CN105363454B - Hydrogenation catalyst - Google Patents
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- CN105363454B CN105363454B CN201410428177.1A CN201410428177A CN105363454B CN 105363454 B CN105363454 B CN 105363454B CN 201410428177 A CN201410428177 A CN 201410428177A CN 105363454 B CN105363454 B CN 105363454B
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Abstract
The present invention relates to a kind of hydrogenation catalyst, mainly solve to there is technical issues that in existing carboxylate hydrogen addition technology that hydrogen ester is lower than excessively high, feed stock conversion and selectivity of product.The present invention is by using by weight percentage, including following components：A) 10~50% copper or its oxide；B) 0~20% selected from least one of II B races of the periodic table of elements element or its oxide；C) 0~5% from least one of V A races of the periodic table of elements element or its oxide；D) 40~70% carrier, carrier are selected from least one of silica, aluminium oxide and molecular sieve；Wherein, the technical solution for being zero when component b) and component c) is different, which preferably solves the problems, such as this, in the industrial production available for carboxylate Hydrogenation alcohol.
Description
Technical field
The invention belongs to field of catalytic chemistry, more particularly to a kind of carboxylic ester hydrogenation catalyst.
Background technology
Ethyl alcohol is widely used in the industries such as food, medicine, chemical industry, fuel, national defence, as a kind of highly important cleaning combustion
Material and gasoline anti-knock agent component, can be greatly lowered the pollutant emission of burning.China is world's second largest gasoline production and disappears
Fei Guo, in Waste Era of Oil, replacement of fuel is to ensure one of national energy security and the cost-effective approach of reduction.Research shows that
Using E10 vehicle-use alcohol gasolines (ethyl alcohol 10%), octane number can improve 3%, can emission reduction CO25~30%, emission reduction CO2About 10%.
Therefore, development ethanol petrol is to improving environment, realizing that sustainable development is of great significance.
Along with the development of fiber, coating, binder industry, China's acetic acid industry production capacity Rapid Expansion, China in 2010
Accumulative 383.80 ten thousand tons of glacial acetic acid of production, increases by 29.29% on a year-on-year basis, significantly supply exceed demand for production of acetic acid, and Business Economic Benefit is big
Width declines.National polyvinyl alcohol production capacity reaches 87.7 ten thousand tons within 2011, about 1,450,000 tons of by-product methyl acetate.Due to methyl acetate
Market capacity is very limited (~5 ten thousand tons/year), and most enterprises can only be by hydrolyzing, separating and recovering acetic acid and methanol loop at present
It uses, retracting device technological process is complicated, and investment is high, high energy consumption.If being ethyl alcohol and methanol by acetate hydro-conversion, both may be used
Existing procedure can be simplified, realize energy-saving, and can solve the problems, such as byproduct outlet, eliminate PVA expand can bottleneck, expand
Acetic acid/methyl acetate downstream product chain improves added value of product and device overall economic efficiency.Therefore, exploitation feed coal is through vinegar
Acid/methyl acetate synthesis ethyl alcohol technology breaks away from the predicament that supply exceed demand of of poor benefits, product for current acetic acid and PVA industries, hair
Alternative fuel is opened up, ensures national energy security, there is great strategic significance and good development prospect.The Cu of commercial Application is urged at present
There is very big gap in agent, it is difficult to adapt in acetic acid industry material quality through ordinary wave in terms of hydrogenation activity, selectivity, hydrogen ester ratio
Dynamic requirement.Therefore, hydrogenation catalyst need to have low hydrogen ester ratio, preferable activity and selectivity, be used 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 titanium dioxide
On zirconium, in being reacted for methyl acetate preparation of ethanol through hydrogenation, methyl acetate conversion ratio is 80%, and ethanol selectivity is relatively low, only
68%.For this method using noble metal as active component, cost is higher and catalyst recovery processing is complicated, is unfavorable for industrial metaplasia
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 aluminium oxide or Ludox, is prepared using the precipitation method, and the precipitating reagent is carbonate, ammonium hydroxide or urea.
It is roasted 2~5 hours at gained reactive precursor is 2~24 hours, 350~500 DEG C dry at 60~120 DEG C.Implement in example, it should
Catalyst is used for acetate preparation of ethanol through hydrogenation, and acetic acid ester conversion rate is 80~90%, while required hydrogen/ester mole is higher,
Minimum 70：1.This method H2Consumption is big, more demanding to consersion unit.
CN102093162A discloses a kind of method with 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 at least one in silicate, Ludox, esters of silicon acis
Kind.The catalyst is in the reaction of methyl acetate preparation of ethanol through hydrogenation, the Mass Selective of ethyl alcohol to be 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, accounts for 5
~40%；Carrier silicas or aluminium oxide, account for 20~50%.It is in case study on implementation, the catalyst is anti-for acetic acid ester through hydrogenation
Ying Zhong, feed stock conversion are distributed in 70~85%, ethanol selectivity 79~81%.
In conclusion the Cu catalyst of prior art preparation is applied to during acetate preparation of ethanol through hydrogenation, there are hydrogen
The shortcomings such as ester is lower than high, feed stock conversion and ethanol selectivity.
Invention content
The first technical problem to be solved by the present invention is than excessively high, raw material in existing carboxylate hydrogen addition technology there are hydrogen ester
Conversion ratio is low, the technical barrier of alcohol selectivity and poor catalyst stability, provides a kind of new hydrogenation catalyst, which uses
In carboxylate Hydrogenation for alcohol react in have hydrogen ester than it is low, feed stock conversion is high, alcohol high selectivity and catalyst stability are good
The advantages of.The two of technical problem solved by the invention are to provide a kind of with solving the corresponding catalyst of one of technical problem
Purposes.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of hydrogenation catalyst, with weight
Percentages, including following components：
A) 10~50% copper or its oxide；
B) 0~15% selected from least one of II B races of the periodic table of elements element or its oxide；
C) 0~5% from least one of V A races of the periodic table of elements element or its oxide；
D) 40~70% carrier, carrier are selected from least one of silica, aluminium oxide and molecular sieve；
Wherein, it is zero when component b) and component c) is different.
In above-mentioned technical proposal, by weight percentage, in catalyst the content of copper or its oxide be preferably 15~
40%, more preferably 20~40%；Selected from least one of II B races of the periodic table of elements element or its oxide in catalyst
Content be preferably 1~15%, more preferably 2~10%；Selected from least one of V A races of the periodic table of elements in catalyst
The content of element or its oxide is preferably 0.001~3%, more preferably 0.01~2%；The dosage of carrier is preferably 40~
65%, more preferably 45~65%.
In above-mentioned technical proposal, selected from least one of II B races of the periodic table of elements element or its oxide in catalyst
The mixture of one kind preferably in ZnO, CdO, more preferably ZnO and CdO；By weight percentage, the ratio of ZnO and CdO
Preferably 1:1~9:1, more preferably 4:1~9:1.
In above-mentioned technical proposal, selected from least one of V A races of the periodic table of elements element or its oxide in catalyst
Preferably P2O5、Bi2O3In one kind, more preferably P2O5And Bi2O3Mixture；By weight percentage, P2O5And Bi2O3's
Ratio is preferably 9:1~19:1, more preferably 14:1~19:1
In above-mentioned technical proposal, carrier is preferably at least one of silica, molecular sieve in catalyst, is more preferably divided
Son sieve, the one kind of molecular sieve in MCM-48, SBA-15, ZSM-5.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：A kind of hydrogenation catalyst, feature
Be using ester and hydrogen as raw material, reaction temperature be 120~350 DEG C, reaction pressure be 0.5~5.0MPa, hydrogen/ester molar ratio
It is 5:1~35:1, volume space velocity is 0.5~20 hour-1Under conditions of, raw material and above-mentioned catalyst haptoreaction make in raw material
Carboxylate be hydroconverted into alcohol.
In above-mentioned technical proposal, reaction temperature is preferably 180~300 DEG C, and reaction pressure is preferably 2.0~4.0MPa, and hydrogen/
Ester molar ratio is preferably 15:1~30:1, volume space velocity is preferably 0.6~10 hour-1。
The selection that the catalyst of the present invention is suitable for carboxylate adds hydrogen, and carboxylate is C2~C20 carboxylates, can be straight chain
Or branch；Preferably Dichlorodiphenyl Acetate ester plus hydrogen, more preferably Dichlorodiphenyl Acetate methyl esters or ethyl acetate plus hydrogen；Target product alcohol is preferred
For low-carbon alcohols, more preferably methanol, ethyl alcohol, propyl alcohol or butanol.
The present invention proposes a kind of preparation method of hydrogenation catalyst, by added in into carrier mantoquita, builder salts it is mixed
Salting liquid is closed, heated, dry, roasting, compression molding obtains copper-based catalysts.What Pass through above-mentioned technical proposal obtained copper-based urges
Agent, active component high degree of dispersion realize uniform on micro-scale so that active component obtains catalyst during the reaction
To abundant exposure, so as to improve the activity of catalyst；Carrier presents neutral, it is suppressed that the life of by-product ether, aldehyde and higher alcohols
Into improving selectivity of the catalyst to product.In addition, the addition of co-catalyst is conducive to Proper Match catalyst redox
Performance can also be effectively prevented growing up for the active component crystal grain of catalyst during the reaction, so as to improve catalysis indirectly
The activity of agent extends the service life of catalyst.The especially addition of V A races P, Bi, increases active component in catalyst
With the synergistic effect of co-catalysis component, hence it is evident that change the texture of catalyst, reduce the reduction temperature of active ingredient copper.It is heavier
It wants, the addition of V A races element significantly enhances H2In the adsorbance of catalyst surface, the catalytic performance of catalyst obtains
It is promoted.The catalyst of the present invention is when for acetate selective hydrogenation with low hydrogen ester than, high feed stock conversion and high
Ethanol selectivity, and catalyst keeps higher activity and stability.
Catalyst composition in the present invention is tested using x-ray fluorescence analysis (XRF), after sample compression molding,
The characteristic spectral line intensity of atom is measured on the ZSX-100e4580 types XRF (Rigaku), is contained so as to find out component in sample
Amount.The catalyst prepared using the present invention is 230 DEG C in reaction temperature, reaction pressure is using methyl acetate and hydrogen as raw material
3.0MPa, hydrogen/ester molar ratio are 25:1, volume space velocity is 1.0 hours-1Under conditions of, methyl acetate conversion ratio ＞ 99%, ethyl alcohol
Selective ＞ 99%, catalyst continuous operation 3000 hours still keep higher activity and stability, achieve preferable technology
Effect.
In concept used in the present invention, the conversion ratio of acetate preparation of ethanol through hydrogenation and selective calculation formula are as follows：
The present invention will be further described below by way of examples, but these embodiments are not anyway to this hair
Bright range is construed as limiting.
Specific embodiment
【Embodiment 1】
150 grams of gamma-alumina powder, 3 grams of sesbania powders are weighed, are mixed, add in 180 milliliters of polyethylene containing mass concentration 5%
The aqueous solution of 3 grams of alcoholic solution, 4.5 grams of nitric acid, extrusion, wet bar through 50 DEG C after 1000 DEG C are roasted 4 hours, are obtained for dry 24 hours
Alumina catalyst support.With deionized water pre-preg carrier, then drain away the water.Weigh 60.4 grams of nitrate trihydrate copper, 110.2 gram of six water
Zinc nitrate is made into 0.8mol/L solution, and dipping drains, 120 DEG C of drying 4 hours, and 450 DEG C roast 6 hours, obtained catalyst C1,
Catalyst composition is shown in Table 1.
【Embodiment 2】
90 grams of gamma-alumina powder, 1.8 grams of sesbania powders are weighed, are mixed, add in 108 milliliters of poly- second containing mass concentration 5%
The aqueous solution of 1.8 grams of enolate solution, 2.7 grams of nitric acid, extrusion, wet bar roast 4 hours for dry 24 hours through 50 DEG C after 1000 DEG C,
Obtain alumina catalyst support.With deionized water pre-preg carrier, then drain away the water.Weigh 302 grams of nitrate trihydrate copper, 18.4 grams of nitre
Sour cadmium is made into 0.8mol/L solution, and dipping drains, 120 DEG C of drying 4 hours, and 450 DEG C roast 6 hours, and obtained catalyst C2 is urged
Agent composition is shown in Table 1.
【Embodiment 3】
90 grams of gamma-alumina powder, 1.8 grams of sesbania powders are weighed, are mixed, add in 108 milliliters of poly- second containing mass concentration 5%
The aqueous solution of 1.8 grams of enolate solution, 2.7 grams of nitric acid, extrusion, wet bar roast 4 hours for dry 24 hours through 50 DEG C after 1000 DEG C,
Obtain alumina catalyst support.With deionized water pre-preg carrier, then drain away the water.Weigh 302 grams of nitrate trihydrate copper, 18.4 gram six
Water zinc nitrate, 9.2 grams of cadmium nitrates are made into 0.8mol/L solution, and dipping drains, 120 DEG C of drying 4 hours, 450 DEG C of roastings 6 hours,
Catalyst C3 is made, catalyst composition is shown in Table 1.
【Embodiment 4】
90 grams of gamma-alumina powder, 1.8 grams of sesbania powders are weighed, are mixed, add in 108 milliliters of poly- second containing mass concentration 5%
The aqueous solution of 1.8 grams of enolate solution, 2.7 grams of nitric acid, extrusion, wet bar roast 4 hours for dry 24 hours through 50 DEG C after 1000 DEG C,
Obtain alumina catalyst support.With deionized water pre-preg carrier, then drain away the water.Weigh 302 grams of nitrate trihydrate copper, 33.0 gram six
Water zinc nitrate, 1.8 grams of cadmium nitrates are made into 0.8mol/L solution, and dipping drains, 120 DEG C of drying 4 hours, 450 DEG C of roastings 6 hours,
Catalyst C4 is made, catalyst composition is shown in Table 1.
【Embodiment 5】
90 grams of gamma-alumina powder, 1.8 grams of sesbania powders are weighed, are mixed, add in 108 milliliters of poly- second containing mass concentration 5%
The aqueous solution of 1.8 grams of enolate solution, 2.7 grams of nitric acid, extrusion, wet bar roast 4 hours for dry 24 hours through 50 DEG C after 1000 DEG C,
Obtain alumina catalyst support.With deionized water pre-preg carrier, then drain away the water.Weigh 302 grams of nitrate trihydrate copper, 29.4 gram six
Water zinc nitrate, 3.7 grams of cadmium nitrates are made into 0.8mol/L solution, and dipping drains, 120 DEG C of drying 4 hours, 450 DEG C of roastings 6 hours,
Catalyst C5 is made, catalyst composition is shown in Table 1.
【Embodiment 6】
80 grams of white carbons (mesh number 1500), 1.6 grams of sesbania powders are weighed, are mixed, add in 96 milliliters is containing mass concentration
The aqueous solution of 40% 50 grams of silicon sol solution, extrusion, wet bar through 50 DEG C after 500 DEG C are roasted 4 hours, are obtained for dry 24 hours
Carrier silicas.283.9 grams of nitrate trihydrate copper will be contained, 6.2 gram of five water bismuth nitrate is made into 0.8mol/L solution, dipping, drain,
It is 10 hours dry through 90 DEG C, it is roasted 10 hours at 400 DEG C, obtains catalyst C6, catalyst composition is shown in Table 1.
【Embodiment 7】
100 grams of white carbons (mesh number 1200), 1.2 grams of sesbania powders are weighed, are mixed, 120 milliliters is added in and contains mass concentration
The aqueous solution of 75 grams of silicon sol solution, 6.9 grams of phosphoric acid for 40%, extrusion, wet bar roast for dry 24 hours through 50 DEG C after 500 DEG C
It burns 4 hours, obtains carrier silicas.181.2 grams of nitrate trihydrate copper will be contained and be made into 0.8mol/L solution, impregnate, drain, through 90
It DEG C dry 10 hours, is roasted 10 hours at 400 DEG C, obtains catalyst C7, catalyst composition is shown in Table 1.
【Embodiment 8】
150 grams of white carbons (mesh number 1200), 3.0 grams of sesbania powders are weighed, are mixed, 180 milliliters is added in and contains mass concentration
The aqueous solution of 104 grams of silicon sol solution, 6.2 grams of phosphoric acid for 30%, extrusion, wet bar dry 24 hours after 500 DEG C through 50 DEG C
Roasting 4 hours, obtains carrier silicas.181.2 grams of nitrate trihydrate copper will be contained, 1.04 gram of five water bismuth nitrate is made into 0.8mol/L
Solution, dipping, drains, 10 hours dry through 90 DEG C, is roasted 10 hours at 400 DEG C, obtains catalyst C8, and catalyst composition is shown in Table
1。
【Embodiment 9】
150 grams of white carbons (mesh number 1200), 3.0 grams of sesbania powders are weighed, are mixed, 180 milliliters is added in and contains mass concentration
The aqueous solution of 104 grams of silicon sol solution, 6.6 grams of phosphoric acid for 40%, extrusion, wet bar dry 24 hours after 500 DEG C through 50 DEG C
Roasting 4 hours, obtains carrier silicas.181.2 grams of nitrate trihydrate copper will be contained, 0.52 gram of five water bismuth nitrate is made into 0.8mol/L
Solution, dipping, drains, 10 hours dry through 90 DEG C, is roasted 10 hours at 400 DEG C, obtains catalyst C9, and catalyst composition is shown in Table
1。
【Embodiment 10】
Weigh 283.88 grams of nitrate trihydrate copper, 6.24 grams of bismuth nitrates are made into 0.6mol/L solution, under stirring, be added to 100
In gram H-type MCM-48 molecular sieves (pure silicon molecular sieve), dipping drains, 90 DEG C of drying 10 hours, in 600 DEG C of roastings 10 hours, obtains
To catalyst C10, catalyst composition is shown in Table 1.
【Embodiment 11】
Weigh 283.88 grams of nitrate trihydrate copper, 6.24 grams of bismuth nitrates are made into 0.6mol/L solution, under stirring, be added to 100
In gram H-type SBA-15 molecular sieves (pure silicon molecular sieve), dipping drains, 90 DEG C of drying 10 hours, in 600 DEG C of roastings 10 hours, obtains
To catalyst C10, catalyst composition is shown in Table 1.
【Embodiment 12】
Weigh 283.88 grams of nitrate trihydrate copper, 6.24 grams of bismuth nitrates are made into 0.6mol/L solution, under stirring, be added to 100
In gram H-type ZSM-5 molecular sieve (pure silicon molecular sieve), dipping drains, 90 DEG C of drying 10 hours, in 600 DEG C of roastings 10 hours, obtains
To catalyst C10, catalyst composition is shown in Table 1.
【Embodiment 13】
It weighs 90.6 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrates, 6.9 grams of phosphoric acid and is made into 0.8mol/L solution, stir
Under, 400 grams of the silicon sol solution that mass concentration is 30% is added in, is stirred evenly, 80 DEG C of drying 10 hours, in 600 DEG C of roastings 10
Hour, compression molding obtains catalyst C13, and catalyst composition is shown in Table 1.
【Embodiment 14】
It weighs 90.6 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrates, 4.1 grams of phosphoric acid and is made into 0.8mol/L solution, stir
Under, 413.3 grams of the silicon sol solution that mass concentration is 30% is added in, is stirred evenly, 80 DEG C of drying 10 hours are roasted at 600 DEG C
10 hours, compression molding obtained catalyst C14, and catalyst composition is shown in Table 1.
【Embodiment 15】
It weighs 90.6 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrates, 0.0014 gram of phosphoric acid and is made into 0.8mol/L solution,
Under stirring, 433.3 grams of the silicon sol solution that mass concentration is 30% is added in, is stirred evenly, 80 DEG C of dryings 10 hours, at 600 DEG C
Roasting 10 hours, compression molding obtain catalyst C15, and catalyst composition is shown in Table 1.
【Embodiment 16】
It weighs 90.6 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrates, 2.8 grams of phosphoric acid and is made into 0.8mol/L solution, stir
Under, 420 grams of the silicon sol solution that mass concentration is 30% is added in, is stirred evenly, 80 DEG C of drying 10 hours, in 600 DEG C of roastings 10
Hour, compression molding obtains catalyst C16, and catalyst composition is shown in Table 1.
【Embodiment 17】
It weighs 90.6 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrates, 0.014 gram of phosphoric acid and is made into 0.8mol/L solution, stir
It mixes down, adds in 433.3 grams of the silicon sol solution that mass concentration is 30%, stir evenly, 80 DEG C of drying 10 hours are roasted at 600 DEG C
It burns 10 hours, compression molding obtains catalyst C17, and catalyst composition is shown in Table 1.
【Embodiment 18】
Weigh 181.2 grams of nitrate trihydrate copper, 36.7 grams of zinc nitrate hexahydrates, 1.8 grams of cadmium nitrates, 0.01 gram of five water bismuth nitrate,
0.1 gram of phosphoric acid is made into 0.8mol/L solution, under stirring, adds in 322 grams of the silicon sol solution that mass concentration is 40%, stirring is equal
It is even.80 DEG C of dryings 10 hours roast 10 hours at 600 DEG C, and compression molding obtains catalyst C18, and catalyst composition is shown in Table 1.
【Embodiment 19】
Weigh 181.2 grams of nitrate trihydrate copper, 66.1 grams of zinc nitrate hexahydrates, 3.7 grams of cadmium nitrates, 0.21 gram of bismuth nitrate, 2.6 grams
Phosphoric acid is made into 0.6mol/L solution, under stirring, is added in 116 grams of H-type ZSM-5 molecular sieves (pure silicon molecular sieve), impregnates, drip
Dry, 90 DEG C of drying 10 hours roast 10 hours at 600 DEG C, obtain catalyst C19, catalyst forms and is shown in Table 1.
【Embodiment 20】
302 grams of nitrate trihydrate copper, 18.4 grams of cadmium nitrates, 0.4 gram of bismuth nitrate, 2.8 grams of phosphoric acid and 0.1 gram of potassium nitrate is weighed to match
It into 0.6mol/L solution, under stirring, is added in 85.6 grams of H-type beta-molecular sieves, impregnates, drain, 90 DEG C of dryings 10 hours, 600
DEG C roasting 10 hours, obtains catalyst C20, catalyst composition is shown in Table 1.
【Comparative example 1】
Comparative example catalyst is prepared according to the patent CN102872878A methods provided, by 60.4 grams of copper nitrates, 10.0
Gram aluminum nitrate, 74.4 grams of zinc nitrates, 3.0 grams of lanthanum nitrates are placed in beaker, are added in 500 grams of distilled water and are made it completely dissolved, are denoted as
Solution 1；305 grams of the ammonium hydroxide of mass fraction 10% is prepared, is denoted as solution 2；Under condition of heating and stirring by solution 1 and solution 2 simultaneously
Addition is precipitated, and keeps 80 DEG C of temperature, controls terminal pH7.0, and aging 3 hours is filtered, washing, 80 DEG C of dryings 15 hours,
400 DEG C roast 6 hours, and compression molding obtains catalyst B1, and catalyst composition is shown in Table 1.
Table 1
| Embodiment is numbered | Catalyst is numbered | Catalyst forms, weight percent |
| 1 | C1 | 10CuO-15ZnO-75Al2O3 |
| 2 | C2 | 50CuO-5CdO-45Al2O3 |
| 3 | C3 | 50CuO-2.5ZnO-2.5CdO-45Al2O3 |
| 4 | C4 | 50CuO-4.5ZnO-0.5CdO-45Al2O3 |
| 5 | C5 | 50CuO-4.0ZnO-1.0CdO-45Al2O3 |
| 6 | C6 | 47CuO-3Bi2O3-50SiO2 |
| 7 | C7 | 30CuO-5P2O5-65SiO2 |
| 8 | C8 | 30CuO-4.5P2O5-0.5Bi2O3-65SiO2 |
| 9 | C9 | 30CuO-4.75P2O5-0.25Bi2O3-65SiO2 |
| 10 | C10 | 47CuO-3Bi2O3-50MCM-48 |
| 11 | C11 | 47CuO-3Bi2O3-50SBA-15 |
| 12 | C12 | 47CuO-3Bi2O3-50ZSM-5 |
| 13 | C13 | 15CuO-20ZnO-5P2O5-60SiO2 |
| 14 | C14 | 15CuO-20ZnO-3P2O5-62SiO2 |
| 15 | C15 | 15CuO-20ZnO-0.001P2O5-64.999SiO2 |
| 16 | C16 | 15CuO-20ZnO-2P2O5-63SiO2 |
| 17 | C17 | 15CuO-20ZnO-0.01P2O5-64.99SiO2 |
| 18 | C18 | 30CuO-5ZnO-0.5CdO-0.1P2O5-0.005Bi2O3- 64.4SiO2 |
| 19 | C19 | 30CuO-9ZnO-1CdO-1.9P2O5-0.1Bi2O3- 58ZSM-5 |
| 20 | C20 | 50CuO-5CdO-2P2O5-0.2Bi2O3-42.8SiO2 |
| Comparative example 1 | B1 | 51.7CuO-2La2O3-3.2Al2O3-43.1ZnO |
【Embodiment 21~43】
This example demonstrates that application of the 0 gained catalyst of Examples 1 to 2 in the reaction of carboxylate preparation of ethanol through hydrogenation.
1~20 each 30ml of gained catalyst of the embodiment of the present invention is taken, is restored 10 hours under 300 DEG C of pure hydrogen.With carboxylic
Acid esters and pure hydrogen are raw material, change process conditions and are tested, are analyzed using on-line chromatograph, reaction result is shown in Table 2.
【Comparative example 2】
1 reducing condition of comparative example weighs B1 catalyst 30mL, activation phenomenon hydrogen and nitrogen with reference to patent CN102872878A
The gaseous mixture (hydrogen volume score is 15%) of gas, restores 10 hours at 250 DEG C.It is carried out using acetate and pure hydrogen as raw material
Experiment, is analyzed, reaction result is shown in Table 2 using on-line chromatograph.
Table 2
Claims (8)
1. a kind of hydrogenation catalyst, by weight percentage, including following components：
A) 10~50% copper or its oxide；
B) mixture of 0~20% ZnO and CdO；
C) 0~5% P2O5And Bi2O3Mixture；
D) 40~70% carrier, carrier are selected from least one of silica, aluminium oxide and molecular sieve；
Wherein, component c) is not zero.
2. hydrogenation catalyst according to claim 1, it is characterised in that by weight percentage, copper or its oxygen in catalyst
The content of compound is 15~40%.
3. hydrogenation catalyst according to claim 1, it is characterised in that by weight percentage, the mixture of ZnO and CdO
Content be 1~15%.
4. hydrogenation catalyst according to claim 3, it is characterised in that by weight percentage, the mixture of ZnO and CdO
Content be 2~10%.
5. hydrogenation catalyst according to claim 1, it is characterised in that by weight percentage, P2O5And Bi2O3Mixing
The content of object is 0.001~3%.
6. hydrogenation catalyst according to claim 5, it is characterised in that by weight percentage, P2O5And Bi2O3Mixing
The content of object is 0.01~2%.
7. hydrogenation catalyst according to claim 1, it is characterised in that in the mixture of ZnO and CdO, ZnO and CdO's
Weight ratio is 1:1~9:1.
8. hydrogenation catalyst according to claim 1, it is characterised in that in P2O5And Bi2O3Mixture in, P2O5With
Bi2O3Weight ratio be 9:1~19:1.
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|---|---|---|---|
| CN201410428177.1A CN105363454B (en) | 2014-08-27 | 2014-08-27 | Hydrogenation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410428177.1A CN105363454B (en) | 2014-08-27 | 2014-08-27 | Hydrogenation catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN105363454A CN105363454A (en) | 2016-03-02 |
| CN105363454B true CN105363454B (en) | 2018-06-08 |
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| CN201410428177.1A Active CN105363454B (en) | 2014-08-27 | 2014-08-27 | Hydrogenation catalyst |
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| CN109482192B (en) * | 2018-11-30 | 2021-09-07 | 万华化学集团股份有限公司 | Preparation method and application of catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation |
| GB202213961D0 (en) | 2022-09-23 | 2022-11-09 | Johnson Matthey Plc | Copper-containing hydrogenation catalysts for the hydrogenolysis of esters |
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| CN101176848A (en) * | 2007-11-12 | 2008-05-14 | 青岛科技大学 | Catalyzer for preparing 1, 3-trimethylene glycol from 3-hydracrylic acid ester through hydrogenation and preparation method thereof |
| CN101992115A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | High selective catalyst |
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| CN101176848A (en) * | 2007-11-12 | 2008-05-14 | 青岛科技大学 | Catalyzer for preparing 1, 3-trimethylene glycol from 3-hydracrylic acid ester through hydrogenation and preparation method thereof |
| CN101992115A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | High selective catalyst |
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| Cu/Bi/Al2O3催化剂制备及表征;黄秋锋等;《福建化工》;20031231(第4期);第5页右栏第1段、第1.1.2节 * |
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