CN109926055B - Preparation method and application of catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation - Google Patents
Preparation method and application of catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation Download PDFInfo
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Abstract
The invention discloses a preparation method of a copper-based hydrogenation catalyst for preparing alpha-phenylethyl alcohol by acetophenone liquid phase hydrogenation, wherein the catalyst is prepared by adopting a coprecipitation method, and the preparation method is characterized in that a coprecipitation operation is carried out on a water solution containing a precipitator, silica sol and a salt solution in a high-shear reactor; the salt solution is prepared by dissolving soluble metal salt corresponding to a catalyst active component copper oxide and an auxiliary agent in water; the invention also discloses the prepared catalyst and application thereof. According to the invention, the high-shear reactor is adopted for coprecipitation reaction in the catalyst preparation process, so that the coprecipitation reaction can be completed in a short time, the catalyst preparation efficiency is improved, the wastewater treatment difficulty is reduced, the activity and the service life of the catalyst are obviously improved, and the product yield is correspondingly improved.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a preparation method of a catalyst for preparing alpha-phenethyl alcohol by acetophenone liquid phase hydrogenation and application of the prepared catalyst.
Background
Alpha-phenylethyl alcohol is an important chemical product and has wide application in the pharmaceutical industry and the spice manufacturing industry. In the perfumery industry, α -phenylethyl alcohol is widely used for fragrance blending and as a main ingredient of the floral fragrance of roses for the synthesis of various rose oils, essential oils. Alpha-phenylethyl alcohol is an important drug intermediate in the synthesis of many drugs, such as ibuprofen, which is an important raw material for the synthesis of non-steroidal tranquilizers.
The copper-based hydrogenation catalyst is a hydrogenation catalyst with better performance, particularly has better carbonyl hydrogenation effect, the effective catalyst adopted for hydrogenating the acetophenone to generate the alpha-phenethyl alcohol comprises a copper-based catalyst and a noble metal catalyst, and the copper-based catalyst has good activity and proper price as the acetophenone hydrogenation catalyst, so the copper-based catalyst is used as the better acetophenone hydrogenation catalyst. For example, EP- ｃA-0714877 describes ｃA process for the preparation of alphｃA-phenylethanol by hydrogenation of acetophenone using ｃA copper-based catalyst comprising at least one alkaline earth metal carbonate and/or at least one alkaline earth metal compound.
In the reaction process, the alpha-phenethyl alcohol is dehydrated to generate the styrene along with the rise of the reaction, and the styrene is continuously hydrogenated to generate the ethylbenzene under the condition of the existence of the hydrogen and the catalyst. On the other hand, the catalyst becomes more active under high temperature conditions. Operation at higher temperatures increases the conversion of acetophenone, but decreases the yield of alpha-phenylethyl alcohol, which in turn affects the selectivity of the reaction. Therefore, how to prepare a catalyst which has better acetophenone hydrogenation activity and high alpha-phenethyl alcohol yield when being operated at low temperature is a problem to be solved.
The copper-silicon catalyst adopted in the prior art is mostly prepared by a deposition-precipitation method or a coprecipitation method, the catalyst prepared by the deposition-precipitation method relates to ammonia evaporation operation, a large amount of wastewater containing ammonia nitrogen is generated, and the catalyst is easy to inactivate due to olefin polymerization or active particle growth. Co-precipitation, for example, see CN102941097B for a method for preparing a copper-based catalyst by co-precipitation, a solution containing a metal salt corresponding to an active component (copper) and an auxiliary agent and a precipitant are co-precipitated in a silica sol, and then subjected to a treatment including aging, washing, and calcining to obtain a catalyst. However, the copper oxide particles in the catalyst prepared by the coprecipitation method are generally large in size and poor in activity. How to develop a catalyst with good low-temperature activity, low cost, high yield, long service life and less three wastes is the key of the industrialized application of the acetophenone hydrogenation catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for preparing alpha-phenethyl alcohol by acetophenone liquid phase hydrogenation and the prepared catalyst, the catalyst prepared by the method obviously inhibits side reactions such as hydrogenolysis and the like, and has high activity and good selectivity; meanwhile, the catalyst has excellent liquid resistance and high strength after reduction and liquid phase hydrogenation reaction.
In order to achieve one aspect of the above purpose, the invention adopts the following technical scheme:
a preparation method of a copper-based hydrogenation catalyst, wherein the catalyst is prepared by adopting a coprecipitation method, and is characterized in that a coprecipitation operation is carried out on an aqueous solution containing a precipitator, silica sol and a salt solution in a high-shear reactor; the salt solution is prepared by dissolving soluble metal salt corresponding to the active component copper oxide of the catalyst and the auxiliary agent in water.
According to the preparation method of the present invention, preferably, the catalyst composition comprises: the copper oxide content is from 30 to 70%, preferably from 40 to 60%, such as 50%, based on the weight of the catalyst; the auxiliary M is 0.5 to 10%, preferably 2 to 6%, such as 3%, 4% or 5%; the silica is present in the range of 25-65%, preferably 35-55%, such as 40%, 45% or 50%, to better improve the catalyst activity. In the present invention, the contents are all mass contents unless otherwise specified.
According to the preparation method of the invention, preferably, the auxiliary agent is MgO, CaO or CeO 2 、TiO 2 And Al 2 O 3 One or more of; further preferably, the auxiliary agent is MgO and Al 2 O 3 And the molar ratio of MgO: al (Al) 2 O 3 Is 1:3-3:1, preferably 1:2-2: 1. Found out thatAfter the completion of precipitation, a stable hydrotalcite compound can be obtained by roasting, which is beneficial to the fixation of an auxiliary agent.
In the present invention, the precipitant is a substance that can react with metal ions in a mixed salt solution to form a corresponding precipitate. According to the preparation method of the invention, preferably, during the coprecipitation operation, the precipitant aqueous solution is firstly mixed with silica sol, and the obtained mixed solution is then subjected to the coprecipitation operation with the salt solution; further preferably, the silica sol is alkaline silica sol, and the pH value is 8.0-10.0; the precipitant is one or more of potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate, urea and ammonia water.
It is understood by those skilled in the art that each metal salt forming the salt solution is a soluble salt of the corresponding metal, such as one or more of a nitrate, a hydrochloride, and an acetate. In the present invention, the concentration of the metal salt in the salt solution may be 0.3 to 2mol/L, preferably 0.5 to 1.0 mol/L;
in a preferred embodiment, the salt solution is added with small molecular weight polyol before the coprecipitation, and the addition amount can be 0.5-3%, preferably 1-2% of the mass of the salt solution. The small molecular polyol refers to polyol with molecular weight not more than 600. Researches find that the small molecular polyol is added in the invention, so that the structure collapse caused by catalyst dehydration can be effectively prevented, and the pore-forming effect can be achieved; the polyhydric alcohol compound is preferably one or more of propylene glycol, glycerol, butanediol, sorbitol and polyethylene glycol, more preferably a mixture of glycerol and polyethylene glycol, and the mixing mass ratio is glycerol: polyethylene glycol (molecular weight may be 200-600) of 0.5:1 to 4:1, preferably glycerol: the polyethylene glycol is 1:1-2: 1.
In a preferred embodiment, the salt solution is added with a surfactant before the coprecipitation, and the addition amount of the surfactant is 0.5-3%, preferably 1-2% of the mass of the salt solution; researches show that the surfactant is added into the salt solution, and the surfactant can obtain better dispersion effect in a high-shear reactor; the surfactant is preferably one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, OP-10, Tween 80, TX-100 and fatty acid methyl ester sodium sulfonate, and is further preferably sodium dodecyl benzene sulfonate.
In the present invention, the co-precipitation reaction for preparing the catalyst is carried out in the high shear reactor, which is well known in the art, preferably a rotor and stator coupled high shear reactor, such as a Fisco-1S high shear reactor from Frank, at a speed of not less than 5000rpm, preferably not less than 10000rmp, such as 15000rmp, 20000rmp, 30000rmp or 50000rmp, etc. Preferably, the space between the rotor and the stator is 0.2-1mm, such as 0.5 or 0.8mm, and in addition, the gear can adopt a stainless steel blade with 4-10 teeth, such as the size of the gear is 10-30 mm.
According to the preparation method of the invention, the preparation method further comprises the treatment processes of aging, washing and roasting the materials after the coprecipitation reaction in the high shear reactor to obtain the catalyst; wherein the temperature of the coprecipitation reaction process and the aging process is preferably 60-90 ℃, such as 70 or 80 ℃; the specific reaction to form precipitates and the aging process of the precipitates are well known in the art, and the reaction to form precipitates can be completed within 1 hour, half hour, 10min or 5min, and then aged for 1-3 h. The aged slurry can be filtered, washed, dried and roasted to obtain a catalyst; the filtration, washing, drying and roasting processes can adopt the filtration and washing processes commonly used in the field, and are catalyst treatment processes commonly used in the field. In one embodiment, the firing temperature is 300-700 ℃, such as 400, 500, or 600 ℃; the calcination time is 4-12h, such as 6, 8 or 10 h.
In order to realize one aspect of the purpose, the invention also provides the application of the catalyst prepared by the method in the preparation of alpha-phenylethyl alcohol by acetophenone liquid phase hydrogenation.
The catalyst has corresponding catalytic activity after reduction activation, and is used for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation.
In a preferred embodiment, the reduction of the catalyst according to the inventionThe method for activation comprises the following steps: keeping the volume space velocity of the mixed gas of hydrogen and nitrogen at 300- -1 Preferably, the temperature of the reactor is firstly raised to 160-180 ℃, the physical water absorbed by the catalyst is removed at constant temperature for 1-2H, and then H with the volume fraction not more than 10v percent is introduced 2 After the pre-reduction of the catalyst for at least 0.5H, such as 1H, 1.5H or 2H, for example, (5 v% + -2 v%) H2, the proportion of the hydrogen in the hydrogen and nitrogen mixture is gradually increased, such as gradually increased to 10 v%, 20 v%, 50 v% or 100%, the hot spot temperature of the catalyst bed in the process is controlled not to exceed 300 ℃, such as 280 ℃, and finally increased to 200-.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the process of preparing the catalyst, a high-shear reactor is adopted for coprecipitation reaction, so that the coprecipitation reaction can be completed in a short time, the preparation efficiency of the catalyst is improved, the treatment difficulty of wastewater is reduced, the activity and the service life of the catalyst are obviously improved, and the product yield is correspondingly improved;
(2) before the coprecipitation reaction, the micromolecular polyol and the surfactant are added, and the high-shear reactor is matched to act, so that the micromolecular polyol and the surfactant can be uniformly dispersed in a reaction system, the catalyst structure can be kept stable, the multilevel pores can be manufactured, the mass transfer effect in the reaction process can be facilitated, and the activity of the catalyst can be improved.
Detailed Description
The process of the present invention will be described in detail with reference to examples, but is not limited to the examples.
The content of copper ions in the hydrogenation liquid is measured by an inductively coupled plasma emission spectrometer (ICP).
Chromatographic analysis conditions: the analysis was carried out using a DB-5MS (30 m.times.0.25 mm.times.0.25 μm) column, under the following operating conditions: keeping the temperature at 50 ℃ for 2 minutes, heating to 80 ℃ at 5 ℃/min, keeping the temperature for 0min, heating to 240 ℃ at 15 ℃/min, and keeping the temperature for 5 min. The injector temperature was 260 ℃ and the detector temperature was 260 ℃.
The high-shear reactor is Fisco-1S high-shear reactor manufactured by Fruke company
Unless otherwise specified, the reagents used below were all analytical grade.
Example 1
157.04gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、38.3gAl(NO 3 ) 3 ·9H 2 O is dissolved in 1630g of water to prepare a salt-forming aqueous solution. 4.61g of glycerol, 4.61g of polyethylene glycol (molecular weight 400, the same applies hereinafter) and 18.45g of sodium dodecylbenzenesulfonate were dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 234g of a 30% by weight alkaline silica sol were slowly added to the aqueous solution of the prepared precipitant.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 80 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 4min, and aging for 2h at 80 ℃ to obtain slurry. Then washing, filtering, drying and finally roasting at 400 ℃ for 8 h. Thus obtaining the No. 1 catalyst.
And (3) catalyst reduction: the # 1 catalyst was charged to a fixed bed hydrogenation reactor at a 50ml loading. The reactor temperature was first raised to 160 ℃ and N was passed in 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 240 ℃ to be reduced for 3h under the pure hydrogen atmosphere. Volume space velocity of gas 500h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2MPa, the reaction temperature is about 60 ℃, the H2/acetophenone molar ratio is 30:1, and the acetophenone liquid hourly space velocity is 0.4 g/g/H.
Example 2
157.04gCu (NO) 3 ) 2 ·3H 2 O、33.1g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 1100g of water to prepare a salt-forming aqueous solution. 3.29g of glycerol, 2g of polyethylene glycol and 13.16g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 234g of a 30% by weight alkaline silica sol were slowly added to the aqueous solution of the precipitation agent.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 80 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 4min, and aging for 2h at 80 ℃ to obtain slurry. Then washing, filtering, drying and finally roasting at 400 ℃ for 8 h. Thus obtaining the 2# catalyst.
And (3) catalyst reduction: the # 2 catalyst was charged to a fixed bed hydrogenation reactor at a 50ml loading. The reactor temperature was first raised to 160 ℃ and N was passed in 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 240 ℃ to be reduced for 3h under the pure hydrogen atmosphere. Volume space velocity of gas 500h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 30:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 3
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 4.3g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 4min, and then aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 3# catalyst.
And (3) catalyst reduction: the No. 3 catalyst is filled into a fixed bed hydrogenation reactor, and the catalyst loading is 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under the pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 4
Mixing 235.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 O is dissolved in 1460g of water to prepare a salt-forming aqueous solution. 25.9g of glycerol, 25.9g of polyethylene glycol and 34.5g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 156g of 30% by weight alkaline silica sol were slowly added to the aqueous solution of the prepared precipitant.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 60 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 4min, and then aging for 6h at 60 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 600 ℃ for 4 h. Thus obtaining the 4# catalyst.
And (3) catalyst reduction: the catalyst is fixed in a fixed wayThe loading in the bed hydrogenation reactor was 50 ml. The reactor temperature was first raised to 180 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 250 ℃ to be reduced for 3h under the pure hydrogen atmosphere. Volume space velocity of gas 1000h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 3MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 5
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 6.71g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 6min, and then aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 5# catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of the hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the temperature of the hot spot of the catalyst bed layer in the process is controlled not to exceed 280 ℃,finally, the temperature is increased to 230 ℃ and the reduction is carried out for 4h under pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 6
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O and 2.6g of nano titanium dioxide are dissolved in 878.3g of water to prepare a salt-forming aqueous solution (the nano titanium dioxide generates liquid phase sol in the water and can be well dispersed in the aqueous solution). 8.71g of glycerol, 8.71g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 8min, and then aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the No. 6 catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under the pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the acetophenone to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 7
196.6gCu (NO) 3 ) 2 ·3H 2 O、10.95g Ca(NO 3 ) 2 .4H 2 O、19.2g Al(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of propylene glycol, 10g of sorbitol and 19.74g of sodium fatty acid methyl ester sulfonate were dissolved in the salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a parallel flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotation speed of 10000rpm, setting the precipitation time to be 8min, and aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 8# catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under the pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 8
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、6.56gCe(NO 3 ) 3 ·6H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 8.71g of butanediol and 19.74g of sodium lauryl sulfate were dissolved in the salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 29000rpm, setting the precipitation time to be 6min, and then aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 8# catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under the pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Example 9
The difference from example 1 is that the salt solution is not added with small molecule polyol and surfactant, and the rest is the same as example 1. Thus obtaining the 1-1# catalyst.
Comparative example 1
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 8.71g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 1min, and then aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 9# catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under the pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Comparative example 2
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 8.71g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting a rotating speed of 19000rpm, setting the precipitation time to be 15min, and then aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 10# catalyst.
And (3) catalyst reduction: loading catalyst in fixed bed hydrogenation reactorIs 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot spot temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under the pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Comparative example 3
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 8.71g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 3000rpm, precipitating for 4min, and aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 11# catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 Removing physical water adsorbed by the catalyst at constant temperature for 0.5H, and introducing H with volume fraction of 5 v% 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the hot point temperature of a catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to obtain pure hydrogenAnd reducing for 4h under an atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Comparative example 4
196.6gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、19.2gAl(NO 3 ) 3 ·9H 2 Dissolving O in 930g of water to prepare a salt aqueous solution. 8.71g of glycerol, 8.71g of polyethylene glycol and 19.74g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 199g of 30 wt.% alkaline silica sol were slowly added to the prepared aqueous precipitant solution.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 70 ℃ by adopting the rotating speed of 50000rpm, setting the precipitation time to be 4min, and aging for 4h at 70 ℃ to obtain slurry. Then washing, filtering, drying and roasting at 500 ℃ for 6 h. Thus obtaining the 12# catalyst.
And (3) catalyst reduction: the catalyst was loaded in a fixed bed hydrogenation reactor at a loading of 50 ml. The reactor temperature was first raised to 170 ℃ and N was passed through 2 The physical water absorbed by the catalyst is removed after the constant temperature is kept for 0.5H, and then H with the volume fraction of 5v percent is introduced 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of hydrogen in the mixed gas of hydrogen and nitrogen is gradually increased to 10 v%, 50 v% and 100%, the temperature of the hot spot of the catalyst bed layer in the process is controlled not to exceed 280 ℃, and finally the temperature is increased to 230 ℃ to be reduced for 4h under pure hydrogen atmosphere. Volume space velocity of gas 800h -1 。
And then evaluating the performance of the activated catalyst, wherein the evaluation conditions of the catalyst are as follows: the reaction pressure is 2.5MPa, the reaction temperature is 60 ℃, and H 2 The mol ratio of the raw materials to the acetophenone is 50:1, and the hourly space velocity of the acetophenone liquid is 0.4 g/g/h.
Comparative example 5
157.04gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、38.3gAl(NO 3 ) 3 ·9H 2 O is dissolved in 1630g of water to prepare a salt-forming aqueous solution. 4.61g of glycerol, 4.61g of polyethylene glycol and 18.45g of sodium dodecylbenzenesulfonate are dissolved in a salt solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 234g of a 30% by weight alkaline silica sol were slowly added to the aqueous solution of the prepared precipitant.
The coprecipitation reaction is carried out in a conventional reactor with paddle stirring at a speed of 300 rpm. Controlling the temperature in the reaction kettle at 80 ℃, precipitating for 60min, and aging for 2h at 80 ℃ to obtain slurry. Then washing, filtering, drying and finally roasting at 400 ℃ for 8 h. Thus obtaining the 13# catalyst.
The reduction and evaluation conditions were the same as in example 1.
Comparative example 6
157.04gCu (NO) 3 ) 2 ·3H 2 O、16.5g Mg(NO 3 ) 2 .6H 2 O、38.3gAl(NO 3 ) 3 ·9H 2 O is dissolved in 1630g of water to prepare a salt-forming aqueous solution.
150g of sodium carbonate was prepared as a 15 wt% aqueous solution, i.e., a precipitant aqueous solution. 234g of a 30% by weight alkaline silica sol were slowly added to the aqueous solution of the prepared precipitant.
And adding the two solutions into a high-shear reactor in a concurrent flow manner, controlling the temperature in the reaction kettle to be 80 ℃ by adopting the rotating speed of 19000rpm, setting the precipitation time to be 4min, and aging for 2h at 80 ℃ to obtain slurry. Then washing, filtering, drying and finally roasting at 400 ℃ for 8 h. Thus obtaining the 14# catalyst.
The reduction and evaluation conditions were the same as in example 1.
The above examples and comparative examples were sampled and analyzed at a reaction time of 50 hours, and the results of catalyst performance evaluation are shown in Table 1.
TABLE 1 evaluation results of catalyst Properties
Claims (19)
1. A preparation method of a copper-based hydrogenation catalyst, wherein the catalyst is prepared by adopting a coprecipitation method, and is characterized in that a coprecipitation operation is carried out on an aqueous solution containing a precipitator, silica sol and a salt solution in a high-shear reactor; the salt solution is prepared by dissolving soluble metal salt corresponding to a catalyst active component copper oxide and an auxiliary agent in water;
in the catalyst, based on the total weight of the catalyst, the content of copper oxide is 30-70%, the content of auxiliary agent is 0.5-10%, and the content of silicon dioxide is 25-65%; the auxiliary agent is MgO, CaO or CeO 2 、TiO 2 And Al 2 O 3 One or more of;
before the coprecipitation of the salt solution, small molecular polyol is added into the salt solution; wherein the addition amount of the small molecular polyol is 0.5-3% of the mass of the salt solution; the micromolecular polyol compound is a mixture of glycerol and polyethylene glycol, and the mixing mass ratio is that the glycerol: polyethylene glycol is 0.5:1-4: 1.
2. The process according to claim 1, wherein the catalyst comprises 40 to 60% by weight of copper oxide, 2 to 6% by weight of an auxiliary and 35 to 55% by weight of silica, based on the total weight of the catalyst.
3. The method according to claim 1 or 2, wherein the auxiliary agent is MgO and Al 2 O 3 And the molar ratio of MgO: al (aluminum) 2 O 3 Is 1:3-3: 1.
4. The method according to claim 3, wherein MgO and Al are contained in the auxiliary 2 O 3 Molar ratio of MgO: al (Al) 2 O 3 Is 1:2-2: 1.
5. The method according to claim 1, wherein the aqueous solution of the precipitant is mixed with the silica sol and then subjected to the coprecipitation operation with the salt solution in the coprecipitation operation.
6. The production method according to claim 5, wherein the silica sol is an alkaline silica sol, and the pH value is 8.0 to 10.0; the precipitant is one or more of potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate, urea and ammonia water.
7. The production method according to claim 1 or 2, wherein the concentration of the metal salt in the salt solution is 0.3 to 2 mol/L.
8. The method of claim 7, wherein the metal salt concentration in the salt solution is 0.5 to 1.0 mol/L.
9. The method according to claim 7, wherein the salt solution is added with a surfactant before the coprecipitation; wherein the addition amount of the surfactant is 0.5-3% of the mass of the salt solution.
10. The preparation method of claim 9, wherein the small molecule polyol is added in an amount of 1-2% by mass of the salt solution; the addition amount of the surfactant is 1-2% of the mass of the salt solution.
11. The method of claim 9,
the surfactant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, OP-10, Tween 80, TX-100 and sodium fatty acid methyl ester sulfonate.
12. The production method according to claim 11,
the surfactant is sodium dodecyl benzene sulfonate.
13. The production method according to claim 12,
the micromolecular polyol compound is a mixture of glycerol and polyethylene glycol, and the mixing mass ratio is that the glycerol: polyethylene glycol is 1:1-2: 1.
14. The production method according to claim 1 or 2,
the high-shear reactor is a rotor and stator coupled high-shear reactor, and the running speed of the rotor is not less than 5000 rpm.
15. The method of claim 14, wherein the rotor operating rate is not less than 10000 rmp.
16. The method as claimed in claim 14, wherein the gap between the mover and the stator is 0.2-1 mm.
17. The method of claim 1, further comprising a treatment process of aging, washing and calcining the material after the coprecipitation reaction in the high shear reactor to obtain a catalyst; wherein the temperature of the coprecipitation reaction process and the aging process is 60-90 ℃; the roasting temperature is 300-700 ℃, and the roasting time is 4-12 h.
18. Use of the catalyst prepared by the preparation method of any one of claims 1-17 in the preparation of alpha-phenylethyl alcohol by liquid phase hydrogenation of acetophenone.
19. The use of claim 18, wherein the catalyst is subjected to reductive activation before catalytic hydrogenation of acetophenone for producing alpha-phenylethyl alcohol;
the method for reductive activation of the catalyst comprises: keeping the volume space velocity of the mixed gas of hydrogen and nitrogen at 300- -1 Introducing H with a volume fraction of not more than 10 v% 2 The mixed gas of hydrogen and nitrogen pre-reduces the catalyst for at least 0.5h, then gradually increases the proportion of hydrogen in the mixed gas of hydrogen and nitrogen, controls the hot spot temperature of the catalyst bed layer not to exceed 300 ℃, finally heats to 250 ℃ and reduces for 2-5h under the pure hydrogen atmosphere to obtain the activated catalyst.
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| US4251672A (en) * | 1978-08-25 | 1981-02-17 | Exxon Research & Engineering Co. | Process for hydrogenating organic compounds with coprecipitated copper-nickel-silica catalysts |
| US5663458A (en) * | 1994-12-02 | 1997-09-02 | Sumitomo Chemical Company, Limited. | Process for producing α-phenylethyl alcohol |
| CN105363456A (en) * | 2015-11-05 | 2016-03-02 | 华东理工大学 | Copper-based catalyst and preparation method and application thereof |
| CN106582652A (en) * | 2015-10-16 | 2017-04-26 | 上海华谊能源化工有限公司 | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof |
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| US4251672A (en) * | 1978-08-25 | 1981-02-17 | Exxon Research & Engineering Co. | Process for hydrogenating organic compounds with coprecipitated copper-nickel-silica catalysts |
| US5663458A (en) * | 1994-12-02 | 1997-09-02 | Sumitomo Chemical Company, Limited. | Process for producing α-phenylethyl alcohol |
| CN106582652A (en) * | 2015-10-16 | 2017-04-26 | 上海华谊能源化工有限公司 | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof |
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