CN103331167A - Catalyst for directly preparing ethanol from acetic acid, preparation method and application - Google Patents
Catalyst for directly preparing ethanol from acetic acid, preparation method and application Download PDFInfo
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- CN103331167A CN103331167A CN2013103059750A CN201310305975A CN103331167A CN 103331167 A CN103331167 A CN 103331167A CN 2013103059750 A CN2013103059750 A CN 2013103059750A CN 201310305975 A CN201310305975 A CN 201310305975A CN 103331167 A CN103331167 A CN 103331167A
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Abstract
The invention discloses a catalyst for directly preparing ethanol from an acetic acid. The catalyst consists of 3 to 10 mass percent of carrier, 20 to 60 mass percent of active ingredient and 35 to 70 mass percent of auxiliary, wherein alumina is adopted as the carrier; a copper oxide is adopted as the active ingredient; a zinc oxide is adopted as the auxiliary. The invention also discloses a preparation method for the catalyst.
Description
Technical field
The invention belongs to the catalytic chemistry field, more specifically, the present invention relates to a kind of for the catalyst that is directly prepared ethanol by acetic acid.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to above-mentioned catalyst and directly prepare application in the ethanol at acetic acid.
Background technology
Ethanol is as a kind of basic Organic Chemicals, of many uses at chemical industry and other industrial circle can be used as disinfectant, solvent, also can be used as Organic Chemicals, be used for the manufacturing of paint, coating, dyestuff, printing ink and medicine etc., in addition also mainly as vehicle fuel.At present, about 3,000,000 tons, annual growth rate is 8%-10% to Chinese chemical industry with ethanol market annual requirement.In the alcohol fuel field, the Chinese market current needs are about 1,500,000 tons/year, estimate in the industry to welcome quick growth, and the year two thousand twenty is expected to reach 1,000 ten thousand tons.
The production method of ethanol has ethylene hydration method and grain fermentation method, the industrial alcohol of China more than 70% based on the production of grain fermentation method, the annual a large amount of grain of consumption that needs, for fear of striving grain with the people, the end of the year 2006, emergency notice is assigned by National Development and Reform Committee, and the raw material of China's alcohol fuel project should be adhered to based on non-grain.
Chinese newly-built acetic acid device was gone into operation successively in recent years, domestic acetic acid production capacity sharply increases, and the apparent consumption figure of acetic acid tends to be steady, cause production capacity seriously superfluous, acetic acid hydrogenation ethanol processed, both can take full advantage of superfluous acetic acid resource, can provide new raw material sources for the development of alcohol fuel again.Economic aspect, 1.5 tons of acetic acid of acetic acid ethanol processed can be produced 1 ton of ethanol, and technical process is simple, and the product purity height is compared with current grain fermentation legal system ethanol, has bigger cost advantage.
At present, even domestic not by the direct patent report of ethanol processed of acetic acid, disclosed patent report has been arranged, but great majority lack commercial operation abroad.For example, patent US2,607,807 have reported on ruthenium catalyst, the yield of acetic acid ethanol processed can reach 88% under the pressure of 70-95MPa, and the yield of ethanol only is 40% under the pressure of 20MPa.
U.S. Celanese Corp. is devoted to the research of acetic acid alcohol catalysis agent processed and technology in recent years always, discloses a series of patents.
For example, patent US2011/0245546A1 is active component with Pt-Co or Pd-Co, with graphite, high-purity Si O
2With calcium silicates etc. be the preparing carriers loaded catalyst, the ethanol yield reaches as high as 68.2%, the catalyst of this moment consists of Pt1wt%-Co10wt%/SiO
2
Patent US2010/0029995A1 is active component with Pt-Sn, with graphite, high-purity Si O
2With calcium silicates etc. be the preparing carriers loaded catalyst, the ethanol yield reaches as high as 79.4%, the catalyst of this moment consists of Pt1wt%-Sn1wt%/SiO
2
Patent US2011/0098501A1 is active component with Pt-Sn or Re-Pd, with high-purity Si O
2Be the preparing carriers loaded catalyst, the ethanol yield reaches as high as 54%, and the catalyst of this moment consists of Pt0.5wt%-Sn0.5wt%/SiO
2
Patent US2011/0082322A1 is active component with Pt1.6wt%-Sn1wt%, when with high-purity Si O
2-TiO
2(10wt%) be carrier, the ethanol yield reaches as high as 73.6%, when with high-purity Si O
2-Al
2O
3(7wt%) be carrier, the ethanol yield reaches as high as 86.8%.
In addition, also have at SiO
2Add the report of carrier improvers such as calcium silicates, magnesium silicate, zinc oxide in the carrier, the yield of its ethanol is all lower.
The acetic acid of Celanese Corp. ethanol processed is simple, and operating pressure generally is about 2.2MPa, and operating pressure is low, and commercial operation is big.Yet the catalyst that Celanese Corp. develops is noble metal catalyst, and the content of noble metal platinum (Pt) is higher, and all more than 0.1wt%, great majority are more than 0.5-2wt%, and this makes that the catalyst cost of preparation is higher.
Summary of the invention
The object of the present invention is to provide a kind of for the catalyst that is directly prepared ethanol by acetic acid.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned catalyst.
For achieving the above object, catalyst provided by the invention is made up of carrier, active component and auxiliary agent; Wherein:
Described carrier is aluminium oxide, quality percentage composition 3-10%;
Described active component is cupric oxide, and the quality percentage composition is 20-60%;
Described auxiliary agent is zinc oxide, and the quality percentage composition is 35-70%.
The method of the above-mentioned catalyst of preparation provided by the invention, its step comprises:
(1) aluminum saline solution is added in the alkaline sedimentation agent solution, precipitation reaction takes place at 50-90 ℃ in the control temperature, and control pH value was 6.5-7.5 when precipitation reaction was finished, and obtained precipitated liquid 1;
(2) salting liquid with copper and zinc adds in the alkaline sedimentation agent solution, and the control temperature at 50-80 ℃ precipitation reaction takes place, and control pH value was 7.0-7.5 when precipitation reaction was finished, and obtained precipitated liquid 2;
(3) in the ratio of catalyst, precipitated liquid 1 is added in the precipitated liquid 2, stir, under 50-90 ℃ of temperature, wore out 0.5-5 hour, filtration, washing, the dry catalyst precursor that gets, catalyst precursor namely gets granular material after roasting;
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get target product, wherein the addition of graphite is the 1-2% of granular material quality percentage composition, and the addition of deionized water is the 3-8% of granular material quality percentage composition.
Wherein, the aluminium salt in the step (1) is aluminium acetate, aluminum sulfate or aluminum nitrate, is preferably aluminum nitrate.
Wherein, the alkaline precipitating agent in step (1) and the step (2) is carbonate or bicarbonate, is preferably sodium carbonate, potash, sodium acid carbonate or saleratus.
Wherein, the baking temperature in the step (3) is 110-120 ℃, and be 2-8 hour drying time.
Wherein, the sintering temperature in the step (3) is 300-350 ℃, and roasting time is 4-8 hour.
Catalyst provided by the invention can be applied in by acetic acid and directly prepare in the reaction of ethanol, and acetic acid and hydrogen react under catalyst action in 200-300 ℃ (preferred temperature 220-280 ℃), and acetic acid is ethanol by selective hydrogenating reduction.
Wherein, the mol ratio of acetic acid and hydrogen is 100:1-1:100, and the pressure of hydrogen is 0.1-5Mpa, and preferred mol ratio is 1:2-1:100, and the pressure of hydrogen is 1.0-4MPa.
Its composition of catalyst of the present invention all is base metal, the catalyst raw material is easy to get, with low cost, not only reduced the cost of the catalyst that obtains, and catalyst of the present invention can be with high conversion and high yield by acetic acid selectivity ground preparation ethanol, and its catalytic efficiency is higher than existing expensive noble metal catalyst.
The specific embodiment
In order to overcome the cost problem of existing catalyst that directly prepares the reaction of ethanol for acetic acid, the invention provides and a kind ofly directly prepare the low-cost of ethanol and can business-like catalyst for acetic acid.
On the one hand, the invention provides a kind of for the catalyst that is directly prepared ethanol by acetic acid, described catalyst comprises carrier, active component and auxiliary agent, described carrier is aluminium oxide, described active component is cupric oxide, and described auxiliary agent is zinc oxide, and the quality percentage composition of each component is respectively: aluminium oxide 3-10%, cupric oxide 20-60%, zinc oxide 35-70%.
On the other hand, the invention provides a kind of method for preparing above-mentioned catalyst, described method comprises:
(1) soluble-salt with aluminium is mixed with the aqueous solution that molar concentration is 0.5-2.0mol/L, alkaline precipitating agent is mixed with the aqueous solution that molar concentration is 0.5-2.0mol/L, aluminum salt solution is added in the precipitant solution, precipitation reaction takes place at 50-90 ℃ in the control temperature, control pH value was 6.5-7.5 when precipitation reaction was finished, and obtained precipitated liquid 1.
(2) nitrate with copper and zinc is made into the aqueous solution that the metal ion total mol concentration is 0.5-2.0mol/L, alkaline precipitating agent is mixed with the aqueous solution that molar concentration is 0.5-2.0mol/L, the salting liquid of copper and zinc is added in the precipitant solution, precipitation reaction takes place at 50-80 ℃ in the control temperature, control pH value was 7.0-7.5 when precipitation reaction was finished, and obtained precipitated liquid 2.
(3) according to the proportion of composing of catalyst, precipitated liquid 1 is added in the precipitated liquid 2, fully stir, under 50-90 ℃ of temperature aging 0.5-5 hour, after filtration, washing, dry catalyst precursor, catalyst precursor namely got granular material after roasting.
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get catalyst sample.
In the above-mentioned method for preparing catalyst, the soluble-salt of described aluminium is aluminium acetate, aluminum sulfate or aluminum nitrate, is preferably aluminum nitrate.
In the above-mentioned method for preparing catalyst, described alkaline precipitating agent is carbonate or bicarbonate, is preferably sodium carbonate, potash, sodium acid carbonate or saleratus.
In the above-mentioned method for preparing catalyst, described baking temperature is 110-120 ℃, and be 2-8 hour drying time.
In the above-mentioned method for preparing catalyst, described sintering temperature is 300-350 ℃, and roasting time is 4-8 hour.
In the above-mentioned method for preparing catalyst, the addition of described graphite is the 1-2% of granular material, and the addition of deionized water is the 3-8% of granular material.
In yet another aspect, the invention provides above-mentioned catalyst and directly prepare purposes in the ethanol at acetic acid, wherein acetic acid is by being ethanol with hydrogen reaction by selective hydrogenating reduction.
In a preferred embodiment, describedly directly prepare being reflected in the gas phase and under 200-300 ℃ temperature of ethanol by acetic acid and carry out.
In a preferred embodiment, be 100:1-1:100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in the described gas phase is 0.1-5MPa.
In a further preferred embodiment, describedly directly prepare being reflected under 220-280 ℃ the temperature of ethanol by acetic acid and carry out.
In a further preferred embodiment, be 1:2-1:100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in the described gas phase is 2.0-4MPa.
Embodiment 1
Adopt the present invention to prepare acetic acid hydrogenation alcohol catalysis agent processed:
(1) be that aluminum nitrate solution and the 0.06L concentration of 1mol/L is the sodium carbonate liquor of 1mol/L with 0.04L concentration, be under the condition of 500rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 85 ℃, the control pH value in reaction is 7.5-8, neutralization finishes the back stirred 20 minutes, obtained precipitated liquid 1;
(2) be that the copper nitrate of 1mol/L and mixed solution and the 1.2L concentration of zinc nitrate are the sodium carbonate liquor of 1mol/L with 1.2L concentration, be under the condition of 500rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 80 ℃, the control pH value in reaction is 7.0-7.5, neutralization finishes the back stirred 30 minutes, obtained precipitated liquid 2; The mol ratio of copper and zinc is 0.5:1 in the mixed solution of described copper nitrate and zinc nitrate;
(3) precipitated liquid 1 is added in the precipitated liquid 2, continue to stir 50 minutes, under 80 ℃ of temperature aging 1 hour, after filtration, wash Na to the slurry
+Content got catalyst precursor in dry 8 hours down at 120 ℃ then less than 0.05wt%, and catalyst precursor after 4 hours, namely gets granular material through 450 ℃ of roastings, and wherein cupric oxide is 31wt%, and zinc oxide is 65wt%, and aluminium oxide is 4wt%.
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get catalyst sample.Described graphite addition is the 2wt% of granular material, and deionized addition is the 5wt% of granular material.
Embodiment 2
Adopt the present invention to prepare acetic acid hydrogenation alcohol catalysis agent processed:
(1) be that aluminum nitrate solution and the 0.12L concentration of 2mol/L is the sodium bicarbonate solution of 2mol/L with 0.04L concentration, be under the condition of 800rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.2-7.5, neutralization finishes the back stirred 20 minutes, obtained precipitated liquid 1;
(2) be that the copper nitrate of 0.5mol/L and mixed solution and the 4.4L concentration of zinc nitrate are the sodium bicarbonate solution of 0.5mol/L with 2.2L concentration, be under the condition of 800rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.0-7.2, neutralization finishes the back stirred 20 minutes, obtained precipitated liquid 2; The mol ratio of copper and zinc is 0.4:1 in the mixed solution of described copper nitrate and zinc nitrate;
(3) precipitated liquid 1 is added in the precipitated liquid 2, continue to stir 40 minutes, under 65 ℃ of temperature, wore out 2 hours, after filtration, wash to the slurry Na+ content less than 0.05wt%, then 110 ℃ down dry 12 hours catalyst precursor, catalyst precursor is through 300 ℃ of roastings after 8 hours, namely get granular material, wherein cupric oxide is 25wt%, and zinc oxide is 67wt%, and aluminium oxide is 8wt%.
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get catalyst sample.Described graphite addition is the 1wt% of granular material, and deionized addition is the 8wt% of granular material.
Embodiment 3
Adopt the present invention to prepare acetic acid hydrogenation alcohol catalysis agent processed:
(1) be that aluminum nitrate solution and the 0.09L concentration of 0.5mol/L is the sodium carbonate liquor of 0.5mol/L with 0.06L concentration, be under the condition of 800rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.5-8, neutralization finishes the back stirred 10 minutes, obtained precipitated liquid 1;
(2) be that the copper nitrate of 2mol/L and mixed solution and the 0.65L concentration of zinc nitrate are the sodium carbonate liquor of 2mol/L with 0.65L concentration, be under the condition of 800rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.0-7.5, neutralization finishes the back stirred 10 minutes, obtained precipitated liquid 2; The mol ratio of copper and zinc is 0.58:1 in the mixed solution of described copper nitrate and zinc nitrate;
(3) precipitated liquid 1 is added in the precipitated liquid 2, continue to stir 40 minutes, under 70 ℃ of temperature, wore out 1.5 hours, after filtration, wash to the slurry Na+ content less than 0.05wt%, then 110 ℃ down dry 10 hours catalyst precursor, catalyst precursor is through 400 ℃ of roastings after 6 hours, namely get granular material, wherein cupric oxide is 37wt%, and zinc oxide is 60wt%, and aluminium oxide is 3wt%.
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get catalyst sample.Described graphite addition is the 2wt% of granular material, and deionized addition is the 3wt% of granular material.
Embodiment 4
Adopt the present invention to prepare acetic acid hydrogenation alcohol catalysis agent processed:
(1) be that aluminum nitrate solution and the 0.3L concentration of 1mol/L is the sodium bicarbonate solution of 1mol/L with 0.1L concentration, be under the condition of 1000rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.2-7.5, neutralization finishes the back stirred 30 minutes, obtained precipitated liquid 1;
(2) be that the copper nitrate of 1mol/L and mixed solution and the 2.2L concentration of zinc nitrate are the sodium bicarbonate solution of 1mol/L with 1.1L concentration, be under the condition of 1000rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.0-7.2, neutralization finishes the back stirred 30 minutes, obtained precipitated liquid 2; The mol ratio of copper and zinc is 0.3:1 in the mixed solution of described copper nitrate and zinc nitrate;
(3) precipitated liquid 1 is added in the precipitated liquid 2, continue to stir 40 minutes, under 65 ℃ of temperature, wore out 2 hours, after filtration, wash to the slurry Na+ content less than 0.05wt%, then 110 ℃ down dry 12 hours catalyst precursor, catalyst precursor is through 350 ℃ of roastings after 8 hours, namely get granular material, wherein cupric oxide is 20wt%, and zinc oxide is 70wt%, and aluminium oxide is 10wt%.
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get catalyst sample.Described graphite addition is the 2wt% of granular material, and deionized addition is the 6wt% of granular material.
Embodiment 5
Adopt the present invention to prepare acetic acid hydrogenation alcohol catalysis agent processed:
(1) be that aluminum nitrate solution and the 0.3L concentration of 0.5mol/L is the sodium bicarbonate solution of 0.5mol/L with 0.1L concentration, be under the condition of 500rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.2-7.5, neutralization finishes the back stirred 40 minutes, obtained precipitated liquid 1;
(2) be that the copper nitrate of 1mol/L and mixed solution and the 2.4L concentration of zinc nitrate are the sodium carbonate liquor of 1mol/L with 1.2L concentration, be under the condition of 500rpm in stir speed (S.S.), and carry out neutralization reaction in the stream adding reactor, the control reaction temperature is 60 ℃, the control pH value in reaction is 7.0-7.2, neutralization finishes the back stirred 40 minutes, obtained precipitated liquid 2; The mol ratio of copper and zinc is 1.8:1 in the mixed solution of described copper nitrate and zinc nitrate;
(3) precipitated liquid 1 is added in the precipitated liquid 2, continue to stir 40 minutes, under 65 ℃ of temperature, wore out 2 hours, after filtration, wash to the slurry Na+ content less than 0.05wt%, then 110 ℃ down dry 12 hours catalyst precursor, catalyst precursor is through 300 ℃ of roastings after 8 hours, namely get granular material, wherein cupric oxide is 60wt%, and zinc oxide is 35wt%, and aluminium oxide is 5wt%.
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get catalyst sample.Described graphite addition is the 2wt% of granular material, and deionized addition is the 7wt% of granular material.
Catalyst sample is estimated
Used reactor is stainless steel tubular type reactor, the catalyst that embodiment 1-5 is made and the catalyst (being numbered Celanese 1-5 respectively) of aforementioned Celanese Corp. place middle part, reactor flat-temperature zone, do supporter with stainless (steel) wire and quartz sand up and down.Reaction raw materials is acetic acid and hydrogen, acetic acid is carried and metering by measuring pump, hydrogen measures by high-pressure cylinder output and with mass flowmenter, the mol ratio of acetic acid and hydrogen is 1:5, acetic acid and hydrogen mixed before reactor and enter in the reactor together, react under the pressure of 225 ℃ and 2.2MPa, extraction part reaction effluent is through gas chromatographic analysis composition and content.
For the reaction that directly prepares ethanol by acetic acid, can adopt conventional method for example to adopt Agilent-6890 gas-chromatography that product is carried out qualitative and quantitative analysis.Before the analysis, demarcate gas-chromatography with calibrating gas and the normal fluid of known composition.Wherein, prepass fid detector and PLOT Q capillary chromatographic column are used for the possible following product of analytical reactions: methane, ethene, ethane, propylene, propane, methyl alcohol, ethanol, acetaldehyde, acetone, methyl acetate, ethyl acetate and acetic acid.Back passage TCD detector and 5A molecular sieve chromatography post are used for analyzing possible following product: carbon dioxide etc.
The data of gathering are handled by the following method:
Conversion ratio X: the acetic acid that expression takes place to transform accounts for the molar percentage as the acetic acid of raw material.The conversion ratio of acetic acid is to calculate as follows according to data from gas chromatography:
Selective S: represent that a certain product is based on the molar percentage that transforms the acetic acid that falls.Selectively being to calculate as follows according to data from gas chromatography, is example with ethanol:
Yield Y: represent that a certain product is based on the mole percent of raw acetic acid.The yield of a certain product calculates as follows:
Above embodiment has described the program for the preparation of the various catalyst that use in the method for the invention.
The evaluating catalyst result is referring to table 1.
From the evaluating catalyst result of table 1 as can be seen: (1) catalyst according to the invention (catalyst of embodiment 1-5) can be by acetic acid selectivity ground preparation ethanol, and the conversion ratio of acetic acid all is higher than 99%, the yield of ethanol all is higher than 97%, and the yield of ethyl acetate is lower than 2%; (2) catalyst according to the invention (catalyst of embodiment 1-5) aspect the ethanol yield apparently higher than the noble metal catalyst (Celanese 1-5 catalyst) of existing Celanese Corp..
In addition, became originally from catalyst, the load capacity of platinum is more than the 0.5wt% in the catalyst of Celanese, calculates by 1% platinum load capacity roughly, and every gram platinum calculates by 400 yuan (RMB), and then the cost of catalyst per ton is at least 4,000,000 yuan.And in catalyst according to the invention, the catalyst composition is base metal, and raw material is easy to get, and is with low cost, well below the cost of Celanese catalyst, therefore has big cost advantage, is more suitable for industrial applications from economic angle.
Below the present invention is described in detail, but the present invention is not limited to the specific embodiment described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, can make other changes and distortion.Scope of the present invention is limited by the claim of application.
Table 1
Claims (10)
1. a catalyst that is used for directly being prepared by acetic acid ethanol is made up of carrier, active component and auxiliary agent; Wherein:
Described carrier is aluminium oxide, quality percentage composition 3-10%;
Described active component is cupric oxide, and the quality percentage composition is 20-60%;
Described auxiliary agent is zinc oxide, and the quality percentage composition is 35-70%.
2. the method for preparing the described catalyst of claim 1, its step comprises:
(1) aluminum saline solution is added in the alkaline sedimentation agent solution, precipitation reaction takes place at 50-90 ℃ in the control temperature, and control pH value was 6.5-7.5 when precipitation reaction was finished, and obtained precipitated liquid 1;
(2) salting liquid with copper and zinc adds in the alkaline sedimentation agent solution, and the control temperature at 50-80 ℃ precipitation reaction takes place, and control pH value was 7.0-7.5 when precipitation reaction was finished, and obtained precipitated liquid 2;
(3) in the ratio of catalyst, precipitated liquid 1 is added in the precipitated liquid 2, stir, under 50-90 ℃ of temperature, wore out 0.5-5 hour, filtration, washing, the dry catalyst precursor that gets, catalyst precursor namely gets granular material after roasting;
(4) add graphite in step (3) the gained granular material and deionized water is beaten sheet, namely get target product, wherein the addition of graphite is the 1-2% of granular material quality percentage composition, and the addition of deionized water is the 3-8% of granular material quality percentage composition.
3. method according to claim 2, wherein, the aluminium salt described in the step (1) is aluminium acetate, aluminum sulfate or aluminum nitrate.
4. method according to claim 2, wherein, the alkaline precipitating agent described in step (1) and the step (2) is carbonate or bicarbonate.
5. method according to claim 2, wherein, the baking temperature described in the step (3) is 110-120 ℃, be 2-8 hour drying time.
6. method according to claim 2, wherein, the sintering temperature described in the step (3) is 300-350 ℃, roasting time is 4-8 hour.
7. the described catalyst of claim 1 is in the purposes that is directly prepared by acetic acid in the ethanol, and acetic acid and hydrogen react under catalyst action in 200-300 ℃, and acetic acid is ethanol by selective hydrogenating reduction.
8. purposes according to claim 7, wherein, the mol ratio of acetic acid and hydrogen is 100:1-1:100, the pressure of hydrogen is 0.1-5MPa.
9. purposes according to claim 7, wherein, the mol ratio of making acetic acid and hydrogen is 1:2-1:100, the pressure of hydrogen is 1.0-4MPa.
10. purposes according to claim 7, wherein, acetic acid and hydrogen react in 220-280 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772143A (en) * | 2014-01-08 | 2014-05-07 | 上海海源化工科技有限公司 | Method for preparing industrial ethanol from acetic acid |
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| CN102333588A (en) * | 2009-10-26 | 2012-01-25 | 国际人造丝公司 | Be used for preparing the catalyst of ethanol by acetate |
| CN102688758A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
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| CN101157041A (en) * | 2007-07-30 | 2008-04-09 | 山东师范大学 | A preparation method of nanometer cuprum base methanol synthetic catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772143A (en) * | 2014-01-08 | 2014-05-07 | 上海海源化工科技有限公司 | Method for preparing industrial ethanol from acetic acid |
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Application publication date: 20131002 |