg (NO
3)
2or KNO
3.
3. preparation method as claimed in claim 1, is characterized in that the precipitating reagent described in step 2 is Na
2cO
3, NaOH or ammoniacal liquor.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230458A (en) * | 1998-03-26 | 1999-10-06 | 中国科学院大连化学物理研究所 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
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| US20130225876A1 (en) * | 2012-02-29 | 2013-08-29 | Celanese International Corporation | Hydrogenation Catalyst Using Multiple Impregnations of an Active Metal Solution |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230458A (en) * | 1998-03-26 | 1999-10-06 | 中国科学院大连化学物理研究所 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
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