CN105435798B - Carboxylate hydrogenation copper base catalyst - Google Patents
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Abstract
The present invention relates to a kind of carboxylate hydrogenation copper base catalyst, mainly solve in existing carboxylate hydrogen addition technology that there are the technical problems that hydrogen ester is lower than excessively high, feed stock conversion and selectivity of product is poor.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) 0~10% from least one of VI B races of the periodic table of elements element or its oxide；D) 30~75% 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) different, preferably solves the problems, such as this, can be used in the industrial production of carboxylate Hydrogenation alcohol.
Description
Technical field
The invention belongs to field of catalytic chemistry, more particularly to a kind of carboxylate hydrogenation copper base catalyst.
Background technology
Ethyl alcohol is widely used in the industries such as food, medicine, chemical industry, fuel, national defence, is fired as a kind of highly important cleaning
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 one of to ensure national energy security and reduce cost-effective approach.Studies have shown that
Using E10 vehicle-use alcohol gasolines (ethyl alcohol 10%), octane number can be improved 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, obviously 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 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 the reaction of methyl acetate preparation of ethanol through hydrogenation, methyl acetate conversion ratio to be 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 and its preparation method and application of acetate preparation of ethanol through hydrogenation, urges
The main catalytic group of agent is divided into 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 relatively high,
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 that there are hydrogen esters than excessively high, raw material in existing carboxylate hydrogen addition technology
Conversion ratio is low, alcohol selectivity and poor catalyst stability technical barrier, provides a kind of new hydrogenation copper base catalyst, the catalysis
Agent has hydrogen ester than low, feed stock conversion is high, alcohol high selectivity and catalyst stabilization in being reacted for alcohol for carboxylate Hydrogenation
The good advantage of property.The two of technical problem solved by the invention are to provide one kind and solve the corresponding catalysis of one of technical problem
The purposes of agent.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of carboxylate hydrogenation copper base is urged
Agent, 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) 0~15% from least one of VI B races of the periodic table of elements element or its oxide；
D) 30~75% carrier, carrier are selected from least one of silica, aluminium oxide and molecular sieve.
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 periodic table of elements element or its oxide in catalyst
Content is preferably 1~15%, and more preferably 2~8%；Selected from least one of VI B races of periodic table of elements element in catalyst
Or the content of its oxide is preferably 0.5~6%, more preferably 1~4%；The dosage of carrier is preferably 40~65%, more preferably
It is 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 9:1~19:1, more preferably 14:1~19:1.
In above-mentioned technical proposal, selected from least one of IV B races of the periodic table of elements element or its oxide in catalyst
Preferably Cr2O3、MoO3In one kind, more preferably Cr2O3And MoO3Mixture；By weight percentage, Cr2O3And MoO3
Ratio be preferably 1:14~1:4, more preferably 1:9~1:4.
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, MCM-41, SBA-15.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：A kind of carboxylate hydrogenation copper base is urged
Agent, it is characterised in that it is 120~350 DEG C in reaction temperature using ester and hydrogen as raw material, reaction pressure is 0.5~5.0MPa,
Hydrogen/ester molar ratio is 5:1~35:1, volume space velocity is 0.5~20 hour-1Under conditions of, raw material contacts instead with above-mentioned catalyst
It answers, the carboxylate in raw material is made to 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, preferably Dichlorodiphenyl Acetate ester plus hydrogen, more preferably pair
Methyl acetate or ethyl acetate plus hydrogen；Target product alcohol is preferably low-carbon alcohols, more preferably methanol, ethyl alcohol, propyl alcohol or butanol.
The present invention proposes a kind of preparation method of carboxylate hydrogenation copper base catalyst, by into carrier be added mantoquita,
The mixing salt solution of builder salts, heated, dry, roasting, molding obtains copper-based catalysts.What Pass through above-mentioned technical proposal obtained
Copper-based catalysts, active component high degree of dispersion realize uniform on micro-scale so that catalyst is active during the reaction
Component is fully exposed, to improve the activity of catalyst；Carrier presents neutral, it is suppressed that by-product ether, aldehyde and more carbon
The generation of alcohol improves selectivity of the catalyst to product.Wherein, VI B races chromium, the molybdenum element of addition promote the new object of copper, zinc
The generation of phase is improved through the enhancing of copper zinc synergistic effect, CuO dispersion degrees in high-temperature roasting rear catalyst, and reduction temperature is notable
It reduces, while H2Adsorption capacity enhances.Catalyst after reduction is in ester through hydrogenation reaction, catalytic activity and stability obviously to carry
It is high.The catalyst of the present invention is when for acetate selective hydrogenation with low hydrogen ester than, high feed stock conversion and high second
Alcohol 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 that atom is measured on the ZSX-100e4580 types XRF (Rigaku), contains 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, air speed is 1.0 hours-1Under conditions of, methyl acetate conversion ratio > 99%, ethyl alcohol selection
Property > 99%, catalyst continuous operation 3000 hours still keeps higher activity and stability, achieves preferable technology effect
Fruit.
In concept used in the present invention, carboxylate Hydrogenation for alcohol conversion ratio and molar selectivity calculation formula such as
Under：
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 implementation mode
【Embodiment 1】
30.2 grams of nitrate trihydrate copper, 55.1 grams of zinc nitrate hexahydrates are weighed, 275.8 gram of nine water aluminum nitrate is placed in three-necked flask
In, 1000 grams of distilled water are added and make it completely dissolved, 90 DEG C are heated under stirring；It weighs 133.4 grams of sodium carbonate and is placed in burning
In cup, 1000 grams of distilled water are added and make it completely dissolved, moves in dropping funel, obtains precipitating reagent.In three-necked flask, salt-mixture
The precipitating reagent of preparation is added dropwise under solution heating stirring state, after being added dropwise, return stirring 5 hours is filtered, washed, and 80 DEG C dry
Dry 12 hours, 450 DEG C roasted 6 hours, after compression molding, catalyst C1 were made, catalyst composition is shown in Table 1.
【Embodiment 2】
302 grams of nitrate trihydrate copper, 146.9 grams of zinc nitrate hexahydrates are weighed, 220.7 gram of nine water aluminum nitrate is placed in three-necked flask
In, 2000 grams of distilled water are added and make it completely dissolved, 90 DEG C are heated under stirring；It weighs 185.9 grams of sodium carbonate and is placed in burning
In cup, 2000 grams of distilled water are added and make it completely dissolved, moves in dropping funel, obtains precipitating reagent.In three-necked flask, salt-mixture
The precipitating reagent of preparation is added dropwise under solution heating stirring state, after being added dropwise, return stirring 5 hours is filtered, washed, and 80 DEG C dry
Dry 12 hours, 450 DEG C roasted 6 hours, after compression molding, catalyst C2 were made, catalyst composition is shown in Table 1.
【Embodiment 3】
241.6 grams of nitrate trihydrate copper, 73.4 grams of zinc nitrate hexahydrates are weighed, 367.8 gram of nine water aluminum nitrate is placed in three-necked flask
In, 2000 grams of distilled water are added and make it completely dissolved, 90 DEG C are heated under stirring；It weighs 222.0 grams of sodium carbonate and is placed in burning
In cup, 2000 grams of distilled water are added and make it completely dissolved, moves in dropping funel, obtains precipitating reagent.In three-necked flask, salt-mixture
The precipitating reagent of preparation is added dropwise under solution heating stirring state, after being added dropwise, return stirring 5 hours is filtered, washed, and 80 DEG C dry
Dry 12 hours, 450 DEG C roasted 6 hours, after compression molding, catalyst C3 were made, catalyst composition is shown in Table 1.
【Embodiment 4】
Weigh 241.6 grams of nitrate trihydrate copper, 66.1 grams of zinc nitrate hexahydrates, 3.7 grams of cadmium nitrates, 367.8 gram of nine water aluminum nitrate
It is placed in three-necked flask, 2000 grams of distilled water is added and make it completely dissolved, 90 DEG C are heated under stirring；Weigh 221.5 grams
Sodium carbonate is placed in beaker, and 2000 grams of distilled water are added and make it completely dissolved, moves in dropping funel, obtains precipitating reagent.Three mouthfuls
In flask, the precipitating reagent of preparation is added dropwise under mixing salt solution heating stirring state, after being added dropwise, return stirring 5 hours, mistake
Filter, washing, 80 DEG C of drying 12 hours, 450 DEG C roast 6 hours, after compression molding, catalyst C4 are made, catalyst is formed and is shown in Table
1。
【Embodiment 5】
Weigh 241.6 grams of nitrate trihydrate copper, 68.5 grams of zinc nitrate hexahydrates, 2.5 grams of cadmium nitrates, 367.8 gram of nine water aluminum nitrate
It is placed in three-necked flask, 2000 grams of distilled water is added and make it completely dissolved, 90 DEG C are heated under stirring；Weigh 221.6 grams
Sodium carbonate is placed in beaker, and 2000 grams of distilled water are added and make it completely dissolved, moves in dropping funel, obtains precipitating reagent.Three mouthfuls
In flask, the precipitating reagent of preparation is added dropwise under mixing salt solution heating stirring state, after being added dropwise, return stirring 5 hours, mistake
Filter, washing, 80 DEG C of drying 12 hours, 450 DEG C roast 6 hours, after compression molding, catalyst C5 are made, catalyst is formed and is shown in Table
1。
【Embodiment 6】
Weigh 241.6 grams of nitrate trihydrate copper, 69.8 grams of zinc nitrate hexahydrates, 1.8 grams of cadmium nitrates, 367.8 gram of nine water aluminum nitrate
It is placed in three-necked flask, 2000 grams of distilled water is added and make it completely dissolved, 90 DEG C are heated under stirring；Weigh 221.7 grams
Sodium carbonate is placed in beaker, and 2000 grams of distilled water are added and make it completely dissolved, moves in dropping funel, obtains precipitating reagent.Three mouthfuls
In flask, the precipitating reagent of preparation is added dropwise under mixing salt solution heating stirring state, after being added dropwise, return stirring 5 hours, mistake
Filter, washing, 80 DEG C of drying 12 hours, 450 DEG C roast 6 hours, after compression molding, catalyst C6 are made, catalyst is formed and is shown in Table
1。
【Embodiment 7】
It weighs 120.8 grams of nitrate trihydrate copper and is made into 0.4mol/L solution；24.5 grams of ammonium molybdate tetrahydrates are weighed, under stiring,
466.7 grams of the silicon sol solution that mass concentration is 30% is added, stirs evenly, 80 DEG C of drying 10 hours, roasting 10 is small at 600 DEG C
When, molding obtains catalyst C7, and catalyst composition is shown in Table 1.
【Embodiment 8】
120 grams of white carbons (mesh number 1500), 2.4 grams of sesbania powders are weighed, are mixed, 145 milliliters is added and contains 24.5 gram four
The aqueous solution of water ammonium molybdate, 50 grams of the silicon sol solution that mass concentration is 40%, extrusion, wet bar through 50 DEG C after dry 24 hours in
500 DEG C roast 4 hours, obtain carrier silicas.120.8 grams of nitrate trihydrate copper will be contained and be made into 0.8mol/L solution, impregnated, drip
It is dry, it is 10 hours dry through 90 DEG C, it is roasted 10 hours at 500 DEG C, obtains catalyst C8, catalyst composition is shown in Table 1.
【Embodiment 9】
120 grams of white carbons (mesh number 1500), 2.4 grams of sesbania powders are weighed, are mixed, 145 milliliters is added and contains 22.9 gram four
The aqueous solution of water ammonium molybdate, 50 grams of the silicon sol solution that mass concentration is 40%, extrusion, wet bar through 50 DEG C after dry 24 hours in
500 DEG C roast 4 hours, obtain carrier silicas.120.8 grams of nitrate trihydrate copper will be contained, 7 gram of nine water chromic nitrate is made into
0.8mol/L solution, dipping, drains, 10 hours dry through 90 DEG C, is roasted 10 hours at 500 DEG C, obtains catalyst C9, catalyst
Composition is shown in Table 1.
【Embodiment 10】
120 grams of white carbons (mesh number 1500), 2.4 grams of sesbania powders are weighed, are mixed, 145 milliliters is added and contains 22.1 gram four
The aqueous solution of water ammonium molybdate, 50 grams of the silicon sol solution that mass concentration is 40%, extrusion, wet bar through 50 DEG C after dry 24 hours in
500 DEG C roast 4 hours, obtain carrier silicas.120.8 grams of nitrate trihydrate copper will be contained, 10.5 gram of nine water chromic nitrate is made into
0.8mol/L solution, dipping, drains, 10 hours dry through 90 DEG C, is roasted 10 hours at 500 DEG C, obtains catalyst C10, is catalyzed
Agent composition is shown in Table 1.
【Embodiment 11】
120 grams of white carbons (mesh number 1500), 2.4 grams of sesbania powders are weighed, are mixed, 145 milliliters is added and contains 19.6 gram four
The aqueous solution of water ammonium molybdate, 50 grams of the silicon sol solution that mass concentration is 40%, extrusion, wet bar through 50 DEG C after dry 24 hours in
500 DEG C roast 4 hours, obtain carrier silicas.120.8 grams of nitrate trihydrate copper will be contained, 21 gram of nine water chromic nitrate is made into
0.8mol/L solution, dipping, drains, 10 hours dry through 90 DEG C, is roasted 10 hours at 500 DEG C, obtains catalyst C11, is catalyzed
Agent composition is shown in Table 1.
【Embodiment 12】
It weighs 120.8 grams of nitrate trihydrate copper and is made into 1.0mol/L solution, under stirring, be added to 140 grams of H-type MCM-48 molecules
In sieve, dipping, until maceration extract in colourless, drains, 90 DEG C of dryings 10 hours roast 5 hours at 400 DEG C；Weigh 24.5 gram of four water
Ammonium molybdate is made into 0.8mol/L solution, and dipping drains, and 90 DEG C of dryings 10 hours roast 5 hours at 600 DEG C, obtain catalyst
C12, catalyst composition are shown in Table 1.
【Embodiment 13】
It weighs 120.8 grams of nitrate trihydrate copper and is made into 1.0mol/L solution, under stirring, be added to 140 grams of H-type MCM-41 molecules
In sieve, dipping, until maceration extract in colourless, drains, 90 DEG C of dryings 10 hours roast 5 hours at 400 DEG C；Weigh 24.5 gram of four water
Ammonium molybdate is made into 0.8mol/L solution, and dipping drains, and 90 DEG C of dryings 10 hours roast 5 hours at 600 DEG C, obtain catalyst
C13, catalyst composition are shown in Table 1.
【Embodiment 14】
It weighs 120.8 grams of nitrate trihydrate copper and is made into 1.0mol/L solution, under stirring, be added to 140 grams of H-type SBA-15 molecules
In sieve, dipping, until maceration extract in colourless, drains, 90 DEG C of dryings 10 hours roast 5 hours at 400 DEG C；Weigh 24.5 gram of four water
Ammonium molybdate is made into 0.8mol/L solution, and dipping drains, and 90 DEG C of dryings 10 hours roast 5 hours at 600 DEG C, obtain catalyst
C14, catalyst composition are shown in Table 1.
【Embodiment 15】
It weighs 120.8 grams of nitrate trihydrate copper and is made into 1.0mol/L solution, under stirring, be added to 140 grams of H-type ZSM-5 molecules
In sieve, dipping, until maceration extract in colourless, drains, 90 DEG C of dryings 10 hours roast 5 hours at 400 DEG C；Weigh 24.5 gram of four water
Ammonium molybdate is made into 0.8mol/L solution, and dipping drains, and 90 DEG C of dryings 10 hours roast 5 hours at 600 DEG C, obtain catalyst
C15, catalyst composition are shown in Table 1.
【Embodiment 16】
Weigh that 211.4 grams of nitrate trihydrate copper, 73.5 grams of zinc nitrate hexahydrates, that 24.5 grams of ammonium molybdate tetrahydrates are made into 1.0mol/L is molten
Liquid under stirring, is added ammonium hydroxide, is adjusted to pH value 10, is added in 90 grams of H-type MCM-41 molecular sieves, impregnates repeatedly, until maceration extract
It in colourless, drains, 90 DEG C of dryings 10 hours roast 6 hours at 450 DEG C, obtain catalyst C16, catalyst composition is shown in Table 1.
【Embodiment 17】
Weigh that 211.4 grams of nitrate trihydrate copper, 73.5 grams of zinc nitrate hexahydrates, that 14.7 grams of ammonium molybdate tetrahydrates are made into 1.0mol/L is molten
Liquid under stirring, is added ammonium hydroxide, is adjusted to pH value 10, is added in 98 grams of H-type MCM-41 molecular sieves, impregnates repeatedly, until maceration extract
It in colourless, drains, 90 DEG C of dryings 10 hours roast 6 hours at 450 DEG C, obtain catalyst C17, catalyst composition is shown in Table 1.
【Embodiment 18】
Weigh that 211.4 grams of nitrate trihydrate copper, 73.5 grams of zinc nitrate hexahydrates, that 4.9 grams of ammonium molybdate tetrahydrates are made into 1.0mol/L is molten
Liquid under stirring, is added ammonium hydroxide, is adjusted to pH value 10, is added in 106 grams of H-type MCM-41 molecular sieves, impregnates repeatedly, until dipping
Liquid is drained in colourless, and 90 DEG C of drying 10 hours roast 6 hours at 450 DEG C, obtain catalyst C18, catalyst forms and is shown in Table 1.
【Embodiment 19】
Weigh that 211.4 grams of nitrate trihydrate copper, 73.5 grams of zinc nitrate hexahydrates, that 2.5 grams of ammonium molybdate tetrahydrates are made into 1.0mol/L is molten
Liquid under stirring, is added ammonium hydroxide, is adjusted to pH value 10, is added in 106 grams of H-type MCM-41 molecular sieves, impregnates repeatedly, until dipping
Liquid is drained in colourless, and 90 DEG C of dryings 10 hours roast 3 hours at 450 DEG C；It weighs 8.4 grams of four water-calcium nitrates and is made into 0.6mol/L
Solution, dipping, drains, and 90 DEG C of drying 10 hours roast 3 hours at 450 DEG C, obtains catalyst C19, and catalyst forms and 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, and 500 grams of distilled water are added and make it completely dissolved, are denoted as
Solution 1；305 grams of ammonium hydroxide for preparing mass fraction 10%, is denoted as solution 2；Under condition of heating and stirring simultaneously by solution 1 and solution 2
Addition is precipitated, and 80 DEG C of temperature is kept, and 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.
【Comparative example 2】
60.0 grams of white carbons (mesh number 1500), 24.0 grams of zirconium oxides, 1.68 grams of sesbania powders are weighed, are mixed, are added 100.8
The aqueous solution for 50 grams of the silicon sol solution that milliliter is 40% containing mass concentration, extrusion, wet bar through 50 DEG C after dry 24 hours in
500 DEG C roast 4 hours, obtain ZrO2-SiO2Carrier.289.9 grams of nitrate trihydrate copper will be contained and be made into 0.6mol/L solution, impregnated
ZrO2-SiO2Carrier drains, 10 hours dry through 90 DEG C, is roasted 10 hours at 500 DEG C, obtains catalyst B2, catalyst composition
It is shown in Table 1.
Table 1
| Embodiment is numbered | Catalyst is numbered | Catalyst forms, weight percent (wt.%) |
| 1 | C1 | 10CuO-15ZnO-75Al2O3 |
| 2 | C2 | 50CuO-20CdO-30Al2O3 |
| 3 | C3 | 40CuO-10ZnO-50Al2O3 |
| 4 | C4 | 40CuO-9ZnO-1CdO-50Al2O3 |
| 5 | C5 | 40CuO-9.33ZnO-0.67CdO-50Al2O3 |
| 6 | C6 | 40CuO-9.5ZnO-0.5CdO-50Al2O3 |
| 7 | C7 | 20CuO-10MoO3-70SiO2 |
| 8 | C8 | 20CuO-10MoO3-70SiO2 |
| 9 | C9 | 20CuO-0.67Cr2O3-9.33MoO3-70SiO2 |
| 10 | C10 | 20CuO-1Cr2O3-9MoO3-70SiO2 |
| 11 | C11 | 20CuO-2Cr2O3-8MoO3-70SiO2 |
| 12 | C12 | 20CuO-10MoO3-70MCM-48 |
| 13 | C13 | 20CuO-10MoO3-70MCM-41 |
| 14 | C14 | 20CuO-10MoO3-70SBA-15 |
| 15 | C15 | 20CuO-10MoO3-70ZSM-5 |
| 16 | C16 | 35CuO-10ZnO-10MoO3-45MCM-41 |
| 17 | C17 | 35CuO-10ZnO-6MoO3-49MCM-41 |
| 18 | C18 | 35CuO-10ZnO-2MoO3-53MCM-41 |
| 19 | C19 | 35CuO-10ZnO-1MoO3-1CaO-53MCM-41 |
| Comparative example 1 | B1 | 51.7CuO-2La2O3-3.2Al2O3-43.1ZnO |
| Comparative example 2 | B2 | 48CuO-12ZrO2-40SiO2 |
【Embodiment 20~41】
This example demonstrates that application of 1~19 gained catalyst of embodiment in the reaction of carboxylate preparation of ethanol through hydrogenation.
1~19 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 3】
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 as raw material using acetate and pure hydrogen
Experiment, is analyzed, reaction result is shown in Table 2 using on-line chromatograph.
【Comparative example 4】
2 gained B2 catalyst 30ml of comparative example are taken, are restored 10 hours under 300 DEG C of pure hydrogen.With carboxylate and pure hydrogen
Gas is raw material, changes process conditions and is tested, is analyzed using on-line chromatograph, reaction result is shown in Table 2.
Table 2
Claims (7)
1. a kind of carboxylate hydrogenation copper base catalyst, 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；0 c)~
10% selected from least one of VI B races of the periodic table of elements element or its oxide；D) 30~75% carrier carries
Body is selected from least one of silica, aluminium oxide and molecular sieve；Wherein, it is zero when component b) and component c) different；When
Component b）With component c）It is ZnO selected from least one of II B races of periodic table of elements element or its oxide when not being 0
With the mixture of CdO, weight percent 9:1~19:1；By weight percentage, ZnO and CdO in catalyst
Mixture content be 1~15%；As component b）It is not 0, component c）When being 0, by weight percentage, it is selected from catalyst
The content of at least one of II B races of periodic table of elements element or its oxide is 3~10%, is selected from the periodic table of elements
At least one of II B races element or the mixture that its oxide is ZnO and CdO, weight percent 9:1~
19:1；As component b）It is 0, component c）When not being 0, selected from least one of VI B races of the periodic table of elements element or its oxide
For Cr2O3And MoO3Mixture, weight percent 1:14~1:4, Cr in catalyst2O3And MoO3It is mixed
The content for closing object is 0.5~10%.
2. according to the carboxylate hydrogenation copper base catalyst described in claim 1, it is characterised in that by weight percentage, catalysis
The content of copper or its oxide is 15~40% in agent.
3. carboxylate hydrogenation copper base catalyst according to claim 1, which is characterized in that as component b）With component c）Not
When being 0, by weight percentage, the content of the mixture of ZnO and CdO described in catalyst is 3~10%.
4. according to the carboxylate hydrogenation copper base catalyst described in claim 1, which is characterized in that as component b）With component c）
When not being 0, by weight percentage, described in catalyst selected from least one of VI B races of periodic table of elements element or
The content of its oxide is 0.5~6%.
5. carboxylate hydrogenation copper base catalyst according to claim 4, which is characterized in that as component b）With component c）
When not being 0, by weight percentage, described in catalyst selected from least one of VI B races of periodic table of elements element or
The content of its oxide is 1~4%.
6. according to any one of them carboxylate hydrogenation copper base catalyst of Claims 1 to 5, which is characterized in that as component b）
With component c）When not being 0, described is selected from least one of VI B races of periodic table of elements element or its oxide
Cr2O3、MoO3In one kind.
7. carboxylate hydrogenation copper base catalyst according to claim 6, which is characterized in that as component b）With component c）Not
When being 0, be selected from least one of VI B races of the periodic table of elements element or its oxide are Cr2O3And MoO3's
Mixture, weight percent 1:14~1:4.
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| CN115845869B (en) * | 2022-11-24 | 2024-04-26 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethanol by methyl acetate hydrogenation and preparation method and application thereof |
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| CN102659513A (en) * | 2012-04-28 | 2012-09-12 | 上海戊正工程技术有限公司 | Process for producing alcohol and selectively co-producing 2-butanol by utilizing acetate and matching process system thereof |
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| DE4308120A1 (en) * | 1992-03-21 | 1993-09-23 | Erwin Dr Oser | Oxidn. hydrogenation or hardening catalyst obtd. from metal oxide mixt. - contains catalytic crystallites of varying size, esp. for hydrogenating oil, fat or fatty acid |
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| CN103801315B (en) * | 2012-11-13 | 2018-01-16 | 上海华谊能源化工有限公司 | Catalyst and its preparation and application of a kind of 3 hydroxy methyl propionate Hydrogenation for 1,3 propane diols |
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