CN104148086B - Prepare the catalyst and method of ethanol - Google Patents
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Abstract
The present invention relates to a kind of catalyst and method for preparing ethanol, mainly solve the presence of the technical problem for being difficult to prepare the good ester selective hydrocatalyst of stability in the prior art.The present invention is used in terms of parts by weight including following components：A) 5 ~ 50 parts of metallic coppers or its oxide；B) 0.05 ~ 30 part is selected from least one of alkaline-earth metal or/and transition metal element or its oxide；C) 50 ~ 90 parts of alumina supports；Wherein, the specific surface area of catalyst is 50 ~ 400 meters2/ gram, total pore volume is 0.3 ~ 2.0 ml/g, the pore volume that 30 nanometers of bore dia ＜ accounts for the 5 ~ 60% of total pore volume, the pore volume that 30 ~ 60 nanometers of bore dia accounts for the 20 ~ 75% of total pore volume, 20 ~ 60% technical scheme that the pore volume that 60 nanometers of bore dia ＞ accounts for total pore volume preferably solves the problem, in the industrial production available for acetate preparation of ethanol by hydrogenating.
Description
Technical field
The invention belongs to field of catalytic chemistry, more particularly to a kind of method of acetate preparation of ethanol through hydrogenation.
Background technology
Ethanol is widely used in the industries such as food, medicine, chemical industry, fuel, meanwhile, in Waste Era of Oil, replacement of fuel is
Ensure national energy security and reduce one of cost-effective approach.Ethanol is used as a kind of important clean fuel and gasoline anti-knock agent
Component, can be greatly lowered the pollutant emission of burning, to improving environment, realizing that sustainable development is significant.
On the technology of preparing of ethanol, the method mainly used at present has grain fermentation method, ethylene hydration method, synthesis gas to close
Into ethanol and acetate preparation of ethanol through hydrogenation.According to statistics, the factory of China about more than 95% produces second using grain fermentation method
Alcohol.With the development and the continuous rising of demand of fuel ethanol industrial, there is lack of raw materials, and problem is increasingly serious, causes domestic grain
Increasingly nervous, food shortage price suddenly rises for supply.In addition, the Energy Situation of China is rich coal, deficency, few oil, therefore ethene water
Legal, synthesis gas synthesizing alcohol development is restricted.Along with fiber, coating, binder industry development, China's acetic acid
Industry production capacity Rapid Expansion, accumulative 383.80 ten thousand tons of the glacial acetic acid of production of China in 2010, increases by 29.29%, production of acetic acid on a year-on-year basis
Substantially supply exceed demand, and Business Economic Benefit declines to a great extent.National polyvinyl alcohol production capacity reaches 87.7 ten thousand tons, by-product acetic acid within 2011
About 1,450,000 tons of methyl esters.Because methyl acetate market capacity is very limited（~ 5 ten thousand tons/year）, current most enterprises can only pass through water
Solution, separation and recovery acetic acid and methanol loop are used, and retracting device technological process is complicated, and investment is high, high energy consumption.If passing through acetate
Hydro-conversion is ethanol and methanol, can both simplify existing procedure, realize energy-saving, asking for byproduct outlet can be solved again
Topic, eliminates the bottleneck that PVA expands energy, expands acetic acid/methyl acetate downstream product chain, improves added value of product and device mixed economy
Benefit.Therefore, exploitation feed coal breaks away from benefit through acetic acid/methyl acetate synthesis ethanol technology for current acetic acid and PVA industries
Difference, the product predicament that supply exceed demand, develop alternative fuel, ensure national energy security, with great strategic significance and good hair
Exhibition prospect.The Cu catalyst of current commercial Application is deposited in terms of hydrogenation activity, selectivity, hydrogen ester ratio and anti-impurity jamming performance
In very big gap, it is difficult to adapt to the requirement that material quality is often fluctuated in acetic acid industry.Therefore, hydrogenation catalyst need to have preferable
Active, selective and anti-impurity interference performance, so as to extend catalyst service life.
CN1974510A discloses a kind of method that carboxylic acid and its ester prepare alcohol, and noble ruthenium or palladium are immobilized on into titanium dioxide
On zirconium, in the reaction of methyl acetate preparation of ethanol through hydrogenation, methyl acetate conversion ratio to be 80%, and ethanol selectivity is relatively low, is only
68%.Catalyst recycling prepared by this method is complicated, is unfavorable for industrialized production.
CN101934228A discloses a kind of catalyst of acetate preparation of ethanol through hydrogenation and its preparation method and application, urges
The main catalytic component of agent is copper, and addition auxiliary agent is one kind in several metal oxides of Zn, Mn, Cr, Ca, Ba, Fe, Ni, Mg
Or more than one, carrier is aluminum oxide or Ludox, is prepared using the precipitation method, and the precipitating reagent is carbonate, ammoniacal liquor or urea.
Gained reactive precursor is calcined 2 ~ 5 hours at being dried 2 ~ 24 hours, 350 ~ 500 DEG C at 60 ~ 120 DEG C.Implement in example, the catalysis
Agent is used for acetate preparation of ethanol through hydrogenation, and acetic acid ester conversion rate is 80 ~ 90%, while required hydrogen/ester mol ratio is higher, it is minimum
70：1.This method H2Consumption is big, requires higher to consersion unit.
CN102093162A discloses a kind of method of use acetate preparation of ethanol through hydrogenation, using copper-based catalysts, SiO2
For carrier, at least one of transition metal or/and alkali metal are auxiliary agent, 180 ~ 300 DEG C of reaction temperature, reaction pressure 1.0 ~
Acetate preparation of ethanol through hydrogenation is carried out under the conditions of 5.0MPa.The carrier is derived from least one in silicate, Ludox, esters of silicon acis
Kind.The catalyst uses compression molding, in the reaction of methyl acetate preparation of ethanol through hydrogenation, the Mass Selective of ethanol to be only
57%。
CN102327774A discloses a kind of catalyst of acetate preparation of ethanol through hydrogenation, catalyst chemical composition：Activity
Ni metal accounts for 30 ~ 60%；Promoter metal is the combination of Mg, Zn, Mn, Ni, Sn, Ag, Pd, lanthanide series metal or above-mentioned metal, account for 5 ~
40%；Carrier silicas or aluminum oxide, account for 20 ~ 50%.In case study on implementation, the catalyst is used in acetate hydrogenation reaction,
Feed stock conversion is distributed in 70 ~ 85%, ethanol selectivity 79 ~ 81%.
The content of the invention
One of technical problems to be solved by the invention are to exist to be difficult to prepare the good ester selection of stability in the prior art
Property hydrogenation catalyst technical problem there is provided a kind of catalyst of new acetate preparation of ethanol through hydrogenation, the catalyst has steady
The advantages of qualitative good, low hydrogen ester is easy to shaping than, good conversion ratio and selectivity, catalyst.Technology solved by the invention
The two of problem are to provide a kind of purposes with solving one of technical problem corresponding catalyst.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of catalyst for preparing ethanol,
Including following components in terms of parts by weight：
B) 5 ~ 50 parts of metallic coppers or its oxide；
C) 0.05 ~ 30 part is selected from least one of alkaline-earth metal or/and transition metal element or its oxide；
D) 50 ~ 90 parts of alumina supports；
Wherein, the specific surface area of catalyst is 50 ~ 400 meters2/ gram, total pore volume is 0.3 ~ 2.0 ml/g, bore dia ＜ 30
The pore volume of nanometer accounts for the 5 ~ 60% of total pore volume, and the pore volume that 30 ~ 60 nanometers of bore dia accounts for the 20 ~ 75% of total pore volume, and bore dia ＞ 60 receives
The pore volume of rice accounts for the 20 ~ 60% of total pore volume.
In above-mentioned technical proposal, in terms of parts by weight, the consumption of metallic copper or its oxide is preferably 5 ~ 30 parts, more preferably
For 10 ~ 25 parts；Consumption selected from least one of alkaline-earth metal or/and transition metal element or its oxide is preferably 0.05
~ 20 parts, more preferably 0.1 ~ 10 part；The consumption of alumina support is preferably 60 ~ 85 parts, more preferably 75 ~ 85 parts.
In above-mentioned technical proposal, the specific surface area of catalyst is preferably 50 ~ 300 meters2/ gram, total pore volume is preferably 0.5 ~ 1.5
Ml/g, the pore volume that 30 nanometers of bore dia ＜ preferably accounts for the 20 ~ 45% of total pore volume, and the pore volume that 30 ~ 60 nanometers of bore dia is preferably accounted for
The 20 ~ 40% of total pore volume, the pore volume that 60 nanometers of bore dia ＞ preferably accounts for the 30 ~ 50% of total pore volume.The specific surface area of catalyst is more excellent
Elect 100 ~ 250 meters as2/ gram, total pore volume is more preferably 0.8 ~ 1.2 ml/g, and the pore volume that 30 nanometers of bore dia ＜, which is more preferably, to be accounted for
The 25 ~ 45% of total pore volume, the pore volume that 30 ~ 60 nanometers of bore dia, which is more preferably, accounts for the 25 ~ 35% of total pore volume, 60 nanometers of bore dia ＞'s
Pore volume, which is more preferably, accounts for the 30 ~ 45% of total pore volume.
In above-mentioned technical proposal, the element selected from alkaline-earth metal is preferably selected from least one of calcium, magnesium or barium；It was selected from
The element for crossing metal is preferably selected from least one of manganese, molybdenum, iron, nickel, zinc, lanthanum or cerium；Copper size of microcrystal in catalyst is excellent
Elect 1 ~ 30 nanometer, more preferably 5 ~ 20 nanometers as.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of method for preparing ethanol, its
It is characterised by using acetate and hydrogen as raw material, is 2 in hydrogen/ester mol ratio:1~45:1, air speed is 0.2 ~ 2.0 hour-1, reaction
Temperature is 150 ~ 350 DEG C, and reaction pressure is under the conditions of 0.5 ~ 10.0MPa, raw material and catalyst haptoreaction makes the vinegar in raw material
Acid esters is hydroconverted into ethanol, and catalyst used is in terms of parts by weight including following components：
A) 5 ~ 50 parts of metallic coppers or its oxide；
B) 0.05 ~ 30 part is selected from least one of alkaline-earth metal or/and transition metal element or its oxide；
C) 5 ~ 90 parts of alumina supports；
Wherein, the specific surface area of catalyst is 50 ~ 400 meters2/ gram, total pore volume is 0.3 ~ 2.0 ml/g, bore dia ＜ 30
The pore volume of nanometer accounts for the 5 ~ 60% of total pore volume, and the pore volume that 30 ~ 60 nanometers of bore dia accounts for the 20 ~ 75% of total pore volume, and bore dia ＞ 60 receives
The pore volume of rice accounts for the 20 ~ 60% of total pore volume.
In above-mentioned technical proposal, hydrogen ester mol ratio is preferably 15:1~30:1, air speed is preferably 0.6 ~ 1.5 hour-1, reaction
Temperature is preferably 200 ~ 250 DEG C, and reaction pressure is preferably 1.0 ~ 4.0MPa.
The preparation method of carrier of the present invention include aluminum oxide and modifying agent, peptizing agent, water are mixed in the desired amount, extrusion into
After type, first dried under the conditions of 50 ~ 120 DEG C 1 ~ 24 hour, be then calcined 1 ~ 10 hour at 800 ~ 1150 DEG C, obtain aluminum oxide
Carrier.
The preparation method of catalyst of the present invention is：First with a kind of liquid pre-preg carrier that can be dissolved each other with maceration extract, then use
The mixing salt solution dipping of metallic element containing each component, impregnated carrier is scrubbed, dry, 300 ~ 600 in air atmosphere
DEG C roasting produces finished catalyst.It is that can be used that finished catalyst, which only need to lead to hydrogen reducing in the reactor,.
The present invention catalyst be applied to acetate selection be hydrogenated with, preferably Dichlorodiphenyl Acetate methyl esters or ethyl acetate plus
Hydrogen.
During the catalyst of the present invention is used for acetate preparation of ethanol through hydrogenation, copper, Cu oxide and its mixture are
Main active component, therefore the high dispersive of active component is reactivity and the key factor of catalyst stability.Present invention system
Standby load type metal catalyst, metallic atom is dispersed on carrier with little particle or cluster form, the copper on catalyst point
There is a kind of inverse relation in divergence, the size of copper particle and the decentralization in carrier surface add to catalyst with copper particle size
Hydrogen performance, life-span and stability can all have a huge impact.When copper size of microcrystal is larger, the decentralization on carrier is poor,
Cause the activated centre of catalyst not enough, directly affect the Hydrogenation of catalyst, long-play can influence the longevity of catalyst
Life and stability.And copper size of microcrystal it is smaller when, preferably, be present the activated centre of abundance in decentralization on carrier, easily lead
Cause the dehydration etherificate side reaction of the hydro carbons such as acetate excessive hydrogenation generation methane, ethane and product alcohol.Therefore, it is being catalyzed
When agent is designed, copper size of microcrystal will select an appropriate scope.In addition, product also easily occurs for the more acidity of carrier surface
Etherificate, the acetalation of intermediate product.In order to solve this problem, alumina support of the present invention has relatively low acid
Amount, it is larger can several apertures and abundant mesoporous, both ensure that the high dispersive of active component, and in turn ensure that Large ratio surface activity
The good thermal stability of carrier.
The catalyst of the present invention has high feed stock conversion and high ethanol when for methyl acetate selective hydrogenation
Selectivity and catalyst activity keep good.The catalyst prepared using the present invention, using methyl acetate and hydrogen as raw material, anti-
It is 220 DEG C to answer temperature, and reaction pressure is 3.0MPa, and hydrogen/ester mol ratio is 25:1, air speed is 1.0 hours-1Under conditions of, acetic acid
Methyl ester conversion rate ＞ 98%, ethanol liquid phase selective ＞ 98%, catalyst is continuously run 1000 hours, achieves preferable technology effect
Really.
In concept used in the present invention, in the reaction of acetate preparation of ethanol through hydrogenation, acetic acid ester conversion rate and ethanol liquid phase
Selective calculation formula is as follows：
Below by embodiment, the invention will be further elaborated, but these embodiments are not anyway to this hair
Bright scope is construed as limiting.
Embodiment
【Embodiment 1】
29 grams of boehmite is weighed, 110 grams of gamma-aluminas, 2.7 grams of sesbania powders, mixing add the poly- of mass concentration 5%
1.4 grams of glycohol solution, 1.4 grams of nitric acid, 200 milliliters of the aqueous solution of two 1.0 grams of water magnesium nitrates, extrusion into 2.5 millimeters of Ф three
Leaf grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support with composite pore structural
A1.With deionized water pre-preg carrier, then drain away the water.Weigh 428 grams of copper nitrates, 1.14 gram of four water manganese nitrate and be made into 0.8M
Solution, is impregnated, colourless to maceration extract, is drained, 120 DEG C of dryings 4 hours, and 450 DEG C are calcined 6 hours, and catalyst C1 is made.Urge
Agent is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Embodiment 2】
116 grams of boehmite is weighed, 258 grams of gamma-aluminas, 7.4 grams of sesbania powders, mixing add the poly- of mass concentration 5%
3.7 grams of glycohol solution, 3.7 grams of nitric acid, 500 milliliters of the aqueous solution that 1.0 grams of four water-calcium nitrate, extrusion into 2.5 millimeters of Ф three
Leaf grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support with composite pore structural
A2.With deionized water pre-preg carrier, then drain away the water.475.6 grams of copper nitrates, 22.9 grams of zinc nitrate hexahydrates are weighed to be made into
0.8M solution, is impregnated, colourless to maceration extract, is drained, 120 DEG C of dryings 4 hours, and 450 DEG C are calcined 6 hours, and catalyst is made
C2.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Embodiment 3】
111.3 grams of boehmite is weighed, 47.7 grams of gamma-aluminas, 4.8 grams of sesbania powders, mixing add mass concentration 5%
3.2 grams of poly-vinyl alcohol solution, 3.5 grams of nitric acid, 500 milliliters of the aqueous solution that 1.9 grams of barium nitrate, extrusion into 2.5 millimeters of Ф three
Leaf grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support with composite pore structural
A3.With deionized water pre-preg carrier, then draining away the water weighs 114.1 grams of copper nitrates, 49.5 gram of six water nickel nitrate and is made into
0.8M solution, is impregnated, colourless to maceration extract, is drained, 120 DEG C of dryings 4 hours；450 DEG C are calcined 6 hours, and catalyst is made
C3.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Embodiment 4】
360 grams of boehmite is weighed, 185 grams of gamma-aluminas, 8.6 grams of sesbania powders, mixing add the poly- of mass concentration 5%
4.3 grams of glycohol solution, 4.3 grams of nitric acid, 200 milliliters of the aqueous solution of two 1.0 grams of water magnesium nitrates, extrusion into 2.5 millimeters of Ф three
Leaf grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support with composite pore structural
A6.With deionized water pre-preg carrier, then drain away the water.190.2 grams of copper nitrates, 46.7 grams of lanthanum nitrate hexahydrates are weighed to be made into
0.6M solution, is impregnated, colourless to maceration extract, is drained, 120 DEG C of dryings 4 hours, and 450 DEG C are calcined 6 hours, and catalyst is made
C4.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Embodiment 5】
21.5 grams of boehmite is weighed, 22 grams of gamma-aluminas, 1.3 grams of sesbania powders, mixing add the poly- of mass concentration 5%
4.3 grams of glycohol solution, 4.3 grams of nitric acid, 400 milliliters of the aqueous solution of two 1.9 grams of water barium nitrates, extrusion into 2.5 millimeters of Ф three
Leaf grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support with composite pore structural
A7.With deionized water pre-preg carrier, then drain away the water.209.2 grams of copper nitrates, 3.1 gram of six water cerous nitrate are weighed to be made into
0.6M solution, is impregnated, colourless to maceration extract, is drained, 120 DEG C of dryings, 450 DEG C of roastings in 4 hours 6 hours, and catalyst is made
C5.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Embodiment 6】
211 grams of boehmite is weighed, 200 grams of gamma-aluminas, 8 grams of sesbania powders, mixing add the poly- second of mass concentration 5%
4.0 grams of enolate solution, 4.0 grams of nitric acid, 600 milliliters of the aqueous solution of two 23.6 grams of water calcium nitrate, three leaves of the extrusion into 2.5 millimeters of Ф
Grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support A4 with composite pore structural.
With deionized water pre-preg carrier, then drain away the water.Weigh 475.6 grams of copper nitrates, 22.9 grams of zinc nitrate hexahydrates and be made into 0.8M
Solution, carries out carrier impregnation, colourless to maceration extract, drains, 120 DEG C of drying 4 hours, and 450 DEG C are calcined 6 hours, obtained catalyst
C6.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Embodiment 7】
289 grams of boehmite is weighed, 183 grams of gamma-aluminas, 9.2 grams of sesbania powders, mixing add the poly- of mass concentration 5%
4.6 grams of glycohol solution, 4.6 grams of nitric acid, 680 milliliters of the aqueous solution of two 15.4 grams of water magnesium nitrates, extrusion into 2.5 millimeters of Ф three
Leaf grass, wet bar is dried 24 hours through 50 DEG C and is calcined 4 hours after 1000 DEG C, obtains the alumina support with composite pore structural
A5.With deionized water pre-preg carrier, then drain away the water.19.0 grams of copper nitrates, 108.2 gram of nine water ferric nitrate are weighed to be made into
0.8M solution, is impregnated, colourless to maceration extract, is drained, 120 DEG C of dryings, 450 DEG C of roastings in 4 hours 6 hours, and catalyst is made
C7.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
【Comparative example 1】
Weigh 300 grams of boehmite, 9 grams of sesbania powders, 45 grams of graphite, mixing, extrusion into 2.5 millimeters of Ф clover,
Wet bar is dried 4 hours through 120 DEG C and is calcined 4 hours after 1000 DEG C, obtains carrier D1.Using the same operating procedure of embodiment 1
And catalyst CD1 is made in condition.Catalyst is constituted and specific surface area, pore volume, pore size distribution are shown in Table 1.
Table 1
【Embodiment 8】
This example demonstrates that application of the gained catalyst of embodiment 1 ~ 7 in methyl acetate or ethyl acetate selection hydrogenation.
Each 30mL of gained catalyst of the embodiment of the present invention 1 ~ 7 is taken, using pure hydrogen, 11h is reduced at 300 DEG C.With acetic acid
Ester and pure hydrogen are raw material, change process conditions and are tested, are analyzed using on-line chromatograph, the reaction result of 200 hours is shown in Table
2。
【Comparative example 2】
The gained catalyst 30ml of comparative example 1 is taken, is reduced 10 hours under 300 DEG C of pure hydrogen.With acetate and pure hydrogen
Tested, analyzed using on-line chromatograph for raw material, reaction result is shown in Table 2.
Table 2
【Embodiment 9】
This example demonstrates that the gained catalyst C3 of embodiment 3 is 1000 small in methyl acetate or ethyl acetate selection hydrogenation
When result of the test.
The gained catalyst C3 30mL of the embodiment of the present invention 3 are taken, using pure hydrogen, 11h is reduced at 300 DEG C.In reaction temperature
230 DEG C of degree, Hydrogen Vapor Pressure 3.0MPa, hydrogen/ester mol ratio 25:1, air speed 1.0 hours-1Under the conditions of react, using on-line analysis, instead
3 should be the results are shown in Table.
【Comparative example 3】
The gained catalyst 30ml of comparative example 1 is taken, is reduced 10 hours under 300 DEG C of pure hydrogen.With the same original of embodiment 9
Material, reaction condition are tested, and reaction result is shown in Table 3.
Table 3
Claims (8)
1. a kind of catalyst for preparing ethanol, including following components in terms of parts by weight：
A) 5~30 parts of metallic coppers or its oxide；
B) 0.05~20 part is selected from least one of alkaline-earth metal and transition metal element or its oxide；
C) 60~90 parts of alumina supports；
Wherein, the specific surface area of catalyst is 50~400 meters2/ gram, total pore volume is 0.3~2.0 ml/g, and bore dia ＜ 30 receives
The pore volume of rice accounts for the 5~60% of total pore volume, and the pore volume that 30~60 nanometers of bore dia accounts for the 20~75% of total pore volume, bore dia ＞ 60
The pore volume of nanometer accounts for the 20~60% of total pore volume；
The element of alkaline-earth metal is selected from least one of calcium, magnesium or barium, and for preparing alumina support；The element of transition metal
Selected from least one of manganese, nickel, lanthanum or cerium；
Copper size of microcrystal is 10~30 nanometers.
2. the catalyst according to claim 1 for preparing ethanol, it is characterised in that in terms of parts by weight, alumina support
Consumption is 60~85 parts.
3. the catalyst according to claim 2 for preparing ethanol, it is characterised in that in terms of parts by weight, metallic copper or its oxygen
The consumption of compound is 10~25 parts, the use selected from least one of alkaline-earth metal or/and transition metal element or its oxide
Measure as 0.1~10 part, the consumption of alumina support is 75~85 parts.
4. the catalyst according to claim 1 for preparing ethanol, it is characterised in that the specific surface area of catalyst is 50~300
Rice2/ gram, total pore volume is 0.5~1.5 ml/g, and the pore volume that 30 nanometers of bore dia ＜ accounts for the 20~45% of total pore volume, bore dia
30~60 nanometers of pore volume accounts for the 20~40% of total pore volume, and the pore volume that 60 nanometers of bore dia ＞ accounts for the 30~50% of total pore volume.
5. the catalyst according to claim 4 for preparing ethanol, it is characterised in that the specific surface area of catalyst is 100~
250 meters2/ gram, total pore volume is 0.8~1.2 ml/g, and the pore volume that 30 nanometers of bore dia ＜ accounts for 25~45%, Kong Zhi of total pore volume
The pore volume that 30~60 nanometers of footpath accounts for the 25~35% of total pore volume, and the pore volume that 60 nanometers of bore dia ＞ accounts for the 30~45% of total pore volume.
6. the catalyst according to claim 1 for preparing ethanol, it is characterised in that copper size of microcrystal is 10~20 nanometers.
7. catalyst described in claim 1 is used for the method for preparing ethanol, it is characterised in that using acetate and hydrogen as raw material,
Hydrogen/ester mol ratio is 2:1~45:1, air speed is 0.2~2.0 hour-1, reaction temperature is 150~350 DEG C, and reaction pressure is 0.5
Under the conditions of~10.0MPa, raw material and catalyst haptoreaction make the acetate in raw material be hydroconverted into ethanol, used urges
Agent is in terms of parts by weight including following components：
A) 5~30 parts of metallic coppers or its oxide；
B) 0.05~20 part is selected from least one of alkaline-earth metal and transition metal element or its oxide；
C) 60~90 parts of alumina supports；
Wherein, the specific surface area of catalyst is 50~400 meters2/ gram, total pore volume is 0.3~2.0 ml/g, and bore dia ＜ 30 receives
The pore volume of rice accounts for the 5~60% of total pore volume, and the pore volume that 30~60 nanometers of bore dia accounts for the 20~75% of total pore volume, bore dia ＞ 60
The pore volume of nanometer accounts for the 20~60% of total pore volume；
The element of alkaline-earth metal is selected from least one of calcium, magnesium or barium, and for preparing alumina support；The element of transition metal
Selected from least one of manganese, nickel, lanthanum or cerium；
Copper size of microcrystal is 10~30 nanometers.
8. the method for ethanol is prepared according to claim 7, it is characterised in that hydrogen ester mol ratio is 15:1~30:1, air speed is
0.6~1.5 hour-1, reaction temperature is 200~250 DEG C, and reaction pressure is 1.0~4.0MPa.
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| CN101121120A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Aluminium oxide carrier with composite holes structure and preparation method thereof |
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof |
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| CN1974510B (en) * | 2006-12-12 | 2011-06-08 | 四川大学 | Process for hydrogenating carboxylic acid and its ester to prepare alcohol |
| US8309772B2 (en) * | 2008-07-31 | 2012-11-13 | Celanese International Corporation | Tunable catalyst gas phase hydrogenation of carboxylic acids |
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| 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 |
| CN101121120A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Aluminium oxide carrier with composite holes structure and preparation method thereof |
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof |
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| KR102293261B1 (en) * | 2019-11-15 | 2021-08-23 | 한양대학교 산학협력단 | Supported Copper Catalyst and Selective Hydrogenation of Furan-based Compounds Using the Same |
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