CN102941097B - Industrial catalyst for preparing ethanol with acetic ester by hydrogenation, preparation method of industrial catalyst and application - Google Patents
Industrial catalyst for preparing ethanol with acetic ester by hydrogenation, preparation method of industrial catalyst and application Download PDFInfo
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Abstract
The invention relates to an industrial catalyst for preparing ethanol with acetic ester by hydrogenation. The catalyst comprises, in weight percent, 20-50% of CuO, 10-30% of ZnO, 1-10% of M oxide and 10-69% of SiO2, wherein the M is selected from IIA group or VIII group metals, the SiO2 is amorphous silicon dioxide, the specific surface area of the catalyst is 100-300m<2>/g, and the specific surface area of active copper is 10-20m<2>/g. The preparation process of the catalyst includes the steps: firstly, mixing precursors of metal Cu, Zn and M to prepare water solution I, mixing a Si precursor and a precipitator to prepare water solution II and then mixing and precipitating the solution; and secondly, performing washing, filtering, drying, preforming, roasting, crushing and reducing to obtain the catalyst. The obtained catalyst has high catalytic activity for hydrogenation of the acetic ester and has a certain water resistance and acid resistance, the ethanol has high selectivity, and the service life of the catalyst is prolonged.
Description
Technical field
The industrial catalyst and preparation method thereof and application that the present invention relates to a kind of acetic acid esters preparation of ethanol by hydrogenating, belong to hydrogenation catalyst field.
Background technology
Ethanol is commonly called as alcohol, and it is a kind of inflammable at normal temperatures, volatile colourless transparent liquid.Ethanol has purposes very widely.Ethanol can be made essence, beverage, and the ethanolic solution of variable concentrations is used as disinfectant.Ethanol is again a kind of Organic Chemicals of basis, can prepare acetaldehyde, acetic acid, and ether, ethamine etc., are also to prepare dyestuff, coating, the raw material of the products such as washing agent, it can also be used as diluent, the aspects such as organic solvent.Ethanol adds gasoline as novel clean fuel, can reduce the discharge of pernicious gas, is important developing direction.
At present, industrial general employing fermentation method and ethene aquation legal system are for ethanol.Fermentation method need to consume a large amount of plants, and production cost is higher, and accessory substance is many, is subject to the impact of natural conditions larger.Ethene aquation method needs oil gas, and production cost is directly proportional to crude oil price.The national conditions of China are the few oil of rich coal, need research and development directly or indirectly to prepare the method for ethanol from synthesis gas.Mainly comprise low carbon alcohol by synthetic gas, acetic acid hydrogenation ethanol processed, acetic acid esters preparation of ethanol by hydrogenating etc.It is simple that acetic acid esters preparation of ethanol by hydrogenating has technique, not high to equipment requirement, and conversion ratio and selectively all very high is separated simple, catalyst low cost and other advantages.At present, most widely used in ester through hydrogenation catalyst is copper chromium-based catalysts, and its shortcoming is that crome metal is unfriendly to environment; Also useful noble metal catalyst, shortcoming is that the cost of catalyst is high; Also useful CuZnAl catalyst, although alumina support has played good peptizaiton, side reaction is many, ethanol selectively lower.
Summary of the invention
The object of the present invention is to provide industrial catalyst of a kind of acetic acid esters preparation of ethanol by hydrogenating and preparation method thereof.The cost of material of this catalyst is cheap, and preparation method is simple, and not containing chromium, reduces the pollution to environment.Catalyst by the method preparation has very high catalytic activity to acetic acid esters hydrogenation, and ethanol has very high selective, and has certain water-resistance and acid-resisting, has extended the service life of catalyst.
The present invention is achieved by the following technical solutions:
An industrial catalyst for acetic acid esters preparation of ethanol by hydrogenating, is comprised of the component of following percentage by weight: CuO:20-50%; ZnO:10-30%; The oxide of M: 1-10%; SiO
2: 10-69%.
Wherein, M is selected from II A Zu Huo VIII family metal.
Preferably, M is selected from Ca, Mg, Ba, Co, Fe and Ni.
Preferably, CuO:30-40%; ZnO:15-25%; The oxide of M: 4-6%; SiO
2: 30-50%.
Described SiO
2for amorphous carbon/silicon dioxide.
The present invention also provides a kind of preparation method of industrial catalyst of described acetic acid esters preparation of ethanol by hydrogenating, comprises the following steps:
(1) by measuring than the presoma of metal Cu, Zn and M is mixed and made into solution I;
(2) presoma of Si and precipitant mix are made to solution II;
(3) solution I and solution II are mixed, carry out precipitation reaction;
(4) cyclic washing, be filtered to filtrate for neutral and detect without acid ion, be then dried as catalyst powder;
(5) then compressing tablet, roasting;
(6) broken rear reduction.
Described preparation method's step (6) also can be compressing tablet after first roasting.
Described solution I is the aqueous solution or water-ethanol solution.
Described solution II is the aqueous solution.
The presoma of described Cu, Zn and M is selected from the soluble-salt of Cu, Zn and M.
The presoma of described Cu, Zn and M is selected from nitrate and the acetate of Cu, Zn and M.
The presoma of described Si is selected from Ludox, esters of silicon acis, silicate and metasilicate.
Described precipitating reagent is selected from NaOH, potassium hydroxide, sodium acid carbonate, saleratus, ammoniacal liquor and urea.
In the described solution I of step (1), metal ion total concentration is 0.2-2.0mol/L.
The pH < 2 of the described solution I of step (1).
In the described solution II of step (2), the concentration of precipitating reagent is 0.2-2.0mol/L.
The PH > 10 of the described solution II of step (2).
The hybrid mode of the described solution of step (3) is for being added drop-wise to above-mentioned two kinds of solution in reaction vessel while stirring.
The described precipitation reaction process of step (3) is constant temperature stirring reaction process; The temperature of described precipitation reaction is 50-100 ℃, is preferably 70-85 ℃; The time of described precipitation reaction is 0.5-2 hour, is preferably 1-1.5 hour.
The PH > 7 of the described precipitation reaction mixed solution of step (3).
The washing agent of the described washing of step (4) is deionized water.
The described dry temperature of step (4) is 80-120 ℃, is preferably 90-105 ℃; The described dry time is 2-4 hour, is preferably 3-3.5 hour.
The temperature of the described roasting of step (5) is 300-500 ℃, is preferably 400-450 ℃; The time of roasting is 2-8 hour, is preferably 4-6 hour.
The granularity of the described fragmentation of step (6) is 20-40 order.
The process conditions of the described reduction of step (6): reducing gas is H
2or CO, volumetric concentration 10-100%, the air speed of reducing gas is 3000-10000ml/g-cat.h; Reduction temperature is 200-400 ℃; Reduction pressure is 0.1-3Mpa; Recovery time 4-48 hour.
The specific surface of described catalyst is 100-300m
2/ g, the specific surface of active copper is 10-20m
2/ g.
Preparation method's cost of material of the present invention is cheap, and preparation method is simple, and not containing chromium, reduces the pollution to environment.The catalyst of preparing by the method is to acetic acid esters hydrogenation, particularly methyl acetate and ethyl acetate Hydrogenation have very high catalytic activity for ethanol, ethanol has very high selective, and this catalyst has certain water-resistance and acid-resisting, has extended the service life of catalyst.When hydrogenation reaction temperature is 170-300 ℃, reaction pressure is 1.0-5.0MPa, and the mol ratio of acetic acid esters and hydrogen is 1:10-1:100, and liquid hourly space velocity (LHSV) is 0.5-5g/g-cat.h
-1, the conversion ratio of acetic acid esters can reach 90-99%, ethanol be selectively greater than 96%.
The specific embodiment
By specific instantiation, technical scheme of the present invention is described below.Should be understood that one or more method steps that the present invention mentions do not repel between the step that also has additive method step or clearly mention at these before and after described combination step can also insert additive method step; Should also be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, without essence change technology contents in the situation that, when being also considered as the enforceable category of the present invention.
Embodiment 1
The industrial catalyst of preparing acetic acid esters preparation of ethanol by hydrogenating:
(1) 1.5 liter of copper nitrate solution (content of Cu is 8%wt), and 300 grams of Zn (NO
3)
2.6H
2o, adds 50 grams of Mg (NO
3)
2.6H
2o dissolves, and by deionized water, being diluted to total concentration of metal ions is 0.2mol/L, the pH value <2 of solution;
(2) 300 grams of sodium carbonate, with after deionized water dissolving, add the Ludox of 0.6 liter of 25wt%, and being then diluted to carbonate concentration is 0.2mol/L, the pH value >11 of solution;
(3) under agitation, above-mentioned two kinds of solution are added dropwise in reactor, carry out precipitation reaction, the temperature of reaction is 70 ℃, and solution drips follow-up continuous insulated and stirred 1 hour, the pH value >7 of still liquid;
(4) reacted rear with deionized water cyclic washing, to be filtered to filtrate be neutral, electrical conductivity <1000 μ s/cm; Then at 120 ℃, be dried 4 hours, obtain catalyst powder;
(5) it is cylindric that powder compressing tablet becomes Φ 4 * 4, and at 450 ℃, roasting is 6 hours;
(6) fragmentation, after sieving, collects 20-40 object particle, in temperature, is then that 280 ℃, pressure are that 2.4MPa, reducing atmosphere are that volumetric concentration is 10% and the air speed H that is 6000ml/g-cat.h
2under condition, reduce 6 hours;
It is 139m that BET records specific surface area of catalyst
2/ g, active copper specific area is 12.2m
2/ g.It is 33.8% that ICP records CuO content, and ZnO content is that 21.3%, MgO content is 2.8%, SiO
2content is 42,1%.
Catalytic hydrogenation reaction by the catalyst making for methyl acetate and ethyl acetate, hydrogenation result is as shown in table 1:
Table 1
Embodiment 2
Prepare acetic acid esters hydrogenation catalyst:
(1) 1.5 liter of copper nitrate solution (content of Cu is 8%wt), and 250 grams of Zn (NO
3)
2.6H
2o, adds 30 grams of Co (NO
3)
2.6H
2o dissolves, and by deionized water, being diluted to total concentration of metal ions is 0.2mol/L, the pH value <2 of solution;
(2) 300 grams of sodium carbonate, with after deionized water dissolving, add the Ludox of 0.6 liter of 25wt%, and being then diluted to carbonate concentration is 0.2mol/L, the pH value >11 of solution;
(3) under agitation, above-mentioned two kinds of solution are added dropwise in reactor, carry out precipitation reaction, the temperature of reaction is 70 ℃, and solution drips follow-up continuous insulated and stirred 1 hour, the pH value >7 of still liquid;
(4) reacted rear with deionized water cyclic washing, to be filtered to filtrate be neutral, electrical conductivity <1000 μ s/cm; Then at 120 ℃, be dried 4 hours, obtain catalyst powder;
(5) it is cylindric that powder compressing tablet becomes Φ 4 * 4, and at 450 ℃, roasting is 6 hours;
(6) fragmentation, after sieving, collects 20-40 object particle, then temperature be 280 ℃, pressure be 3MPa, reducing atmosphere be volumetric concentration be 10% and the air speed CO condition that is 6000ml/g-cat.h under reduce 6 hours.
It is 158m that BET records specific surface area of catalyst
2/ g, active copper specific area is 11.4m
2/ g.It is 36.2% that ICP records CuO content, and ZnO content is that 17.8%, CoO content is 1.9%, SiO
2content is 44.1%.
Catalytic hydrogenation reaction by the catalyst making for methyl acetate and ethyl acetate, hydrogenation result is as shown in table 1:
Table 2
Embodiment 3
The industrial catalyst of preparing acetic acid esters preparation of ethanol by hydrogenating:
(1) 1.5 liter of copper nitrate solution (content of Cu is 8%wt), and 200 grams of Zn (NO
3)
2.6H
2o, adds 40 grams of Ca (NO
3)
2.4H
2o dissolves, and by deionized water, being diluted to total concentration of metal ions is 0.2mol/L, the pH value <2 of solution;
(2) 300 grams of sodium carbonate, with after deionized water dissolving, add the Ludox of 0.6 liter of 25%wt, and being then diluted to carbonate concentration is 0.2mol/L, the pH value >11 of solution;
(3) under agitation, above-mentioned two kinds of solution are added dropwise in reactor, carry out precipitation reaction, the temperature of reaction is 80 ℃, and solution drips follow-up continuous insulated and stirred 1 hour, the pH value >7 of still liquid;
(4) reacted rear with deionized water cyclic washing, to be filtered to filtrate be neutral, electrical conductivity <1000 μ s/cm; Then at 120 ℃, be dried 4 hours, obtain catalyst powder;
(5) it is cylindric that powder compressing tablet becomes Φ 4 * 4, and at 450 ℃, roasting is 6 hours;
(6) fragmentation, after sieving, collects 20-40 object particle, in temperature, is then that 280 ℃, pressure are that 3MPa, reducing atmosphere are that volumetric concentration is 10% and the air speed H that is 6000ml/g-cat.h
2under condition, reduce 6 hours;
It is 138m that BET records specific surface area of catalyst
2/ g, active copper specific area is 11.7m
2/ g.It is 40.1% that ICP records CuO content, and ZnO content is that 15.4%, CaO content is 3.1%, SiO
2content is 41.4%.
Catalytic hydrogenation reaction by the catalyst making for methyl acetate and ethyl acetate, hydrogenation result is as shown in table 3:
Table 3
Embodiment 4
The industrial catalyst of preparing acetic acid esters preparation of ethanol by hydrogenating:
(1) 1.5 liter of copper nitrate solution (content of Cu is 8wt%), and 250 grams of Zn (NO
3)
2.6H
2o, adds 25 grams of Ni (NO
3)
2.6H
2o dissolves, and by deionized water, being diluted to total concentration of metal ions is 0.2mol/L, the pH value <2 of solution;
(2) 300 grams of sodium carbonate, with after deionized water dissolving, add the Ludox of 0.6 liter of 25wt%, and being then diluted to carbonate concentration is 0.2mol/L, the pH value >11 of solution;
(3) under agitation, above-mentioned two kinds of solution are added dropwise in reactor, reaction produces precipitation.The temperature of reaction is 80 ℃.Solution is added dropwise to complete follow-up continuation of insurance temperature, stirs the pH value >7 of still liquid 1 hour;
(4) react the rear deionized water cyclic washing of using, be filtered to filtrate for neutral, electrical conductivity <1000 μ s/cm; Then at 120 ℃, be dried 4 hours, obtain catalyst powder;
(5) it is cylindric that powder compressing tablet becomes Φ 4 * 4, and roasting is 6 hours at 450 ℃;
(6) fragmentation, after sieving, collects 20-40 object particle, in temperature, is then that 280 ℃, pressure are that 3MPa, reducing atmosphere are that volumetric concentration is 10% and the air speed H that is 6000ml/g-cat.h
2under condition, reduce 6 hours;
It is 162m that BET records specific surface area of catalyst
2/ g, active copper specific area is 13.5m
2/ g.It is 37.2% that ICP records CuO content, and ZnO content is that 17.1%, NiO content is 2.1%, SiO
2content be 43.6%.
Catalytic hydrogenation reaction by the catalyst making for methyl acetate and ethyl acetate, hydrogenation result is as shown in table 4:
Table 4
Claims (16)
1. an industrial catalyst for acetic acid esters preparation of ethanol by hydrogenating, is comprised of the component of following percentage by weight:
CuO:30-40%; ZnO:15-25%; The oxide of M: 4-6%; SiO
2: wherein, described M is selected from Ca, Mg, Ba, Co, Fe and Ni to 30-50%;
Described catalyst is made by the preparation method who comprises the following steps:
(1) by measuring than the presoma of metal Cu, Zn and M is mixed and made into solution I;
(2) presoma of Si and precipitant mix are made to solution II;
(3) solution I and solution II are mixed, carry out precipitation reaction;
(4) cyclic washing, be filtered to filtrate for neutral and detect without acid ion, be then dried as catalyst powder;
(5) then compressing tablet, roasting;
(6) broken rear reduction;
Wherein, the pH < 2 of the described solution I of step (1), wherein metal ion total concentration is 0.2-2.0mol/L; The PH > 10 of the described solution II of step (2), wherein the concentration of precipitating reagent is 0.2-2.0mol/L; The hybrid mode of the described solution of step (3) is for being added drop-wise to above-mentioned two kinds of solution in reaction vessel while stirring;
The specific surface of described catalyst is 100-300m
2/ g, the specific surface of active copper is 10-20m
2/ g.
2. catalyst as claimed in claim 1, is characterized in that, described SiO
2for amorphous carbon/silicon dioxide.
3. the preparation method of catalyst as claimed in claim 1 or 2, comprises the following steps:
(1) by measuring than the presoma of metal Cu, Zn and M is mixed and made into solution I;
(2) presoma of Si and precipitant mix are made to solution II;
(3) solution I and solution II are mixed, carry out precipitation reaction;
(4) cyclic washing, be filtered to filtrate for neutral and detect without acid ion, be then dried as catalyst powder;
(5) then compressing tablet, roasting;
(6) broken rear reduction.
4. preparation method as claimed in claim 3, is characterized in that, the presoma of described Cu, Zn and M is selected from the soluble-salt of Cu, Zn and M.
5. preparation method as claimed in claim 3, is characterized in that, the presoma of described Cu, Zn and M is selected from nitrate and the acetate of Cu, Zn and M.
6. preparation method as claimed in claim 3, is characterized in that, described solution I is the aqueous solution or water-ethanol solution, and described solution II is the aqueous solution.
7. preparation method as claimed in claim 3, is characterized in that, the presoma of described Si is selected from Ludox, esters of silicon acis, silicate and metasilicate.
8. preparation method as claimed in claim 3, is characterized in that, described precipitating reagent is selected from NaOH, potassium hydroxide, sodium acid carbonate, saleratus, ammoniacal liquor and urea.
9. preparation method as claimed in claim 3, is characterized in that, the pH < 2 of described solution I, and wherein metal ion total concentration is 0.2-2.0mol/L.
10. preparation method as claimed in claim 3, is characterized in that, the PH > 10 of described solution II, and wherein the concentration of precipitating reagent is 0.2-2.0mol/L.
11. preparation methods as claimed in claim 3, is characterized in that, described precipitation reaction process is constant temperature stirring reaction process; The temperature of described precipitation reaction is 50-100 ℃, and the time of described precipitation reaction is 0.5-2 hour.
12. preparation methods as claimed in claim 3, is characterized in that, described dry temperature is 80-120 ℃; The described dry time is 2-4 hour.
13. preparation methods as claimed in claim 3, is characterized in that, the temperature of described roasting is 300-500 ℃, and the time of roasting is 2-8 hour.
14. preparation methods as claimed in claim 3, is characterized in that, the process conditions of described reduction are: reducing gas is H
2or CO, volumetric concentration is 10-100%, the air speed of reducing gas is 3000-10000ml/g-cat.h; Reduction temperature is 200-400 ℃; Reduction pressure is 0.1-3Mpa; Recovery time 4-48 hour.
15. application of catalyst in acetic acid esters preparation of ethanol by hydrogenating technique as claimed in claim 1 or 2.
16. application as claimed in claim 15, is characterized in that, described acetic acid esters is methyl acetate or ethyl acetate.
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| CN103230795A (en) * | 2013-05-31 | 2013-08-07 | 山西盛驰科技有限公司 | Copper-based catalyst for preparing ethanol from acetic acid ester in hydrogenation manner and application of copper-based catalyst |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| CN105399605B (en) * | 2014-09-16 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method of acetate preparation of ethanol by hydrogenating |
| CN105148913B (en) * | 2015-10-08 | 2017-11-07 | 宁波海越新材料有限公司 | A kind of preparation method for the catalyst that MEK is prepared for sec-butyl alcohol |
| CN106040245B (en) * | 2016-06-06 | 2018-12-11 | 北京宝聚能源科技有限公司 | A kind of Co base catalyst and the preparation method and application thereof |
| CN109364923A (en) * | 2018-11-07 | 2019-02-22 | 江苏索普（集团）有限公司 | Copper-based water-fast catalyst M-Cu/SiO2Preparation method and application method |
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| CN102093162A (en) * | 2010-12-13 | 2011-06-15 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester |
| CN102659513A (en) * | 2012-04-28 | 2012-09-12 | 上海戊正工程技术有限公司 | Process for producing alcohol and selectively co-producing 2-butanol by utilizing acetate and matching process system thereof |
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| CN102093162A (en) * | 2010-12-13 | 2011-06-15 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester |
| CN102659513A (en) * | 2012-04-28 | 2012-09-12 | 上海戊正工程技术有限公司 | Process for producing alcohol and selectively co-producing 2-butanol by utilizing acetate and matching process system thereof |
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