CN109894147A - A kind of load type cobalt-base catalyst and preparation method thereof and application method - Google Patents
A kind of load type cobalt-base catalyst and preparation method thereof and application method Download PDFInfo
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Abstract
The present invention relates to a kind of load type cobalt-base catalysts including active component Co, carrier, organic acid and organic solvent, and further relate to the preparation method and application method of the load type cobalt-base catalyst.When load type cobalt-base catalyst of the present invention is used for hydroformylation reaction; compared with existing catalyst; it can inhibit the loss of metallic cobalt significantly, and the catalyst has good stability in use, and is easy after reaction with the separation of product；Meanwhile preparation method of the present invention is simple, and using load type cobalt-base catalyst catalysis hydroformylation reaction when remains high selectivity.
Description
Technical field
The present invention relates to catalytic field, particularly a kind of load type cobalt-base catalyst and preparation method thereof and user
Method.
Background technique
Hydroformylation was had found in the laboratory Oberhausen Ruhrchemie from Germany scientist Otto Roelen in 1938
Reaction, and since the beginning of the fifties builds up first set commercial plant, the research of hydroformylation of olefin contains long do not wane always.Hydrogen
Formylation reaction refers to alkene and synthesis gas (CO+H2) it is raw material, the process of aldehyde is generated under the action of catalyst.F- T synthesis
Reaction realizes the transformation that coal becomes oil, contains a large amount of alkene in Fischer-Tropsch product, alkene is isolated from Fischer-Tropsch product, is passed through after
Hydroformylation reaction obtains aldehyde and further obtains alcohol through reduction, and alcohol can be used to prepare plasticizer, surfactant etc., have
Higher added value, therefore hydroformylation reaction has been one of current industrial most important homogeneous reaction.
Although the reactivity of homogeneous catalyst and selectivity are that heterogeneous catalyst is incomparable, much homogeneously urge
Agent is all merely because catalyst and product are difficult to separate and can not industrialize.In recent years, the research of Immobilized homogenous catalyst
Obtained extensive attention, be broadly divided into two major classes: one kind be it is homogeneous immobilized, another kind of is biphasic catalysis.It is homogeneous immobilized
, organic polymer immobilized including inorganic carrier supports liquid-phase catalyst, supported aqueous phase catalysts.Biphasic catalysis includes liquid liquid
Biphasic catalysis, FBS strategy, Thermoregulated phase separation catalysis, supercritical fluid two-phase, non-aqueous ionic liquid, supercritical fluid-from
Sub- liquid two-phase system etc..Although having emerged in large numbers the concept of many novelties in these catalyst systems, they or metal
It is poor perhaps using expensive organic ligand, solvent or catalyst preparation that component is lost serious perhaps catalyst stability
Process is cumbersome, complex process.
The Chinese patent application of Publication No. CN 102617308A discloses a kind of alkene two-phase hydroformylation process,
In, using Rh-TPPTS as catalyst, using the polyethers guanidine mesylate ionic liquid with room temperature solidifiable characteristic
(PGMILs) " homogeneous reaction, the two-phase laminated flow " of the reaction is realized.Although the selectivity of the high-carbon aldehyde of the reaction is up to 85~99%
And the molar ratio of n-alkanal and iso-aldehyde is 2.0~2.4.But ionic liquid used by this method is expensive and preparation is multiple
Miscellaneous, production cost is higher, limits its industrial applications.
The Chinese patent application of Publication No. CN 104710289A discloses a kind of to be used for using solid heterogeneous catalyst
The method of hydroformylation of olefin, this method are prepared using metal Rh and the mode of porous organic polymer ligand complex
Catalyst, prepared catalyst have the advantages that homogeneous catalyst, reaction when catalyst activity and product yield all compared with
Height, but Polymeric ligands synthesis technology itself is complicated, higher cost.
In Low-Pressure Hydroformylation of Middle Olefins over Co and Rh
Supported on Active Carbon Catalysts, Energy&Fuels 2003,17 is mentioned in 810-816 article
, cobalt-base catalyst is used to be readily formed the loss that carbonyl cobalt causes catalyst when hydroformylation reaction, and it is active to decline, it is active
The number of dropouts of metal can reach 20%, and when improving pressure to 5.0MPa, number of dropouts is up to 50%.This not only loses more
The advantage that phase catalyst is separated and recycled, it is also difficult to the work of homogeneous catalysis and heterogeneous catalysis is distinguished in a reaction system
Property.
Therefore, in multiphase hydroformylation reaction, for the losing issue of catalyst activity metal, there is presently no in reality
Available more perfect solution in the course of industrialization on border.
Summary of the invention
In view of the above technical problems, the present invention provides one kind and can effectively inhibitory activity component be lost in catalysis reaction, and
Simple load type cobalt-base catalyst of preparation method and preparation method thereof and application method.
To achieve the above object with additional other purposes or benefit, the invention discloses following technical solutions.
In one aspect, the present invention relates to a kind of load type cobalt-base catalysts, wherein the catalyst includes with parts by weight
The following ingredient of number meter: 0.1-10 parts of active component Co；75-98 parts of carrier；1-15 parts of organic acid；Organic solvent, weight are
200-1100 times of the organic acid.
On the other hand, the present invention relates to a kind of methods for preparing above-mentioned load type cobalt-base catalyst, wherein the method
Include the following steps:
(1) precursor of active component Co is dissolved in solvent, obtains the solution containing active component Co；
(2) by carrier impregnation in the solution containing active component Co, at room temperature as stirring is ultrasonically treated,
Obtain mixed solution；
(3) mixed solution is removed into solvent under vacuum conditions, obtains solid mixture；
(4) solid mixture is successively dried, roasted and reduction treatment, obtain semi-finished product catalyst；
(5) organic acid is dissolved in organic solvent, obtains the solution of organic acid；
(6) the semi-finished product catalyst is placed in the solution of the organic acid, is stirred so that the organic acid wraps up institute
Active component Co is stated, the load type cobalt-base catalyst is obtained.
It yet still another aspect, the present invention relates to a kind of hydrogen formyls using above-mentioned load type cobalt-base catalyst catalysis chain olefin
Change the method for reaction, wherein the method includes under the action of the load type cobalt-base catalyst, making the chain olefin same
CO and H2Reaction generates aldehyde.
Beneficial effects of the present invention:
Load type cobalt-base catalyst provided by the invention can not only significant ground inhibitory activity metal loss, also have with it is equal
The selectivity that phase cobalt carbonyl catalyst compares favourably, and separated with product easy after reacting, it had both avoided present in homogeneous catalyst
Catalyst and product separation and Recycling, in turn avoid conventional heterogeneous catalyst and form carbonyl cobalt being lost cobalt
Problem has good prospects for commercial application.
Detailed description of the invention
Fig. 1 shows the Co/SiO of semi-finished product obtained in preparation example 12The XRD diagram of catalyst.
Fig. 2 shows the Co/SiO of semi-finished product obtained in preparation example 12The transmission electron microscope image of catalyst.
Specific embodiment
Following illustrative embodiment is only for explaining the solution of the present invention, and is not intended to any
Mode limits the protection scope of the application.
In the present invention, unless otherwise indicated, term " room temperature " refers to 20 DEG C -40 DEG C.
In one embodiment, the present invention relates to a kind of load type cobalt-base catalysts, wherein the catalyst include with
The following ingredient of parts by weight meter: 0.1-10 parts of active component Co；75-98 parts of carrier；1-15 parts of organic acid；Organic solvent,
Weight is 200-1100 times of organic acid.
In of the invention one illustrative embodiment, the catalyst includes that parts by weight are the described of 0.9-9
Active component Co.
In of the invention one illustrative embodiment, the active component Co can be from including cobalt nitrate, chlorine
Change one of group of cobalt, acetylacetone cobalt and carbonyl cobalt or a variety of, but not limited to this.
In of the invention one illustrative embodiment, the carrier can be for selected from SiO2、α-Al2O3、SiC、
Si3N4、C3N4With one of MCM-48 molecular sieve or a variety of, but not limited to this.
In further preferred embodiment, the specific surface area of the carrier is 10-850m2/ g, Kong Rongwei 0.05-
1.0cm3/ g, pore-size distribution is in the range of 2-30nm.
In of the invention one illustrative embodiment, the organic acid can for selected from formic acid, oxalic acid, citric acid and
One of tartaric acid is a variety of, but not limited to this.
In of the invention one illustrative embodiment, the organic solvent can be selected from toluene, N, N- dimethyl methyl
Amide (DMF), dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, ethyl alcohol, methanol or its any mixture, but not limited to this.
In another embodiment, the present invention relates to a kind of methods for preparing above-mentioned load type cobalt-base catalyst, wherein institute
The method of stating includes the following steps:
(1) precursor of active component Co is dissolved in solvent, obtains the solution containing active component Co；
(2) by carrier impregnation in the solution containing active component Co, at room temperature as stirring is ultrasonically treated,
Obtain mixed solution；
(3) mixed solution is removed into the solvent under vacuum conditions, obtains solid mixture；
(4) solid mixture is successively dried, roasted and reduction treatment, obtain semi-finished product catalyst；
(5) organic acid is dissolved in organic solvent, obtains the solution of organic acid；
(6) the semi-finished product catalyst is placed in the solution of the organic acid, is stirred so that the organic acid wraps up institute
Active component Co is stated, the load type cobalt-base catalyst is obtained.
In of the invention one illustrative embodiment, the solvent in the step (1) can be selected from alcohol and/or water；
The alcohol is for example selected from C1-C4 alcohol, preferred alcohol.It is highly preferred that the active component Co and the solvent in the step (1)
Mass volume ratio is 1:(400-1000).
In of the invention one illustrative embodiment, in the step (1), the precursor of the active component Co
Can be for selected from one of cobalt nitrate, cobalt chloride, acetylacetone cobalt and carbonyl cobalt or a variety of, but it is not limited only to this.
In of the invention one illustrative embodiment, the mass ratio of the carrier and the active component Co is
100:(1-10)。
In of the invention one illustrative embodiment, ultrasonator progress is can be used in the ultrasonic treatment；It is excellent
Selection of land, the power of the ultrasonic treatment is 800W, working frequency 40KHz, and the time is 1-2h.
In of the invention one illustrative embodiment, can by the mixed solution vacuum condition (preferably-
Rotary evaporation is carried out at a temperature of 313K-343K under 0.1MPa) with the revolving speed of 100-300rpm to handle to remove the solvent,
To obtain solid mixture；For example, the temperature of the rotary evaporation can be 320K-325K, revolving speed can be 140-160rpm.
In of the invention one illustrative embodiment, baking oven progress is can be used in the drying；Preferably, described dry
Dry temperature is 333K-393K, and the dry time is 6-12h.
In of the invention one illustrative embodiment, Muffle furnace progress is can be used in the roasting；Preferably, described
The temperature of roasting is 573K-773K, and the time of roasting is 2-6h.
In of the invention one illustrative embodiment, H is can be used in the reduction2The tube furnace of atmosphere carries out；It is excellent
Selection of land, the temperature of the reduction are 573K-973K, and the time of reduction is 2-12h.
In of the invention one illustrative embodiment, the mass ratio of the organic acid and the organic solvent is 1:
(200-1100)。
In of the invention one illustrative embodiment, the organic solvent can be selected from toluene, N, N- dimethyl methyl
Amide (DMF), dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, ethyl alcohol, methanol or its any mixture, but not limited to this.
In addition, the carrier and organic acid that use in above-mentioned preparation method are as defined above.
In of the invention one illustrative embodiment, for the purpose for avoiding organic acid from wasting, the semi-finished product
The mass ratio of catalyst and the organic acid is (50-150): (2-8).
In yet another embodiment, chain olefin is catalyzed using above-mentioned load type cobalt-base catalyst the present invention relates to a kind of
The method of hydroformylation reaction, wherein the method includes under the action of the load type cobalt-base catalyst, making the chain
Alkene is the same as CO and H2Reaction generates aldehyde.
In of the invention one illustrative embodiment, the quality of the load type cobalt-base catalyst and chain olefin
Molar ratio is (50-150): (2-4).
In of the invention one illustrative embodiment, the chain olefin can be C3-C10 chain olefin, such as
C6-C8 chain olefin more preferably for example can be selected from 1- hexene, 2- hexene, 1- octene and/or 2- octene, but be not limited only to this.
In of the invention one illustrative embodiment, the hydroformylation reaction carries out 3- at 373-393K
15h。
In the present invention, by using the load type cobalt-base catalyst prepared in specific method, so as in hydrogen first
Inhibit the loss of the active metal in catalyst in acylation reaction significantly, while also retaining high selectivity, and this is urged
Agent is easy to separate with product, is suitble to industrial applications.
Embodiment
An exemplary embodiment of the present invention will be described below, including the embodiment of the present invention various details to help
In understanding, they should be thought to be only exemplary.Therefore, it will be appreciated by those of ordinary skill in the art that, can be right
The embodiments described herein makes various changes and modifications, without departing from scope and spirit of the present invention.Equally, in order to clear
And simplicity, descriptions of well-known functions and structures are omitted from the following description.
Reagent, material and device as used in the following examples etc., it is unless otherwise specified, commercially available.
Preparation example 1
Weigh 0.75g Co (NO3)2·6H2O is simultaneously dissolved in 200g deionized water, and obtaining active metal Co content is 3wt%
Co (NO3)2Solution.Weigh 5.0g SiO2Carrier (specific surface area 150m2/ g, Kong Rong 0.9m3/ g, average pore size 23.4nm) simultaneously
It is impregnated in above-mentioned solution, ultrasonic treatment 1h (wherein, ultrasonic output power is carried out using ultrasonator with stirring at room temperature
For 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, then by obtained mixed solution in rotary evaporation
In instrument (revolving speed 150rpm) under vacuum (negative pressure -0.1MPa), 323K solvent evaporated, obtain powdered solid mixture.
The solid powder is placed in baking oven under 333K dry 12h, then 4h is roasted under 673K in Muffle furnace, obtains Co3O4/
SiO2.By Co3O4/SiO2In H in tube furnace26h is restored under atmosphere, 673K, wherein hydrogen flow rate is 50ml/min, after reduction
Catalyst be semi-finished product catalyst (i.e. Co/SiO2Catalyst).6mg citric acid is dissolved in 20mmol toluene, lemon is obtained
The above-mentioned semi-finished product catalyst of 100mg is placed in the toluene solution of citric acid as described above by the toluene solution of lemon acid, in
2h is stirred under 373K, arrives load type cobalt-base catalyst after citric acid sufficiently wraps up active metal Co.Wherein, the preparation
The XRD diagram and transmission electron microscope image for the semi-finished product cobalt-base catalyst that example obtains are as depicted in figs. 1 and 2.
Preparation example 2
Weigh 2.47g Co (NO3)2·6H2O is simultaneously dissolved in 200g deionized water, is obtained active metal Co content and is
Co (the NO of 10wt%3)2Solution.Take 5.0g SiO2Carrier (specific surface area 150m2/ g, Kong Rong 0.9m3/ g, average pore size
23.4nm), carrier is immersed in above-mentioned solution, with stirring (wherein, ultrasonic treatment 2h is carried out using ultrasonator at room temperature
Ultrasonic output power is 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, it is then that obtained mixing is molten
Liquid solvent evaporated under vacuum (negative pressure -0.1MPa), 313K in Rotary Evaporators (revolving speed 300rpm), obtains powdered
Solid mixture.The solid powder is placed in baking oven under 363K dry 12h, is then roasted under 573K in Muffle furnace
6h obtains Co3O4/SiO2, by Co3O4/SiO2In H in tube furnace2Reductase 12 h under atmosphere, 973K, wherein hydrogen flow rate be
50ml/min, the catalyst after reduction are semi-finished product catalyst (i.e. Co/SiO2Catalyst).By 8mg dissolving oxalic acid in 25mmol
In n,N-Dimethylformamide (DMF), the DMF solution of oxalic acid is obtained, the semi-finished product catalyst of 50mg is placed in as described above
Oxalic acid DMF solution in, stir 2h under 373K, after oxalic acid sufficiently wraps up active metal Co to get arrive load type cobalt-base
Catalyst.
Preparation example 3
Weigh 0.75g Co (NO3)2·6H2O is simultaneously dissolved in 100g deionized water, and obtaining active metal Co content is 3wt%
Co (NO3)2Solution.Take 5.0g C3N4Carrier (specific surface area 11m2/ g, Kong Rong 0.05m3/ g, average pore size 12nm), this is carried
Body is impregnated in above-mentioned solution, carries out ultrasonic treatment 1h (wherein, ultrasonic output work using ultrasonator with stirring at room temperature
Rate is 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, then steams obtained mixed solution in rotation
The solvent evaporated under vacuum (negative pressure -0.1MPa), 343K is sent out in instrument (revolving speed 100rpm), powdered solid mixing is obtained
Object.The solid powder is placed in baking oven under 393K dry 6h, then 2h is roasted under 773K in Muffle furnace, obtains
Co3O4/C3N4, by Co3O4/C3N4In H in tube furnace28h is restored under atmosphere, 673K, wherein hydrogen flow rate is 50ml/min, also
Catalyst after original is semi-finished product catalyst (i.e. Co/C3N4Catalyst).6mg tartaric acid is dissolved in 30mmol acetone, is obtained
The semi-finished product catalyst of 80mg is placed in the acetone soln of tartaric acid as described above by the acetone soln of tartaric acid, in
2h is stirred under 373K, arrives load type cobalt-base catalyst after tartaric acid sufficiently wraps up active metal Co.
Preparation example 4
It weighs 0.907g acetylacetone cobalt and is dissolved in 100g ethyl alcohol, obtain the Co that active metal Co content is 3wt%
(NO3)2Solution.Take 5.0g α-Al2O3Carrier (specific surface area 78m2/ g, Kong Rong 0.43m3/ g, average pore size 23nm), by this carrier
It is impregnated in above-mentioned solution, ultrasonic treatment 2h (wherein, ultrasonic output power is carried out using ultrasonator with stirring at room temperature
For 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, then by obtained mixed solution in rotary evaporation
In instrument (revolving speed 150rpm) under vacuum (negative pressure -0.1MPa), 323K solvent evaporated, obtain powdered solid mixture.
The solid powder is placed in baking oven under 333K dry 12h, then 6h is roasted under 673K in Muffle furnace, obtains Co3O4/
α-Al2O3, by Co3O4/α-Al2O3In H in tube furnace212h is restored under atmosphere, 573K, wherein hydrogen flow rate is 50ml/min,
Catalyst after reduction is semi-finished product catalyst (i.e. Co/ α-Al2O3Catalyst).It is sub- that 6mg formic acid is dissolved in 30mmol dimethyl
In sulfone (DMSO), the DMSO solution of formic acid is obtained, the semi-finished product catalyst of 50mg is placed in the DMSO of formic acid as described above
In solution, 2h is stirred under 373K, arrives load type cobalt-base catalyst after formic acid sufficiently wraps up active metal Co.
Preparation example 5
It weighs 1.01g cobalt chloride hexahydrate and is dissolved in 50g ethyl alcohol, obtain the CoCl that active metal Co content is 5wt%2
Solution.Take 5.0g MCM-48 molecular sieve carrier (specific surface area 810m2/ g, Kong Rong 0.506m3/ g, average pore size 2.857nm), it will
This carrier impregnation carries out ultrasonic treatment 1h using ultrasonator with stirring in above-mentioned solution, at room temperature, and (wherein, ultrasound is defeated
Power is 800W, working frequency 40KHz out), continue to stir 12h after ultrasonic, is then revolving obtained mixed solution
Turn in evaporimeter (revolving speed 150rpm) solvent evaporated under vacuum (negative pressure -0.1MPa), 323K, it is mixed to obtain powdered solid
Close object.The solid powder is placed in baking oven under 333K dry 12h, then 6h is roasted under 673K in Muffle furnace, obtains
Co3O4/ MCM-48, by Co3O4/ MCM-48 is in tube furnace in H212h is restored under atmosphere, 573K, wherein hydrogen flow rate is 50ml/
Min, the catalyst after reduction are semi-finished product catalyst (i.e. Co/MCM-48 catalyst).6mg citric acid is dissolved in 25mmol tetra-
In hydrogen furans, the tetrahydrofuran solution of citric acid is obtained, the semi-finished product catalyst of 100mg is placed in citric acid as described above
Tetrahydrofuran solution in, stir 2h under 373K, after citric acid sufficiently wraps up active metal Co to get arrive load type cobalt-base
Catalyst.
Preparation example 6
It weighs 0.726g cobalt octacarbonyl to be dissolved in 50g ethyl alcohol, obtains the Co that active metal Co content is 5wt%2(CO)8
Solution.Take 5.0g Si3N4Molecular sieve carrier (specific surface area 66m2/ g, Kong Rong 0.475m3/ g, average pore size 28nm), this is carried
Body is impregnated in above-mentioned solution, carries out ultrasonic treatment 1h (wherein, ultrasonic output work using ultrasonator with stirring at room temperature
Rate is 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, then steams obtained mixed solution in rotation
The solvent evaporated under vacuum (negative pressure -0.1MPa), 323K is sent out in instrument (revolving speed 150rpm), powdered solid mixing is obtained
Object.The solid powder is placed in baking oven under 333K dry 12h, then 6h is roasted under 673K in Muffle furnace, obtains
Co3O4/Si3N4, by Co3O4/Si3N4In H in tube furnace212h is restored under atmosphere, 573K, wherein hydrogen flow rate is 50ml/
Min, the catalyst after reduction are semi-finished product catalyst (i.e. Co/Si3N4Catalyst).6mg citric acid is dissolved in 35mmol ethyl alcohol
In, the ethanol solution of citric acid is obtained, the semi-finished product catalyst of 100mg is placed in the ethanol solution of citric acid as described above
In, 2h is stirred under 373K, arrives load type cobalt-base catalyst after citric acid sufficiently wraps up active metal Co.
Preparation example 7
Weigh 0.247g Co (NO3)2·6H2O is simultaneously dissolved in 50g deionized water, is obtained active metal Co content and is
Co (the NO of 1.0wt%3)2Solution.Take 5.0g SiC carrier (specific surface area 35.6m2/ g, Kong Rong 0.154m3/ g, average pore size
17.43nm), carrier is immersed in above-mentioned solution, ultrasonic treatment 2h (its is carried out using ultrasonator with stirring at room temperature
In, ultrasonic output power is 800W, working frequency 40KHz), continue to stir 12h, the mixing that then will be obtained after ultrasonic
Solution solvent evaporated under vacuum (negative pressure -0.1MPa), 323K in Rotary Evaporators (revolving speed 150rpm), obtains powdered
Solid mixture.The solid powder is placed in baking oven under 363K dry 12h, is then roasted under 573K in Muffle furnace
6h obtains Co3O4/ SiC, by Co3O4/ SiC is in tube furnace in H2Reductase 12 h under atmosphere, 973K, wherein hydrogen flow rate is 50ml/
Min, the catalyst after reduction are semi-finished product catalyst (i.e. Co/SiC catalyst).By 2mg dissolving oxalic acid in 30mmol tetrahydro furan
It mutters in (THF), obtains the THF solution of oxalic acid, the 150mg semi-finished product catalyst is placed in the THF solution of oxalic acid as described above
In, 2h is stirred under 373K, arrives load type cobalt-base catalyst after oxalic acid sufficiently wraps up active metal Co.
Embodiment 1
The load type cobalt-base catalyst of the package of citric acid obtained in preparation example 1 by 100mg is added to intermittent reaction
In kettle, 4mmol raw material 1- hexene is added into the batch reactor, is then filled with 5MPa synthesis gas (CO:H thereto2=1:
1) 3h, is reacted under 373K, product is analyzed using Agilent-7890A gas-chromatography after reaction, the Agilent-7890A
Gas chromatograph is furnished with PLOT-Al2O3Column (1 μm of the μ m of 50m × 530), HP-INNO Wax column (0.5 μm of the μ m of 30m × 320),
Front and back detector is fid detector, carries out quantitative calculating to reaction product as internal standard compound using biphenyl.It 30 DEG C of initial temperature, protects
Stay time 4min, 10 DEG C/min of heating rate, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Embodiment 2
The load type cobalt-base catalyst of the package of tartaric acid obtained in preparation example 3 by 80mg is added to batch reactor
In, 4mmol raw material 2- hexene is added into the batch reactor, is then filled with 5MPa synthesis gas (CO:H thereto2=1:
1) 15h, is reacted under 393K, product is analyzed using Agilent-7890A gas-chromatography after reaction, the Agilent-
7890A gas chromatograph is furnished with PLOT-Al2O3Column (1 μm of the μ m of 50m × 530), the HP-INNO Wax column (μ m of 30m × 320 0.5
μm), front and back detector is fid detector, carries out quantitative calculating to reaction product as internal standard compound using biphenyl.Initial temperature 30
DEG C, retention time 4min, 10 DEG C/min of heating rate, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Embodiment 3
The load type cobalt-base catalyst of the package of formic acid obtained in preparation example 4 by 50mg is added to batch reactor
In, 4mmol raw material 1- octene is added into the batch reactor, is then filled with 5MPa synthesis gas (CO:H thereto2=1:
1) 15h, is reacted under 393K, product is analyzed using Agilent-7890A gas-chromatography after reaction, the Agilent-
7890A gas chromatograph is furnished with PLOT-Al2O3Column (1 μm of the μ m of 50m × 530), the HP-INNO Wax column (μ m of 30m × 320 0.5
μm), front and back detector is fid detector, carries out quantitative calculating to reaction product as internal standard compound using biphenyl.Initial temperature 30
DEG C, retention time 4min, 10 DEG C/min of heating rate, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Embodiment 4
The load type cobalt-base catalyst of the package of oxalic acid obtained in preparation example 2 by 50mg is added to batch reactor
In, 4mmol raw material 2- octene is added into the batch reactor, is then filled with 5MPa synthesis gas (CO:H thereto2=1:
1) 5h, is reacted under 393K, product is analyzed using Agilent-7890A gas-chromatography after reaction, the Agilent-7890A
Gas chromatograph is furnished with PLOT-Al2O3Column (1 μm of the μ m of 50m × 530), HP-INNO Wax column (0.5 μm of the μ m of 30m × 320),
Front and back detector is fid detector, carries out quantitative calculating to reaction product as internal standard compound using biphenyl.It 30 DEG C of initial temperature, protects
Stay time 4min, 10 DEG C/min of heating rate, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Embodiment 5
The load type cobalt-base catalyst of the package of oxalic acid obtained in preparation example 7 by 150mg is added to batch reactor
In, 2mmol raw material 1- hexene is added into the batch reactor, is then filled with 5MPa synthesis gas (CO:H thereto2=1:
1) 5h, is reacted under 393K, product is analyzed using Agilent-7890A gas-chromatography after reaction, the Agilent-7890A
Gas chromatograph is furnished with PLOT-Al2O3Column (1 μm of the μ m of 50m × 530), HP-INNO Wax column (0.5 μm of the μ m of 30m × 320),
Front and back detector is fid detector, carries out quantitative calculating to reaction product as internal standard compound using biphenyl.It 30 DEG C of initial temperature, protects
Stay time 4min, 10 DEG C/min of heating rate, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Embodiment 6
Load type cobalt-base catalyst in the embodiment 1 of 100mg is recycled, catalyst is centrifuged out from solution
Come, then dried, roasted, restored, the toluene solution of citric acid package, then rejoined in batch reactor,
4mmol raw material 1- hexene is added into the batch reactor, is then filled with 5MPa synthesis gas (CO:H thereto2=1:1), in
5h is reacted under 373K, product is analyzed using Agilent-7890A gas-chromatography after reaction, the Agilent-7890A gas phase
Chromatograph is furnished with PLOT-Al2O3Column (1 μm of the μ m of 50m × 518), HP-INNO Wax column (0.5 μm of the μ m of 30m × 320), front and back
Detector is fid detector, carries out quantitative calculating to reaction product as internal standard compound using biphenyl.30 DEG C of initial temperature, when reservation
Between 4min, 10 DEG C/min of heating rate, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Comparative example 1
Weigh 0.75g Co (NO3)2·6H2O is simultaneously dissolved in 100g deionized water, and obtaining active metal Co content is 3wt%
Co (NO3)2Solution.Take 5.0g SiO2Carrier (specific surface area 150m2/ g, Kong Rong 0.9m3/ g, average pore size 23.4nm), by this
Carrier impregnation carries out ultrasonic treatment 1h using ultrasonator with stirring in above-mentioned solution, at room temperature, and (wherein, ultrasound exports
Power is 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, is then rotating obtained mixed solution
In evaporimeter (revolving speed 150rpm) under vacuum condition, 323K solvent evaporated, obtain powdered solid mixture.This is consolidated
Body powder is placed in baking oven under 333K dry 12h, then roasts 6h under 673K in Muffle furnace, obtains Co3O4/SiO2, will
Co3O4/SiO2In H in tube furnace26h, hydrogen flow rate 50ml/min are restored under atmosphere, 673K, by the catalyst after reduction
With the cobalt-base catalyst compared.
The above-mentioned cobalt-base catalyst of 100mg is added in batch reactor, then thereto be added 20mmol toluene,
4mmol raw material 1- hexene, and it is then filled with 5MPa synthesis gas (CO:H thereto2=1:1), 5h is reacted under 373K, after reaction
Product is analyzed using Agilent-7890A gas-chromatography, which is furnished with PLOT-Al2O3
Column (1 μm of the μ m of 50m × 518), HP-INNO Wax column (0.5 μm of the μ m of 30m × 320), front and back detector is fid detector,
Quantitative calculating is carried out to reaction product as internal standard compound using biphenyl.30 DEG C of initial temperature, retention time 4min, 10 DEG C of heating rate/
Min, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Comparative example 2
Weigh 0.75g Co (NO3)2·6H2O is simultaneously dissolved in 100g deionized water, and obtaining active metal Co content is 3wt%
Co (NO3)2Solution.Take 5.0g Si3N4Carrier (specific surface area 66m2/ g, Kong Rong 0.475m3/ g, average pore size 28nm), by this
Carrier impregnation carries out ultrasonic treatment 2h using ultrasonator with stirring in above-mentioned solution, at room temperature, and (wherein, ultrasound exports
Power is 800W, working frequency 40KHz), continue to stir 12h after ultrasonic, is then rotating obtained mixed solution
In evaporimeter (revolving speed 150rpm) under vacuum condition, 323K solvent evaporated, obtain powdered solid mixture.This is consolidated
Body powder is placed in baking oven under 333K dry 12h, then roasts 6h under 673K in Muffle furnace, obtains Co3O4/Si3N4,
By Co3O4/Si3N4In H in tube furnace26h, hydrogen flow rate 50ml/min are restored under atmosphere, 673K, by the catalysis after reduction
The agent cobalt-base catalyst compared.
The above-mentioned cobalt-base catalyst of 80mg is added in batch reactor, then thereto be added 20mmol toluene,
4mmol raw material 1- hexene, and it is then filled with 5MPa synthesis gas (CO:H thereto2=1:1), 5h is reacted under 373K, after reaction
Product is analyzed using Agilent-7890A gas-chromatography, which is furnished with PLOT-Al2O3
Column (1 μm of the μ m of 50m × 518), HP-INNO Wax column (0.5 μm of the μ m of 30m × 320), front and back detector is fid detector,
Quantitative calculating is carried out to reaction product as internal standard compound using biphenyl.30 DEG C of initial temperature, retention time 4min, 10 DEG C of heating rate/
Min, 198 DEG C of final temperature, retention time 40min.Analysis the results are shown in Table 1.
Table 1: the evaluation result for the catalyst that embodiment 1-6 and comparative example 1-2 are used
| Embodiment | Cobalt number of dropouts (%) | Conversion ratio (%) | Total aldehyde selectivity (%) | n:i |
| Embodiment 1 | 0.11 | 22.13 | 82.86 | 2.90 |
| Embodiment 2 | 0.27 | 33.72 | 82.56 | 0.67 |
| Embodiment 3 | 0.11 | 42.39 | 77.89 | 2.21 |
| Embodiment 4 | 0.30 | 25.3 | 80.20 | 2.65 |
| Embodiment 5 | 0.07 | 33.32 | 82.32 | 2.56 |
| Embodiment 6 | 1.18 | 19.74 | 83.52 | 3.16 |
| Comparative example 1 | 40.03 | 60.98 | 90.46 | 3.06 |
| Comparative example 2 | 38.12 | 50.00 | 80.12 | 3.02 |
Wherein, n:i indicates the ratio of n-alkanal and iso-aldehyde in product.
By the above results of table 1 it is found that for the cobalt-base catalyst of comparative example, made in preparation example 1-7 of the present invention
Standby load type cobalt-base catalyst activity and selectivity with higher in hydroformylation of olefin, and during the reaction
The loss of active metal cobalt is inhibited significantly.
Above-mentioned specific embodiment, does not constitute a limitation on the scope of protection of the present invention.Those skilled in the art should be bright
It is white, design requirement and other factors are depended on, various modifications, combination, sub-portfolio and substitution can occur.It is any
Made modifications, equivalent substitutions and improvements etc. within the spirit and principles in the present invention, should be included in the scope of the present invention
Within.
Claims (10)
1. a kind of load type cobalt-base catalyst, wherein the catalyst includes following ingredient based on parts by weight: active component
0.1-10 parts of Co；75-98 parts of carrier；1-15 parts of organic acid；Organic solvent, weight are 200-1100 times of the organic acid.
2. load type cobalt-base catalyst according to claim 1, wherein the catalyst includes that parts by weight are 0.9-9
The active component Co；It is further preferred that it includes cobalt nitrate, cobalt chloride, acetylacetone,2,4-pentanedione that the active component Co, which is derived from,
One of group of cobalt and carbonyl cobalt is a variety of；
Preferably, the carrier is selected from SiO2、α-Al2O3、SiC、Si3N4、C3N4With one of MCM-48 molecular sieve or more
Kind；It is further preferred that the specific surface area of the carrier is 10-850m2/ g, Kong Rongwei 0.05-1.0cm3/ g, pore-size distribution exist
In the range of 2-30nm；
Preferably, the organic acid is selected from one of formic acid, oxalic acid, citric acid and tartaric acid or a variety of；
Preferably, the organic solvent be selected from toluene, n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone,
Tetrahydrofuran, ethyl alcohol, methanol or its any mixture.
3. a kind of method for preparing load type cobalt-base catalyst of any of claims 1 or 2, wherein the method includes as follows
Step:
(1) precursor of active component Co is dissolved in solvent, obtains the solution containing active component Co；
(2) carrier impregnation, at room temperature as stirring is ultrasonically treated, is obtained in the solution containing active component Co
Mixed solution；
(3) mixed solution is removed into solvent under vacuum conditions, obtains solid mixture；
(4) solid mixture is successively dried, roasted and reduction treatment, obtain semi-finished product catalyst；
(5) organic acid is dissolved in organic solvent, obtains the solution of organic acid；
(6) the semi-finished product catalyst is placed in the solution of the organic acid, is stirred so that the organic acid wraps up the work
Property component Co, obtains the load type cobalt-base catalyst.
4. the alcohol for example selects according to the method described in claim 3, the solvent is selected from alcohol and/or water in step (1)
From C1-C4 alcohol, preferred alcohol；
Preferably, the mass volume ratio of the active component Co and the solvent is 1:(400-1000)；
Additionally preferably, the precursor of the active component Co is in cobalt nitrate, cobalt chloride, acetylacetone cobalt and carbonyl cobalt
It is one or more.
5. the method according to claim 3 or 4, in step (2), the carrier is selected from SiO2、α-Al2O3、SiC、
Si3N4、C3N4With one of MCM-48 molecular sieve or a variety of；
Preferably, the mass ratio of the carrier and the active component Co are 100:(1-10)；
Additionally preferably, the ultrasonic treatment is carried out using ultrasonator；Preferably, the power of the ultrasonic treatment is
800W, working frequency 40KHz, and the time is 1-2h.
6. the method according to any one of claim 3-5, wherein by the mixed solution vacuum condition (preferably-
Rotary evaporation is carried out at a temperature of 313K-343K under 0.1MPa) with the revolving speed of 100-300rpm to handle to remove the solvent；
It is further preferred that 320K-325K at a temperature of the rotary evaporation processing carried out with the revolving speed of 140-160rpm；
Or preferably, described dry using baking oven progress；Preferably, the temperature of the drying is 333K-393K, when dry
Between be 6-12h；
Or preferably, the roasting is carried out using Muffle furnace；Preferably, the temperature of the roasting is 573K-773K, roasting
Time is 2-6h；
Or preferably, the reduction uses H2The tube furnace of atmosphere carries out；Preferably, the temperature of the reduction is 573K-
973K, the time of reduction are 2-12h.
7. the method according to any one of claim 3-6, in step (5), the organic acid and the organic solvent
Mass ratio be 1:(200-1100)；
Preferably, the organic acid is selected from one of formic acid, oxalic acid, citric acid and tartaric acid or a variety of；
Additionally preferably, the organic solvent is selected from toluene, n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), third
Ketone, tetrahydrofuran, ethyl alcohol, methanol or its any mixture.
8. the method according to any one of claim 3-7, wherein the matter of the semi-finished product catalyst and the organic acid
Amount is than being (50-150): (2-8).
9. a kind of hydroformylation reaction using the catalysis chain olefin of load type cobalt-base catalyst described in as claimed in claim 1 or 22
Method, wherein the method includes under the action of the load type cobalt-base catalyst, making the chain olefin with CO and H2Instead
Aldehyde should be generated.
10. according to the method described in claim 9, wherein, the quality of the load type cobalt-base catalyst and the chain olefin
Molar ratio is (50-150): (2-4)；
Preferably, the chain olefin is C3-C10 chain olefin, such as C6-C8 chain olefin, more preferably for example selected from 1- oneself
Alkene, 2- hexene, 1- octene and/or 2- octene；
Additionally preferably, the hydroformylation reaction carries out 3-15h at 373-393K.
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