CN103084186A - Catalyst for preparing ethanol directly by acetic acid as well as preparation method and use thereof - Google Patents
Catalyst for preparing ethanol directly by acetic acid as well as preparation method and use thereof Download PDFInfo
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Abstract
The invention provides a catalyst for preparing ethanol directly by acetic acid as well as a preparation method and use thereof. More specific, the invention provides the catalyst for preparing ethanol directly by acetic acid. The catalyst comprises an active ingredient composition loaded on a carrier. The active ingredient composition comprises platinum and stannum as well as any one base metal in a group formed by free copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc. The content of platinum in the catalyst is 0.01-0.09wt%, and the weight ratio of platinum and stannum is Pt/Sn=1. The content of the base metal is 0.01-20wt%. Ethanol can be selectively prepared by the catalyst at a lower temperature, and the loading amount of noble metal platinum in the catalyst is lower, so that the catalyst is lower in cost and is equivalent or better than similar products in level.
Description
Technical field
The invention belongs to the catalytic chemistry field, more specifically, the present invention relates to for the catalyst that is directly prepared ethanol by acetic acid, and its production and use.
Background technology
Ethanol is as a kind of basic organic chemical industry raw material, 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, 3,000,000 tons of left and right, annual growth rate is 8%-10% to China Chemical Industry with ethanol market annual requirement.In the alcohol fuel field, the Chinese market current needs are about 1,500,000 ton/years, estimate in the industry to welcome rapid 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% take the production of grain fermentation method as main, 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 take non-grain as main.
Chinese newly-built acetic acid (namely in recent years, acetic acid) device is gone into operation successively, domestic acetic acid production capacity sharply increases, and the apparent consumption amount of acetic acid tends to be steady, cause production capacity seriously superfluous, acetic acid preparation of ethanol by hydrogenating technique both can take full advantage of superfluous acetic acid resource, can provide for the development of alcohol fuel new raw material sources 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 product purity is high, compares with current grain fermentation legal system ethanol, has larger 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 US 2,607, and 807 have reported on ruthenium catalyst, and the yield of acetic acid ethanol processed can reach 88% under the pressure of 700～950 bar, and the yield of ethanol is only 40% under the pressure of 200 bar.
U.S. Celanese Corp. is devoted to the research of acetic acid alcohol catalysis agent processed and technique in recent years always, discloses a series of patents.
For example, patent US 2011/0245546 A1, take Pt-Co or Pd-Co as active component, with graphite, high-purity Si O
2For carrier prepares loaded catalyst, the ethanol yield reaches as high as 68.2% with calcium silicates etc., and the catalyst of this moment consists of Pt 1wt%-Co 10wt%/SiO
2
Patent US 2010/0029995 A1 is take Pt-Sn as active component, with graphite, high-purity Si O
2For carrier prepares loaded catalyst, the ethanol yield reaches as high as 79.4% with calcium silicates etc., and the catalyst of this moment consists of Pt 1wt%-Sn 1wt%/SiO
2
Patent US 2011/0098501 A1, take Pt-Sn or Re-Pd as active component, with high-purity Si O
2For carrier prepares loaded catalyst, the ethanol yield reaches as high as 54%, and the catalyst of this moment consists of Pt 0.5wt%-Sn 0.5wt%/SiO
2
Patent US 2011/0082322 A1 is take Pt 1.6wt%-Sn 1wt% as active component, 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 the carrier improvers such as calcium silicates, magnesium silicate, zinc oxide in 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 large.Yet, in the catalyst of Celanese Corp., the load capacity of noble metal platinum (Pt) (that is, content) height, all more than 0.1wt%, great majority are more than 0.5～2wt%, and this makes the catalyst cost of preparation high.Simultaneously, though the non-noble metal catalyst of existing employing can reduce costs, its reaction temperature and reaction pressure require high, and condition is harsh, and commercial operation reduces greatly.
Summary of the invention
In order to overcome the problems referred to above of existing catalyst that directly prepare the reaction of ethanol for acetic acid, the purpose of this invention is to provide 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 directly prepared the catalyst of ethanol by acetic acid, described catalyst comprises the active ingredient compositions that loads on carrier, described active ingredient compositions comprises platinum and tin, and select any non-noble metal components in the group that free copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc forms, the content of the platinum in wherein said catalyst is that the weight ratio Pt/Sn of 0.01～0.09wt% and platinum and tin is 1, and the content of wherein said non-noble metal components is 0.01～20wt%.
In a preferred embodiment, described non-noble metal components is copper, molybdenum or nickel.
In a preferred embodiment, described carrier selects any in the group that free silica, aluminium oxide, calcium silicates, carbon, zirconia and titanium oxide form, and is more preferably silica.
On the other hand, the invention provides a kind of method for preparing above-mentioned catalyst, described method comprises: the salting liquid of platinum salting liquid, tin-salt solution and described non-noble metal components is mixed to obtain maceration extract; Described maceration extract is impregnated on described carrier to obtain catalyst precarsor; Obtain described catalyst with described catalyst precarsor being carried out drying and roasting.
In a preferred embodiment, described maceration extract is impregnated on described carrier by equi-volume impregnating.
In a preferred embodiment, described maceration extract is the mixed liquor of the nitrate aqueous solution of the dilute nitric acid solution of the aqueous solution, tin oxalate of chloroplatinic acid and described non-noble metal components.
In a preferred embodiment, described catalyst precarsor under 100～130 ℃ dry 0.5～5 hour and 400～600 ℃ of lower roastings 1～8 hour.
In yet another aspect, the invention provides the purposes of above-mentioned catalyst in directly preparing ethanol by acetic acid, wherein acetic acid is by the selective hydrogenating reduction of quilt is ethanol with hydrogen reaction.
In a preferred embodiment, the described reaction that directly prepares ethanol by acetic acid is carried out in gas phase and at the temperature of 200～300 ℃.
In a further preferred embodiment, be 100: 1～1: 100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in described gas phase is 0.1～3MPa.
In a preferred embodiment, the described reaction that is directly prepared ethanol by acetic acid is carried out at the temperature of 225～280 ℃.
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 described gas phase is 1.0～2.5MPa.
The composition of catalyst of the present invention by using a certain proportion of Pt and Sn and other non-noble metal components is as active component, Pt content in catalyst is reduced to 0.01～0.09wt%, 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 better than or is equivalent to existing expensive noble metal catalyst.
The specific embodiment
The object of the invention is to provide and a kind ofly directly prepares the low-cost of ethanol and can business-like catalyst for acetic acid.Purpose of the present invention realizes by such catalyst: described catalyst comprises the active ingredient compositions that loads on carrier, described active ingredient compositions comprise platinum and tin and select free copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and group that zinc forms in any non-noble metal components, the content of the platinum in wherein said catalyst is that the weight ratio Pt/Sn of 0.01～0.09wt% and platinum and tin is 1, and the content of wherein said non-noble metal components is 0.01～20wt%.
Utilize catalyst of the present invention, under hydrogen atmosphere, the direct selective hydrogenation of acetic acid can be generated ethanol.The reaction equation that acetic acid hydrogenation generates ethanol is as follows:
CH
3COOH+2H
2——→CH
3CH
20H+H
2O
Catalyst of the present invention can use known various carriers for catalyst, and the example is including, but not limited to zeolite, iron oxide, silica, aluminium oxide, titanium oxide, zirconia, magnesia, calcium silicates, carbon, graphite and composition thereof.The carrier that the present invention preferably uses is silica, aluminium oxide, calcium silicates, carbon, zirconia and titanium oxide, more preferably uses silica as the carrier of catalyst of the present invention.
Preferably, the described non-noble metal components for catalyst of the present invention can be selected from the group that following metal consists of: copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc, more preferably, described non-noble metal components is copper, molybdenum or nickel.
In catalyst of the present invention, the content of tin is usually with reference to the content of platinum, because weight ratio Pt/Sn is 1, so if in catalyst, the content of platinum is 0.01 or 0.09wt%, the content of tin is also 0.01 or 0.09wt%.
Catalyst of the present invention can prepare by methods known in the art.Preferably, catalyst of the present invention prepares by the following method, and described method comprises: the salting liquid of platinum salting liquid, tin-salt solution and described non-noble metal components is mixed to obtain maceration extract; Described maceration extract is impregnated on described carrier to obtain catalyst precarsor; Obtain described catalyst with described catalyst precarsor being carried out drying and roasting.
In catalyst preparation process of the present invention, can use any method known in the art to carry out metal impregnation.Preferably, described maceration extract is impregnated on described carrier by equi-volume impregnating, such as but not limited to, the mixed liquor of the nitrate aqueous solution of the aqueous solution by using chloroplatinic acid, the dilute nitric acid solution of tin oxalate and described non-noble metal components floods as maceration extract, for example floods by equi-volume impregnating.
Preferably, in catalyst preparation process of the present invention, by described catalyst precarsor under 100～130 ℃ dry 0.5～5 hour and obtained the catalyst expected in 1～8 hour 400～600 ℃ of lower roastings.
Catalyst of the present invention can be applied to many application, especially can be used for acetic acid by being the reaction that directly prepares ethanol by acetic acid of ethanol by selective hydrogenating reduction with hydrogen reaction.The reaction that is directly prepared ethanol by acetic acid can be carried out under gas phase or liquid-phase condition.Preferably, this reaction is carried out in gas phase (being gaseous state when namely all reactants arrive reactor).Operable reaction temperature is preferably at approximately 200～300 ℃, more preferably 225～280 ℃.Reaction pressure is not key influence factor to this reaction usually, so this reaction pressure can be lower than atmospheric pressure, atmospheric pressure or higher than atmospheric pressure.Yet, preferably, the pressure of this reaction is controlled in the pressure limit of 0.1～3MPa, preferably in the scope of about 1.0～2.5MPa.
Although in theory, in above-mentioned reaction, every mole of acetic acid consumes the hydrogen of 2 moles, but preferably, it is approximately 100: 1～1: 100 as the acetic acid of reactant and the raw materials components mole ratio of hydrogen, it is more preferably 1: 2～1: 100, for example the raw materials components mole ratio of acetic acid and hydrogen is 1: 5, to improve the conversion ratio of acetic acid.
For directly prepared the reaction of ethanol by acetic acid, can adopt conventional method for example to adopt Agilent-6890 gas-chromatography to carry out qualitative and quantitative analysis to product.Before 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.Rear passage TCD detector and 5A molecular sieve chromatography post are used for analyzing possible following product: carbon dioxide etc.
The data that gather are processed by the following method:
Conversion ratio X: the acetic acid that expression occurs 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 to calculate as follows according to data from gas chromatography, take ethanol as example:
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:
Following examples have been described the program for the preparation of the various catalyst that use in the method for the invention.
Embodiment A
Preparation Pt 0.01%-Sn0.01%/SiO
2Catalyst (without non-noble metal components, being used for relatively)
The aqueous solution (0.67ml) of chloroplatinic acid (0.027g) and the dilute nitric acid solution (1ml) of tin oxalate (0.017g) are mixed and add the maceration extract that water is made into 72.6ml, join in 100g silica, the limit edged stirs, with the material that obtains in being heated to gradually the baking oven of 110 ℃ dry 2 hours, then 500 ℃ of (heating rates in Muffle furnace, 2 ℃/min) roasting 4 hours, both catalyst sample.
Embodiment B
Preparation Pt 0.09%-Sn0.09%/SiO
2Catalyst (without non-noble metal components, being used for relatively)
The aqueous solution (6.03ml) of chloroplatinic acid (0.243g) and the dilute nitric acid solution (1ml) of tin oxalate (0.153g) are mixed and add the maceration extract that water is made into 72.6ml, join in 100g silica, the limit edged stirs, with the material that obtains in being heated to gradually the baking oven of 120 ℃ dry 3 hours, then 500 ℃ of (heating rates in Muffle furnace, 2 ℃/min) roasting 4 hours, both catalyst sample.
Embodiment C
Preparation Pt 0.09%-Sn0.09%-Ni15%/SiO
2Catalyst (catalyst according to the invention)
The aqueous solution (6.03ml) of chloroplatinic acid (0.243g), the dilute nitric acid solution (1ml) of tin oxalate (0.153g) and the aqueous solution (50ml) of nickel nitrate (74.17g) are mixed and add the maceration extract that water is made into 72.6ml, join in 100g silica, the limit edged stirs, with the material that obtains in being heated to gradually the baking oven of 110 ℃ dry 2 hours, then 600 ℃ of (heating rates in Muffle furnace, 2 ℃/min) roasting 3 hours, both catalyst sample.
Embodiment D
Preparation Pt 0.09%-Sn0.09%-Cu15%/SiO
2Catalyst (catalyst according to the invention)
The aqueous solution (6.03ml) of chloroplatinic acid (0.243g), the dilute nitric acid solution (1ml) of tin oxalate (0.153g) and the aqueous solution (50ml) of copper nitrate (56.98g) are mixed and add the maceration extract that water is made into 72.6ml, join in 100g silica, the limit edged stirs, with the material that obtains in being heated to gradually the baking oven of 110 ℃ dry 2 hours, then 400 ℃ of (heating rates in Muffle furnace, 2 ℃/min) roasting 4 hours, both catalyst sample.
Embodiment E
Preparation Pt 0.09%-Sn0.09%-Mo15%/SiO
2Catalyst (catalyst according to the invention)
The aqueous solution (6.03ml) of chloroplatinic acid (0.243g), the dilute nitric acid solution (1ml) of tin oxalate (0.153g) and the aqueous solution (50ml) of ammonium molybdate (193.24g) are mixed and add the maceration extract that water is made into 72.6ml, join in 100g silica, the limit edged stirs, with the material that obtains in being heated to gradually the baking oven of 130 ℃ dry 2 hours, then 500 ℃ of (heating rates in Muffle furnace, 2 ℃/min) roasting 4 hours, both catalyst sample.
Catalyst sample is estimated
Reactor used is stainless steel tubular type reactor, the catalyst that embodiment A～E is made and the catalyst (being numbered respectively Celanese 1～5) of aforementioned Celanese Corp. are placed in 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 is exported and is measured with mass flowmenter by high-pressure cylinder, the mol ratio of acetic acid and hydrogen is 1: 5, acetic acid and hydrogen mixed before reactor and enter together in reactor, react under the pressure of 275 ℃ and 2.2MPa, extraction part reaction effluent is through gas chromatographic analysis composition and content.
The evaluating catalyst result is referring to table 1.
Table 1
Can find out from the evaluating catalyst result of table 1: (1) can prepare ethanol by catalysis acetic acid according to the catalyst (wherein the content of platinum is that the weight ratio Pt/Sn of 0.01～0.09wt% and platinum and tin is 1) of embodiment A～E; Yet (embodiment A～B) is aspect the acetic acid conversion ratio or all be significantly less than catalyst according to the invention (catalyst of embodiment D～E contains with good grounds non-noble metal components of the present invention in its active component) aspect the ethanol yield not contain catalyst according to non-noble metal components of the present invention in active component; (2) catalyst according to the invention (catalyst of embodiment D～E) is in by acetic acid selectivity ground preparation ethanol synthesis, the conversion ratio of acetic acid high (more than 96%), the yield of ethanol high (more than 82%); (3) catalyst according to the invention (catalyst of embodiment D～E) aspect the ethanol yield with the noble metals content catalysts (Celanese 1～5) of existing Celanese Corp. be on close level or higher.
In addition, became originally from catalyst, in the catalyst of Celanese, the load capacity of platinum is more than 0.5wt%, calculates by 1% platinum load capacity roughly, and every gram platinum calculates by 400 yuan (RMB), and the cost of catalyst per ton is at least 4,000,000 yuan.And in catalyst according to the invention, content low (being up to the 0.09wt% of whole catalyst) due to precious metals pt, the base metal cost itself that load capacity is higher simultaneously is lower, can not cause too large impact to the catalyst cost, here calculate take the load capacity of platinum as 0.09wt%, the cost of catalyst per ton is less than 400,000 yuan, lower than 1/10th of Celanese catalyst cost, therefore have larger cost advantage, be 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 defined by the following claims.
Claims (13)
1. catalyst that is used for directly being prepared by acetic acid ethanol, described catalyst comprises the active ingredient compositions that loads on carrier, described active ingredient compositions comprises platinum and tin, and select any non-noble metal components in the group that free copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc forms
The content of the platinum in wherein said catalyst is that the weight ratio Pt/Sn of 0.01～0.09wt% and platinum and tin is 1, and the content of wherein said non-noble metal components is 0.01～20wt%.
2. catalyst according to claim 1, is characterized in that, described non-noble metal components is copper, molybdenum or nickel.
3. catalyst according to claim 1, is characterized in that, described carrier selects any in the group that free silica, aluminium oxide, calcium silicates, carbon, zirconia and titanium oxide form.
4. catalyst according to claim 3, is characterized in that, described carrier is silica.
5. method for preparing the described catalyst of any one according to claim 1-4, described method comprises:
The salting liquid of platinum salting liquid, tin-salt solution and described non-noble metal components is mixed to obtain maceration extract;
Described maceration extract is impregnated on described carrier to obtain catalyst precarsor; With
Described catalyst precarsor is carried out drying and roasting and obtains described catalyst.
6. method according to claim 5, is characterized in that, described maceration extract is impregnated on described carrier by equi-volume impregnating.
7. method according to claim 5, is characterized in that, described maceration extract is the mixed liquor of the nitrate aqueous solution of the dilute nitric acid solution of the aqueous solution, tin oxalate of chloroplatinic acid and described non-noble metal components.
8. method according to claim 5, is characterized in that, described catalyst precarsor under 100～130 ℃ dry 0.5～5 hour and 400～600 ℃ of lower roastings 1～8 hour.
9. the purposes of the described catalyst of any one in directly preparing ethanol by acetic acid according to claim 1-4, wherein acetic acid is by being ethanol with hydrogen reaction by selective hydrogenating reduction.
10. purposes according to claim 9, is characterized in that, the described reaction that directly prepares ethanol by acetic acid is carried out in gas phase and at the temperature of 200～300 ℃.
11. purposes according to claim 10 is characterized in that, be 100: 1～1: 100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in described gas phase is 0.1～3MPa.
12. purposes according to claim 9 is characterized in that, the described reaction that is directly prepared ethanol by acetic acid is carried out at the temperature of 225～280 ℃.
13. purposes according to claim 12 is characterized in that, be 1: 2～1: 100 as the acetic acid of reactant and the mol ratio of hydrogen, and the pressure in described gas phase is 1.0～2.5MPa.
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| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
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| CN104557454A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing high-quality ethanol through hydrogenating acetic acid |
| CN104557453B (en) * | 2013-10-23 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of acetic acid preparation of ethanol through hydrogenation |
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| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
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| US9458072B2 (en) | 2014-04-28 | 2016-10-04 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
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| CN105709729B (en) * | 2014-12-03 | 2018-12-28 | 神华集团有限责任公司 | The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol |
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