CN109926055A - The method for preparing catalyst of hydrogenation of acetophenone alpha-phenyl ethyl alcohol and application - Google Patents
The method for preparing catalyst of hydrogenation of acetophenone alpha-phenyl ethyl alcohol and application Download PDFInfo
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Abstract
The invention discloses the preparation methods that a kind of acetophenone liquid-phase hydrogenatin prepares the copper-based hydrogenation catalyst of alpha-phenyl ethyl alcohol, the catalyst is prepared using coprecipitation, it is characterized in that, the aqueous solution containing precipitating reagent, silica solution and the salting liquid is made to carry out co-precipitation operation in high-shear reactor；Wherein, the salting liquid is that soluble metallic salt corresponding with catalyst activity component copper oxide and auxiliary agent is dissolved in water, the salting liquid configured；The invention also discloses the catalyst being prepared and its applications.The present invention carries out coprecipitation reaction using high-shear reactor in preparing catalyst process, it can not only make coprecipitation reaction complete in a relatively short period of time, it improves catalyst preparation efficiency and reduces the processing difficulty of waste water, more allow people it is unexpected be, the activity of catalyst and service life significantly improve, while being correspondingly improved product yield.
Description
Technical field
The invention belongs to technical field of catalytic hydrogenation, and in particular to a kind of acetophenone liquid-phase hydrogenatin alpha-phenyl ethyl alcohol catalyst
Preparation method and catalyst obtained application.
Background technique
Alpha-phenyl ethyl alcohol is a kind of important chemical products, is had a wide range of applications in medical industry and fragrance manufacturing industry.?
In fragrance manufacturing industry, alpha-phenyl ethyl alcohol be widely used in fragrance reconciliation, and as the main component of Rose Essentielle for various attars of rose,
The synthesis of essential oil.Alpha-phenyl ethyl alcohol is important pharmaceutical intermediate, such as this on-steroidal town of brufen in many pharmaceutical synthesis
Determine the important source material of pharmaceutical synthesis.
Copper-based hydrogenation catalyst is a kind of hydrogenation catalyst of better performances, preferable particularly with carbonyl hydrogen effect, and
Hydrogenation of acetophenone, which is generated effective catalyst used by alpha-phenyl ethyl alcohol, copper-based catalysts and noble metal catalyst, copper-based to urge
Agent has good activity and suitable price as hydrogenation of acetophenone catalyst, therefore by as a kind of preferable acetophenone
Hydrogenation catalyst carry out using.Such as it describes a kind of to prepare α-phenylethanol by hydrogenation of acetophenone in EP-A-0714877
Method, this method is used is with copper containing at least one alkaline earth metal carbonate and/or at least one alkaline earth metal compound
Main catalyst.
During the reaction, with the raising of reaction, alpha-phenyl ethyl alcohol dehydration generates styrene, and deposits in hydrogen and catalyst
Under the conditions, styrene will continue to be hydrogenated to ethylbenzene.An other reverse side, catalyst become more have work under the high temperature conditions
Property.Although the operation under higher temperature rises the conversion ratio of acetophenone, the yield of alpha-phenyl ethyl alcohol is reduced, and then influence
The selectivity of reaction.Therefore how to prepare a operation at low temperature has preferable hydrogenation of acetophenone activity, and obtains height
The catalyst of alpha-phenyl ethyl alcohol yield be a problem to be solved.
The copper Si catalyst used in the prior art mostly uses greatly deposition-precipitation or coprecipitation to be prepared, deposition
The catalyst of precipitation method preparation is related to ammonia still process operation, generates largely containing the waste water of ammonia nitrogen, and catalyst is easy because alkene is poly-
It closes or active particle grows up and causes catalyst inactivation.Coprecipitation is co-precipitated for example, see utilizing disclosed in CN102941097B
The method that method prepares copper-based catalysts, for metal salt solution corresponding with active component (copper) and auxiliary agent and precipitating reagent will be contained
It is co-precipitated in silica solution, then carries out including that catalyst is made in the processing such as aging, washing and roasting.However use coprecipitation
Copper oxide particle general size is larger in the catalyst of preparation, and activity is poor.It is good that how low temperature active is developed, at low cost, receipts
Rate is high, last a long time, the catalyst that the three wastes are less is the key that the application of hydrogenation of acetophenone Catalystization.
Summary of the invention
The purpose of the present invention is to provide the preparation methods that a kind of acetophenone liquid-phase hydrogenatin prepares the catalyst of alpha-phenyl ethyl alcohol
And catalyst obtained, the side reactions such as hydrogenolysis are significantly suppressed using catalyst prepared by this method, catalyst activity is high, selects
Selecting property is good；Catalyst has excellent anti-liquid ability simultaneously, high after reduction, liquid-phase hydrogenatin post reaction strength.
One aspect to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of copper-based hydrogenation catalyst, the catalyst are prepared using coprecipitation, which is characterized in that
The aqueous solution containing precipitating reagent, silica solution and the salting liquid is set to carry out co-precipitation operation in high-shear reactor；Wherein,
The salting liquid is that soluble metallic salt corresponding with catalyst activity component copper oxide and auxiliary agent is dissolved in water, and configuration obtains
Salting liquid.
Preparation method according to the present invention, it is preferable that the catalyst composition includes: based on catalyst weight, copper oxide
Content is 30-70%, preferably 40-60%, such as 50%；Auxiliary agent M be 0.5-10%, preferably 2-6%, such as 3%, 4% or
5%；Silica is 25-65%, preferably 35-55%, such as 40%, 45% or 50%, preferably to improve catalyst activity.
In the present invention, if not otherwise specified, the content is mass content.
Preparation method according to the present invention, it is preferable that the auxiliary agent is MgO, CaO, CeO2、TiO2And Al2O3One of
Or it is a variety of；It is further preferred that the auxiliary agent is MgO and Al2O3, and the molar ratio MgO:Al of the two2O3It is excellent for 1:3-3:1
Select 1:2-2:1.The study found that stable hydrotalcite compound can be obtained by roasting after precipitating, be conducive to auxiliary agent
It is fixed.
In the present invention, precipitating reagent, which refers to, can react to form the corresponding object precipitated to the metal ion in mixing salt solution
Matter.Preparation method according to the present invention, it is preferable that when being co-precipitated operation, the precipitating reagent aqueous solution is first mixed with silica solution
It closes, then obtained mixed liquor carries out co-precipitation operation with the salting liquid again；It is further preferred that the silica solution is alkalinity
Silica solution, pH value 8.0-10.0；The precipitating reagent be potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide,
One of ammonium carbonate, ammonium hydrogen carbonate, urea and ammonium hydroxide are a variety of.
It will be appreciated by those skilled in the art that each metal salt for forming salting liquid is the soluble-salt of respective metal, such as nitre
Hydrochlorate, hydrochloride and acetate it is one or more.In the present invention, the metal salt concentrations in the salting liquid can be 0.3-
2mol/L, preferably 0.5-1.0mol/L；
In a preferred embodiment, the salting liquid is before being co-precipitated, wherein also polynary added with small molecule
Alcohol, additive amount can be the 0.5-3%, preferably 1-2% of salting liquid quality.The small molecule polyol refers to that molecular weight is not more than
600 polyalcohol.The study found that in the present invention, small molecule polyol being added and is made when catalyst dehydration can be effectively prevented
At structure collapses, and pore-creating can also be played the role of；Polyol compound be preferably propylene glycol, glycerine, butanediol,
One of sorbierite and polyethylene glycol are a variety of, the mixture of further preferred glycerine and polyethylene glycol, mixing mass ratio
For glycerine: polyethylene glycol (molecular weight can be 200-600) is 0.5:1-4:1, preferably glycerine: polyethylene glycol 1:1-2:
1。
In a preferred embodiment, the salting liquid is before being co-precipitated, wherein it is also added with surfactant,
Additive amount is the 0.5-3%, preferably 1-2% of salting liquid quality；The study found that the present invention adds surface-active in salting liquid
Agent, surfactant can obtain better dispersion effect in high-shear reactor；The surfactant is preferably 12
One of sodium alkyl benzene sulfonate, lauryl sodium sulfate, OP-10, Tween 80, TX-100 and methyl sodiosul foaliphatate are more
Kind, further preferably neopelex.
In the present invention, the coprecipitation reaction for preparing catalyst carries out in the high-shear reactor, the high shear
Reactor be it is known in the art, preferably mover and stator coupling high-shear reactor, such as Fu Luke company Fisco-1S
High-shear reactor, revolving speed not less than 5000rpm, preferably not less than 10000rmp, such as 15000rmp, 20000rmp,
30000rmp or 50000rmp etc..Preferably, between the mover and stator between be divided into 0.2-1mm, such as 0.5 or 0.8mm, separately
Outside, gear can use 4-10 tooth stainless steel blade, for example gear size is 10-30mm.
Preparation method according to the present invention, the preparation method further include anti-to being co-precipitated in the high-shear reactor
Material after answering carries out aging, washing and roasting to obtain the treatment process of catalyst；Wherein, the coprecipitation reaction process and
The temperature of ageing process is preferably 60-90 DEG C, such as 70 or 80 DEG C；Specific reaction forms the process and precipitating aging of precipitating
Process is well known in the art, such as can complete to be formed the reaction process of precipitating in 1h, half an hour, 10min or 5min, then
It can aging 1-3h again.Slurry after aging then can be filtered, washs, dries and roast, and obtain catalyst；The mistake
Filter, washing, dry and roasting process can be used it is commonly used in the art be filtered, washed process, be catalysis commonly used in the art
Agent treatment process.In one embodiment, maturing temperature is 300-700 DEG C, such as 400,500 or 600 DEG C；Calcining time is
4-12h, such as 6,8 or 10h.
One aspect to achieve the above object, the present invention also provides the above-mentioned catalyst being prepared in acetophenone liquid
It is added hydrogen and prepares the application in alpha-phenyl ethyl alcohol.
It will be appreciated by those skilled in the art that the catalyst just has corresponding catalysis work after needing to carry out reduction activation
Property, alpha-phenyl ethyl alcohol is prepared for hydrogenation of acetophenone.
In a preferred embodiment, the method for the reduction activation of catalyst of the present invention includes: holding hydrogen
With the mixed gas volume space velocity 300-1000h of nitrogen-1, temperature of reactor is preferably risen to 160-180 DEG C first, constant temperature 1-2h
The mechanical water of Removal of catalyst absorption, then passes to and is no more than 10v%H containing volume fraction2, such as the institute of (5v% ± 2v%) H2
The gaseous mixture for stating hydrogen and nitrogen gradually mention after prereduction at least 0.5h, such as 1h, 1.5h or 2h to the catalyst
The ratio of hydrogen in high hydrogen and nitrogen mixture, such as step up to 10v%, 20v%, 50v%, 100%, control the mistake
Journey catalyst bed hot(test)-spot temperature is no more than 300 DEG C, such as 280 DEG C, is finally warming up to 200-250 DEG C, such as 230 or 240 DEG C,
Reductase 12-the 5h under pure hydrogen atmosphere, such as 3 or 4h, the catalyst activated.
Compared with prior art, the beneficial effects of the present invention are:
(1) coprecipitation reaction is carried out using high-shear reactor in preparing catalyst process, can not only made coprecipitated
Reaction of forming sediment is complete in a relatively short period of time, improves catalyst preparation efficiency and reduces the processing difficulty of waste water, more people is allowed to envision
Less than the activity of catalyst and service life significantly improve, while being correspondingly improved product yield；
(2) present invention adds small molecule polyol and surfactant before coprecipitation reaction, cooperates high-shear reactor
Effect, can be uniformly dispersed in reaction system, be conducive to catalyst structure and keep stablizing, and manufacture multi-stage porous, favorably
In the effect of mass transmitting of reaction process, the activity of catalyst is improved.
Specific embodiment
The method of the present invention is described in detail below with reference to embodiment, but is not limited to the embodiment.
Content of copper ion is measured using Inductively coupled plasma optical emission spectrometer (ICP) in hydrogenation liquid.
Chromatographiccondition: it is analyzed using DB-5MS (30m × 0.25mm × 0.25 μm) column, concrete operations condition
Are as follows: 50 DEG C are kept for 2 minutes, are warming up to 80 DEG C with 5 DEG C/min, are kept 0min, are warming up to 240 DEG C with 15 DEG C/min, are kept 5min.
Sample injector temperature is 260 DEG C, and detector temperature is 260 DEG C.
High-shear reactor is Fu Luke company Fisco-1S high-shear reactor
If not otherwise specified, reagent used below is that analysis is pure.
Embodiment 1
By 157.04gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、38.3gAl(NO3)3·9H2O is dissolved in 1630g
The aqueous solution of salt is configured in water.By 4.61g glycerine, 4.61g polyethylene glycol (molecular weight 400, similarly hereinafter) and 18.45g 12
Sodium alkyl benzene sulfonate is dissolved in salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 234g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 80 DEG C, sedimentation time 4min, and 80 DEG C of aging 2h obtain slurries later.Then washing, filtering, drying, are finally placed in
8h is roasted at 400 DEG C.Up to 1# catalyst.
Catalyst reduction: by 1# catalyst filling into fixed bed hydrogenation reactor, loadings 50ml.It first will reaction
Device temperature rises to 160 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2
Hydrogen and nitrogen gaseous mixture carry out prereduction 1h, step up the ratio of hydrogen in hydrogen and nitrogen mixture later extremely
10v%, 50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 240 DEG C pure
3h is restored under nitrogen atmosphere.The volume space velocity 500h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2MPa, reaction temperature
About 60 DEG C, H2/ acetophenone molar ratio 30:1, acetophenone liquid hourly space velocity (LHSV) is 0.4g/g/h.
Embodiment 2
By 157.04gCu (NO3)2·3H2O、33.1g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 1100g
The aqueous solution of salt is configured in water.By 3.29g glycerine, 2g polyethylene glycol and 13.16g neopelex are dissolved in salt
In solution.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 234g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 80 DEG C, sedimentation time 4min, and 80 DEG C of aging 2h obtain slurries later.Then washing, filtering, drying, are finally placed in
8h is roasted at 400 DEG C.Up to 2# catalyst.
Catalyst reduction: by 2# catalyst filling into fixed bed hydrogenation reactor, loadings 50ml.It first will reaction
Device temperature rises to 160 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2
Hydrogen and nitrogen gaseous mixture carry out prereduction 1h, step up the ratio of hydrogen in hydrogen and nitrogen mixture later extremely
10v%, 50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 240 DEG C pure
3h is restored under nitrogen atmosphere.The volume space velocity 500h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2MPa, reaction temperature
It is 60 DEG C, H2/ acetophenone molar ratio 30:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 3
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, 4.3g polyethylene glycol and 19.74g neopelex are dissolved in salt
In solution.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 4min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 3# catalyst.
Catalyst reduction: by 3# catalyst filling into fixed bed hydrogenation reactor, loaded catalyst 50ml.First
Temperature of reactor is risen to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to containing volume point
Number 5v%H2Hydrogen and nitrogen gaseous mixture carry out prereduction 1h, step up hydrogen in hydrogen and nitrogen mixture later
Ratio controls the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, is finally warming up to 230 to 10v%, 50v%, 100%
DEG C 4h is restored under pure hydrogen atmosphere.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 4
By 235.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 1460g
The aqueous solution of salt is configured in water.By 25.9g glycerine, 25.9g polyethylene glycol and 34.5g neopelex are dissolved in
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 156g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 60 DEG C, sedimentation time 4min, and 60 DEG C of aging 6h obtain slurries later.Then washing, filtering, drying, are placed in 600 DEG C
Lower roasting 4h.Up to 4# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 180 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 250 DEG C in pure hydrogen atmosphere
Lower reduction 3h.The volume space velocity 1000h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 3MPa, reaction temperature
It is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 5
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, 6.71g polyethylene glycol and 19.74g neopelex are dissolved in
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 6min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 5# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 6
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O, 2.6g nano-titanium dioxide is dissolved in 878.3g water
In be configured to the aqueous solution of salt (nano-titanium dioxide generates aqueous sol in water, can preferably be scattered in aqueous solution).
By 8.71g glycerine, 8.71g polyethylene glycol and 19.74g neopelex are dissolved in salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 8min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 6# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 7
By 196.6gCu (NO3)2·3H2O、10.95g Ca(NO3)2.4H2O、19.2g Al(NO3)3·9H2O is dissolved in 930g
The aqueous solution of salt is configured in water.By 8.71g propylene glycol, 10g sorbierite and 19.74g methyl sodiosul foaliphatate are dissolved in salt
In solution.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 10000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 8min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 8# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 8
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、6.56gCe(NO3)3·6H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, it is molten that 8.71g butanediol and 19.74g lauryl sodium sulfate are dissolved in salt
In liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 29000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 6min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 8# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Embodiment 9
The difference from embodiment 1 is that small molecule polyol and surfactant are not added in salting liquid, remaining is the same as implementation
Example 1.Up to 1-1# catalyst.
Comparative example 1
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, 8.71g polyethylene glycol and 19.74g neopelex are dissolved in
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 1min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 9# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Comparative example 2
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, 8.71g polyethylene glycol and 19.74g neopelex are dissolved in
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 15min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500
6h is roasted at DEG C.Up to 10# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Comparative example 3
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, 8.71g polyethylene glycol and 19.74g neopelex are dissolved in
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 3000rpm, control reactor temperature
It is 70 DEG C, sedimentation time 4min, 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed at 500 DEG C
Roast 6h.Up to 11# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Comparative example 4
By 196.6gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、19.2gAl(NO3)3·9H2O is dissolved in 930g water
In be configured to the aqueous solution of salt.By 8.71g glycerine, 8.71g polyethylene glycol and 19.74g neopelex are dissolved in
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 199g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 50000rpm, control temperature in reaction kettle
Degree is 70 DEG C, sedimentation time 4min, and 70 DEG C of aging 4h obtain slurries later.Then washing, filtering, drying, are placed in 500 DEG C
Lower roasting 6h.Up to 12# catalyst.
Catalyst reduction: catalyst is loaded in fixed bed hydrogenation reactor, loadings 50ml.First by reactor temperature
Degree rises to 170 DEG C and is passed through N2The mechanical water of constant temperature 0.5h Removal of catalyst absorption, then passes to 5v%H containing volume fraction2Hydrogen
The gaseous mixture of gas and nitrogen carries out prereduction 1h, step up later the ratio of hydrogen in hydrogen and nitrogen mixture to 10v%,
50v%, 100% control the process catalyst bed hot(test)-spot temperature no more than 280 DEG C, are finally warming up to 230 DEG C in pure hydrogen atmosphere
Lower reduction 4h.The volume space velocity 800h of gas-1。
Then evaluation can be carried out to the catalyst performance after activation, evaluating catalyst condition: reaction pressure 2.5MPa, reaction temperature
Degree is 60 DEG C, H2/ acetophenone molar ratio 50:1, acetophenone liquid hourly space velocity (LHSV) are 0.4g/g/h.
Comparative example 5
By 157.04gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、38.3gAl(NO3)3·9H2O is dissolved in 1630g
The aqueous solution of salt is configured in water.By 4.61g glycerine, 4.61g polyethylene glycol and the dissolution of 18.45g neopelex
In salting liquid.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 234g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Coprecipitation reaction carries out in the common reactor with blade stirring, speed of agitator 300rpm.Control reaction
Temperature in the kettle is 80 DEG C, sedimentation time 60min, and 80 DEG C of aging 2h obtain slurries later.Then washing, filtering, drying, most
It is placed at 400 DEG C and roasts 8h.Up to 13# catalyst.
Reduction and evaluation condition are the same as embodiment 1.
Comparative example 6
By 157.04gCu (NO3)2·3H2O、16.5g Mg(NO3)2.6H2O、38.3gAl(NO3)3·9H2O is dissolved in 1630g
The aqueous solution of salt is configured in water.
150g sodium carbonate is configured to the aqueous solution i.e. precipitating reagent aqueous solution of 15wt%.By the alkaline silicon of the 30wt% of 234g
Colloidal sol is added slowly in configured precipitating reagent aqueous solution.
Two kinds of solution cocurrents are added in high-shear reactor, using the revolving speed of 19000rpm, control temperature in reaction kettle
Degree is 80 DEG C, sedimentation time 4min, and 80 DEG C of aging 2h obtain slurries later.Then washing, filtering, drying, are finally placed in
8h is roasted at 400 DEG C.Up to 14# catalyst.
Reduction and evaluation condition are the same as embodiment 1.
Above-described embodiment and comparative example are respectively 50h sampling analysis in the reaction time, and catalyst performance evaluation the results are shown in Table
1。
1 catalyst performance evaluation result of table
Claims (10)
1. a kind of preparation method of copper-based hydrogenation catalyst, the catalyst is prepared using coprecipitation, which is characterized in that
The aqueous solution containing precipitating reagent, silica solution and the salting liquid is set to carry out co-precipitation operation in high-shear reactor；Wherein, institute
Stating salting liquid is that soluble metallic salt corresponding with catalyst activity component copper oxide and auxiliary agent is dissolved in water, is configured
Salting liquid.
2. preparation method according to claim 1, which is characterized in that in the catalyst, be based on total catalyst weight, oxygen
Change copper content is 30-70%, and auxiliary agent content is 0.5-10%, dioxide-containing silica 25-65%；
Preferably, oxidation copper content is 40-60%, and auxiliary agent content is 2-6%, dioxide-containing silica 35-55%.
3. preparation method according to claim 1 or 2, which is characterized in that the auxiliary agent is MgO, CaO, CeO2、TiO2And
Al2O3One of or it is a variety of；
Preferably, the auxiliary agent is MgO and Al2O3, and the molar ratio MgO:Al of the two2O3For 1:3-3:1, preferably 1:2-2:1.
4. preparation method according to claim 1, which is characterized in that when being co-precipitated operation, the precipitating reagent aqueous solution
Co-precipitation operation is carried out with the salting liquid again after first mixing with silica solution；
Preferably, the silica solution is alkaline silica sol, pH value 8.0-10.0；The precipitating reagent be potassium carbonate, sodium bicarbonate,
One of saleratus, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, urea and ammonium hydroxide are a variety of.
5. preparation method described in any one of -4 according to claim 1, which is characterized in that the metal salt in the salting liquid is dense
Degree is 0.3-2mol/L, preferably 0.5-1.0mol/L；
Preferably, the salting liquid is before being co-precipitated, wherein being also added with small molecule polyol and/or surfactant；
Wherein, the additive amount of the small molecule polyol is the 0.5-3%, preferably 1-2% of salting liquid quality；The surfactant
Additive amount is the 0.5-3%, preferably 1-2% of salting liquid quality.
6. the preparation method according to any one of claim 5, which is characterized in that
The small molecule polyol compound is one of propylene glycol, glycerine, butanediol, sorbierite and polyethylene glycol or more
Kind, preferably the mixture of glycerine and polyethylene glycol, mixing mass ratio are glycerine: polyethylene glycol=0.5:1-4:1, preferably
It is glycerine: polyethylene glycol=1:1-2:1；
The surfactant is neopelex, lauryl sodium sulfate, OP-10, Tween 80, TX-100 and fat
One or more of sour methyl ester sulfonate, preferably neopelex.
7. preparation method according to claim 1 to 6, which is characterized in that
The high-shear reactor is the high-shear reactor that mover and stator couple, and rotor operation rate is not less than 5000rpm,
Preferably not less than 10000rmp；Preferably, between the mover and stator between be divided into 0.2-1mm.
8. preparation method according to claim 1, which is characterized in that the preparation method further includes in the high shear
Material in reactor after coprecipitation reaction carries out aging, washing and roasting to obtain the treatment process of catalyst；Wherein, described
The temperature of coprecipitation reaction process and ageing process is 60-90 DEG C；Maturing temperature is 300-700 DEG C, calcining time 4-12h.
9. catalyst made from preparation method according to claim 1 to 8 prepares α-in acetophenone liquid-phase hydrogenatin
Application in benzyl carbinol.
10. application according to claim 9, which is characterized in that before catalysis hydrogenation of acetophenone prepares alpha-phenyl ethyl alcohol, to institute
It states catalyst and carries out reduction activation；
The method of the reduction activation of the catalyst includes: the mixed gas volume space velocity 300-1000h for keeping hydrogen and nitrogen-1, it is passed through and is no more than 10v%H containing volume fraction2The hydrogen and nitrogen gaseous mixture to the catalyst carry out prereduction extremely
Few 0.5h, steps up the ratio of hydrogen in hydrogen and nitrogen mixture later, controls the process catalyst bed hot(test)-spot temperature
No more than 300 DEG C, it is finally warming up to the 200-250 DEG C of reductase 12-5h under pure hydrogen atmosphere, the catalyst activated.
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| CN114956135A (en) * | 2022-05-16 | 2022-08-30 | 安徽大学绿色产业创新研究院 | Method for preparing nano magnesium hydroxide flame retardant through high shear force |
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