The specific embodiment
Described carrier-borne transition metal catalysts provided by the invention comprises porous carrier and the transient metal complex that loads on the described porous carrier, gross weight with described catalyst is a benchmark, the content of metallic atom M can be 0.01-50 weight % in the described catalyst, be preferably 0.05-20 weight %, more preferably 0.5-5 weight %.
The general formula of described transient metal complex is R
1(Z)
yMR
2Metal complex, wherein, R
1And R
2Can be for identical or different, and R
1And R
2Separately respectively can be for replacing or unsubstituted cyclopentadienyl group, replacement or unsubstituted indenyl, replacement or unsubstituted fluorenyl.Under the preferable case, R
1And R
2Be respectively cyclopentadienyl group, methyl cyclopentadienyl, ethyl cyclopentadienyl group, propyl group cyclopentadienyl group, butyl cyclopentadienyl group, isopropyl cyclopentadienyl group, indenyl or fluorenyl separately.
In the general structure of described transient metal complex, y is 0 or 1, is preferably 1; Z is for connecting R
1And R
2Linking group, and Z can be the linking group of various routines, for example can be Si (X
1)
2, C (X
2)
2, C (X
3)
2C (X
4)
2, CX
5=CX
6Or C (X
7)
2Si (X
8)
2, wherein, X
1, X
2, X
3, X
4, X
5, X
6, X
7And X
8Can be that alkyl, silicyl, haloalkyl, the carbon number of 1-10 is aryl, halogenated aryl or the halo aralkyl of 6-10 for hydrogen atom, halogen atom or carbon number respectively separately, being preferably alkyl, silicyl, haloalkyl, the carbon number that hydrogen atom or carbon number are 1-4 is aryl, halogenated aryl or the halo aralkyl of 6-8, and X
3And X
4Can be preferably identical for identical or different; X
5And X
6Can be preferably identical for identical or different; X
7And X
8Can be preferably identical for identical or different.Under further preferred situation, Z can be SiH
2, Si (CH
3)
2, Si (C
2H
5)
2, Si (C
3H
7)
2, CH
2, C (CH
3)
2, C (C
2H
5)
2, C (C
3H
7)
2, CH
2CH
2, C (CH
3)
2C (CH
3)
2, C (C
2H
5)
2C (C
2H
5)
2, CH=CH, C (CH
3)=C (CH
3), CH
2SiH
2Or C (CH
3)
2Si (CH
3)
2
M is a transition metal, for example can be manganese, vanadium, chromium, iron or cobalt, most preferably be cobalt, under this preferable case, the catalytic performance excellence of described carrier-borne transition metal catalysts, for example, described carrier-borne transition metal catalysts is adopting acetylene, acetonitrile to prepare to have very high catalytic performance in the reaction system of picoline and reaction generates the selectivity of 2-picoline, thereby makes the conversion ratio of acetonitrile reach more than 85%.
Described transient metal complex can adopt conventional method preparation, for example, can make to replace or the slaine and the halide of transition metal of slaine, replacement or the unsubstituted fluorenyl of slaine, replacement or the unsubstituted indenyl of unsubstituted cyclopentadienyl group, be 1.5-3 with the mol ratio: thus 1, at room temperature, under inert atmosphere such as nitrogen atmosphere, react and made in 1-4 hour; Perhaps can make general structure is R
1ZR
2Organic matter (R wherein
1, R
2With identical in Z and the above-mentioned transient metal complex) with the halide of transition metal, be 0.8-1.4 with the mol ratio: thus 1, at room temperature, reaction made in 1-4 hour under inert atmosphere such as nitrogen atmosphere.The solvent that uses in the described reaction is generally the nonaqueous solvents of the low and easy removal of boiling point, for example can be oxolane, and the described transition metal halide with respect to 1 mole, and the consumption of described solvent can be the 50-1000 milliliter, is preferably the 100-600 milliliter.
In a kind of preferred implementation of the present invention, described porous carrier can be the carrier through dehydration and dehydroxylation, by described porous carrier being dewatered and the dehydroxylation processing, thereby can reduce the influence of moisture content on the described porous carrier or hydroxyl, and then improve the catalyst performance of the carrier-borne transition metal catalysts that finally makes the catalyst performance of transient metal complex.The method that described dehydration and dehydroxylation are handled can be included in vacuum and be below the 5Pa, heated 2-10 hour down at 200-500 ℃, and in the present invention, described vacuum is meant the absolute vacuum degree.Described porous carrier can be TiO
2, zeolite, Al
2O
3And SiO
2In at least a, be preferably SiO
2, SiO
2-TiO
2(SiO
2And TiO
2Mixture), SiO
2-TiO
2-Al
2O
3(SiO
2, TiO
2And Al
2O
3Mixture), most preferably be SiO
2Carrier.
In the present invention, the particle diameter of described porous carrier can be the 1-500 nanometer, is preferably the 10-300 nanometer; Specific area can be the 100-1000 meters squared per gram, is preferably the 200-700 meters squared per gram; Porosity can be 0.32-1.49%, is preferably 0.5-0.81%.Described porosity is meant that the volume of described porous carrier mesopore accounts for the percentage of its cumulative volume.
The present invention also provides the preparation method of described carrier-borne transition metal catalysts, and wherein, described method is included under the existence of solvent porous carrier is contacted with transient metal complex, removes solvent then.The general formula of described transient metal complex is R
1(Z)
yMR
2, wherein, R
1And R
2Identical or different, and R
1And R
2Separately respectively can be for replacing or unsubstituted cyclopentadienyl group, replacement or unsubstituted indenyl, replacement or unsubstituted fluorenyl.Under the preferable case, R
1And R
2Be respectively cyclopentadienyl group, methyl cyclopentadienyl, ethyl cyclopentadienyl group, propyl group cyclopentadienyl group, butyl cyclopentadienyl group, isopropyl cyclopentadienyl group, indenyl or fluorenyl separately.Y is 0 or 1, is preferably 1; Z is for connecting R
1And R
2Linking group, and Z can be the linking group of various routines, for example can be Si (X
1)
2, C (X
2)
2, C (X
3)
2C (X
4)
2, CX
5=CX
6Or C (X
7)
2Si (X
8)
2, wherein, X
1, X
2, X
3, X
4, X
5, X
6, X
7And X
8Can be that alkyl, silicyl, haloalkyl, the carbon number of 1-10 is aryl, halogenated aryl or the halo aralkyl of 6-10 for hydrogen atom, halogen atom or carbon number respectively separately, being preferably alkyl, silicyl, haloalkyl, the carbon number that hydrogen atom or carbon number are 1-4 is aryl, halogenated aryl or the halo aralkyl of 6-8, and X
3And X
4Can be preferably identical for identical or different; X
5And X
6Can be preferably identical for identical or different; X
7And X
8Can be preferably identical for identical or different.Under further preferred situation, Z can be SiH
2, Si (CH
3)
2, Si (C
2H
5)
2, Si (C
3H
7)
2, CH
2, C (CH
3)
2, C (C
2H
5)
2, C (C
3H
7)
2, CH
2CH
2, C (CH
3)
2C (CH
3)
2, C (C
2H
5)
2C (C
2H
5)
2, CH=CH, C (CH
3)=C (CH
3), CH
2SiH
2Or C (CH
3)
2Si (CH
3)
2M is a transition metal, for example can most preferably be cobalt for manganese, vanadium, chromium, iron or cobalt.
In described method, the consumption of described transient metal complex and described porous carrier makes that the metallic atom M that finally makes in the carrier-borne transition metal catalysts is the 0.01-50 weight % of total consumption of described porous carrier and described transient metal complex, be preferably 0.05-20 weight %, more preferably 0.5-5 weight %.
In described method provided by the invention, there is no particular limitation to make the method that described porous carrier contacts with described transient metal complex, can earlier described porous carrier be added in the described solvent and make suspension, then described transient metal complex is added in the suspension of described porous carrier; Also can earlier described transient metal complex be dissolved in the described solvent, then described porous carrier be added in the solution of described transient metal complex; Described porous carrier can also be added in the described solvent and make suspension, simultaneously described transient metal complex is dissolved in the described solvent, the suspension of prepared described porous carrier is mixed with the solution of described transient metal complex.Preferred adopt above-mentioned the third method to feed in raw material, thereby make the described transition metal can be equably attached on the surface of described porous carrier and in the hole.For prevent to dewater, carrier behind the dehydroxylation moisture content in the absorbed air once more, preferably the whole operation process that described transient metal complex is attached on the described porous carrier is carried out under inert atmosphere, for example can carry out under the atmosphere of nitrogen.The condition that described porous carrier contacts with described transient metal complex can comprise: temperature is preferably 0-30 ℃, more preferably room temperature for-20-50 ℃; Be 1-3 hour time of contact, is preferably 1.5-2.5 hour.
In described method provided by the invention, there is no particular limitation for described solvent, as long as can dissolve described transient metal complex, what described solvent for example can be in oxolane, pentane, cyclohexane, benzene and the toluene is at least a.The consumption of described solvent is as long as guarantee that described transient metal complex can dissolve fully, and is preferably suitably excessive, and for example with respect to the described transient metal complex of per 10 grams, the consumption of described solvent can be the 50-300 milliliter, is preferably the 150-250 milliliter.
In a kind of preferred implementation of the present invention, before the preparation method of described carrier-borne transition metal catalysts also is included in and is added to described porous carrier in the described solvent, described porous carrier is dewatered and the dehydroxylation processing, the method that described dehydration and dehydroxylation are handled can comprise makes described porous carrier be below the 5Pa, heat 2-10 hour down at 200-500 ℃ in vacuum, in the present invention, described vacuum is meant the absolute vacuum degree.Further under the preferable case, the preparation method of described carrier-borne transition metal catalysts can also comprise that the described porous carrier that makes through dehydration and dehydroxylation processing is cooled to room temperature in inert atmosphere.
Described porous carrier can be TiO
2, zeolite, Al
2O
3And SiO
2In at least a, be preferably SiO
2, SiO
2-TiO
2(SiO
2And TiO
2Mixture), SiO
2-TiO
2-Al
2O
3(SiO
2, TiO
2And Al
2O
3Mixture), most preferably be SiO
2Carrier.The particle diameter of described porous carrier can be the 1-500 nanometer, is preferably the 10-300 nanometer; Specific area can be the 100-1000 meters squared per gram, is preferably the 200-700 meters squared per gram; Porosity can be 0.32-1.49%, is preferably 0.50-0.81%.Described porosity is meant that the volume of described porous carrier mesopore accounts for the percentage of its cumulative volume.
The present invention also provides a kind of method for preparing picoline, and described method is included in and under the existence of catalyst acetylene is contacted to react with acetonitrile, and wherein, described catalyst is a described carrier-borne transition metal catalysts provided by the invention.In the preferred case, described acetylene is the acetylene gas through deoxidation, processed, and acetylene is carried out the method for deoxidation, processed for conventionally known to one of skill in the art.The condition that described acetylene contacts with acetonitrile can comprise: temperature is 100-200 ℃, is preferably 110-160 ℃; The pressure of acetylene is 0.3-2MPa, is preferably 0.6-1.2MPa, and described acetylene pressure is meant the dividing potential drop of acetylene in the reaction system of acetylene and acetonitrile; Time is 2-5 hour, is preferably 3-4 hour; The weight ratio of the consumption of described catalyst consumption and acetonitrile is 1: 50-10000 is preferably 1: 400-5000; The mol ratio of the consumption of acetylene and acetonitrile can be 1-8: 1, be preferably 1-3.5: 1.The haptoreaction of described acetylene and acetonitrile is preferably carried out under inert atmosphere, for example can carry out under nitrogen atmosphere.
The present invention is further detailed explanation with Comparative Examples by the following examples.
Embodiment 1
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
(1) making 1 kilogram average particulate diameter is that 30 nanometers, specific area are that 507 meters squared per gram, porosity are 0.74% SiO
2Carrier is cooled to room temperature then, thereby obtains 0.994 kilogram dehydration, the SiO of dehydroxylation being to heat 6 hours under the 4Pa under 300 ℃, in vacuum under nitrogen atmosphere
2Carrier;
(2) under nitrogen atmosphere, with the SiO that obtains in (1)
2Carrier is added in 9500 milliliters the oxolane, fully stirs to make suspension;
(3) at room temperature, under nitrogen atmosphere, with 2 moles cyclopentadienyl group sodium and 1.2 moles anhydrous CoCl
2Be added in 300 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transient metal complex shown in the structural formula 1
Structural formula 1:
(4) under nitrogen atmosphere, 0.05 kilogram the transient metal complex shown in structural formula 1 is added in 500 milliliters the oxolane, thereby makes the solution of transient metal complex;
(5) under nitrogen atmosphere, under agitation, at room temperature the described suspension that makes in (2) is added drop-wise in the described solution that makes in (4) gradually, and continue to stir 1.5 hours;
(6) under nitrogen atmosphere, the suspension that obtains in (5) distilled to remove desolvates, thereby obtain carrier-borne transition metal catalysts A1 (by calculate described central metal atom account for described total catalyst weight 1.50%).
Embodiment 2
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
(1) making 1 kilogram average particulate diameter is that 300 nanometers, specific area are that 200 meters squared per gram, porosity are 0.51% SiO
2Carrier is cooled to room temperature then, thereby obtains 0.997 kilogram dehydration, the SiO of dehydroxylation being to heat 2 hours under the 4Pa under 500 ℃, in vacuum under nitrogen atmosphere
2Carrier;
(2) under nitrogen atmosphere, with the SiO that obtains in (1)
2Carrier is added in 9500 milliliters the toluene, fully stirs to make suspension;
(3) at room temperature, under nitrogen atmosphere, with 2 moles tetramethyl-ring pentadienyl sodium and 1.3 moles anhydrous CoCl
2Be added in 250 milliliters the oxolane and carried out haptoreaction 2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transient metal complex shown in the structural formula 2
Structural formula 2
(4) under nitrogen atmosphere, 0.05 kilogram the transient metal complex shown in structural formula 2 is added in 500 milliliters the toluene, thereby makes the solution of transient metal complex;
(5) under nitrogen atmosphere, under agitation, at room temperature the described suspension that makes in (2) is added drop-wise in the described solution that makes in (4) gradually, and continue to stir 2.5 hours;
(6) under nitrogen atmosphere, the suspension that obtains in (5) distilled to remove desolvates, thereby obtain carrier-borne transition metal catalysts A2 (by calculate described central metal atom account for described total catalyst weight 0.94%).
Embodiment 3
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
(1) making 1 kilogram particle diameter is that 10 nanometers, specific area are that 700 meters squared per gram, porosity are 0.79% TiO
2And SiO
2Complex carrier (TiO
2With SiO
2Mol ratio be 1: 70) under 200 ℃, vacuum be under the 4Pa heating 10 hours, under nitrogen atmosphere, be cooled to room temperature then, thereby obtain 0.992 kilogram dehydration, the TiO of dehydroxylation
2-SiO
2Complex carrier;
(2) under nitrogen atmosphere, with the TiO that obtains in (1)
2-SiO
2Complex carrier is added in 9500 milliliters the pentane, fully stirs to make suspension;
(3) at room temperature, under nitrogen atmosphere, with 2 moles indenyl sodium and 1.1 moles anhydrous CoCl
2Be added in 200 milliliters the oxolane and carried out haptoreaction 2.5 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), obtain atropurpureus crystal by evaporative crystallization then, learn that by nuclear magnetic resonance spectroscopy and mass spectral analysis described crystal is the transient metal complex shown in the structural formula 3
Structural formula 3
(4) under nitrogen atmosphere, 0.05 kilogram transient metal complex shown in structural formula 3 is added in 500 milliliters the pentane, thereby makes the solution of transient metal complex;
(5) under nitrogen atmosphere, under agitation, at room temperature the described suspension that makes in (2) is added drop-wise in the described solution that makes in (4) gradually, and continue to stir 2 hours;
(6) under nitrogen atmosphere, the suspension that obtains in (5) distilled to remove desolvates, thereby obtain carrier-borne transition metal catalysts A3 (by calculate described central metal atom account for described total catalyst weight 0.98%).
Embodiment 4
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares described carrier-borne transition metal catalysts, and different is to adopt the transient metal complex shown in the transient metal complex substitute structure formula 1 shown in the structural formula 4,
Structural formula 4
And the preparation method of the transient metal complex shown in the described structural formula 4 as: at room temperature, under nitrogen atmosphere, with 2 moles fluorenyl sodium and 1.2 moles anhydrous CoCl
2Be added in 250 milliliters the oxolane and carried out haptoreaction 2.5 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), make by evaporative crystallization then.Finally obtain carrier-borne transition metal catalysts A4, and central metal atom accounts for 0.73% of described total catalyst weight by calculating wherein.
Embodiment 5
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares described carrier-borne transition metal catalysts, and different is to adopt the transient metal complex shown in the transient metal complex substitute structure formula 1 shown in the structural formula 5,
Structural formula 5
And the preparation method of the transient metal complex shown in the described structural formula 5 as: at room temperature, under nitrogen atmosphere, with 1 mole 2 (3-methyl cyclopentadiene)-monosilanes and 1.1 moles anhydrous CoCl
2Be added in 200 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), make by evaporative crystallization then.Finally obtain carrier-borne transition metal catalysts A5, and central metal atom accounts for 1.15% of described total catalyst weight by calculating wherein.
Embodiment 6
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares described carrier-borne transition metal catalysts, and different is to adopt the transient metal complex shown in the transient metal complex substitute structure formula 1 shown in the structural formula 6,
Structural formula 6
And the preparation method of the transient metal complex shown in the described structural formula 6 as: at room temperature, under nitrogen atmosphere, with 1 mole 2 (3-ethyl cyclopentadiene)-dichlorosilane and 1.1 moles anhydrous CoCl
2Be added in 250 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), make by evaporative crystallization then.Finally obtain carrier-borne transition metal catalysts A6, and central metal atom accounts for 0.83% of described total catalyst weight by calculating wherein.
Embodiment 7
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares described carrier-borne transition metal catalysts, and different is to adopt the transient metal complex shown in the transient metal complex substitute structure formula 1 shown in the structural formula 7,
Structural formula 7
And the preparation method of the transient metal complex shown in the described structural formula 7 as: at room temperature, under nitrogen atmosphere, with 1 mole 2 (3-propyl group cyclopentadiene)-carrene and 1.2 moles anhydrous CrCl
2Be added in 200 milliliters the oxolane and carried out haptoreaction 3.2 hours, the mixture that obtains after the reaction is carried out vacuum filtration (absolute pressure is that vacuum is 0.01MPa), make by evaporative crystallization then.Finally obtain carrier-borne transition metal catalysts A7, and central metal atom accounts for 0.72% of described total catalyst weight by calculating wherein.
Embodiment 8
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
Method according to embodiment 7 prepares described carrier-borne transition metal catalysts, and that different is the Al that uses identical weight
2O
3Carrier replaces SiO wherein
2Carrier, thus carrier-borne transition metal catalysts A8 obtained.
Embodiment 9
Present embodiment is used to illustrate described carrier-borne transition metal catalysts provided by the invention and preparation method thereof.
Method according to embodiment 7 prepares described carrier-borne transition metal catalysts, and that different is used SiO
2Carrier is handled without dehydration and dehydroxylation, thereby obtains carrier-borne transition metal catalysts A9.
Embodiment 10
Present embodiment is used to illustrate the described method for preparing picoline provided by the invention.
The acetonitrile (9756 moles) of the carrier-borne transition metal catalysts A1 that makes among 0.5 kilogram the embodiment 1 and 400 kilograms is added in 1000 liters the reactor, under normal pressure, purged described reactor 0.5 hour with nitrogen, purged 0.1 hour with acetylene gas then through deoxidation, dehydration, in temperature be under 120 ℃ afterwards, pressure is under the 1.0MPa, 34104 moles of the acetylene gas of the deoxidation of injection process continuously again, dehydration, make the pressure in the reactor rise to 1.5MPa (dividing potential drop of acetylene is 0.8MPa), under this temperature and pressure, kept 3 hours.Then, reduce to room temperature, sampling is carried out high performance liquid chromatography-mass spectrometry (HPLC-MS) and is analyzed and to learn that the product that above-mentioned reaction generates is the 2-picoline, and the yield of conversion ratio by calculating acetonitrile and 2-picoline is as shown in table 1 below.
Embodiment 11-18
Present embodiment is used to illustrate the described method for preparing picoline provided by the invention.
Method according to embodiment 10 prepares picoline, and different is, replaces wherein carrier-borne transition metal catalysts A1 with the carrier-borne transition metal catalysts A2-A9 that makes among the embodiment 2-9 respectively.Sampling is carried out high performance liquid chromatography-mass spectrometry (HPLC-MS) and is analyzed and to learn that the product that above-mentioned reaction generates is the 2-picoline then, and the yield of conversion ratio by calculating acetonitrile and 2-picoline is as shown in table 1 below.
Table 1
? |
Carrier-borne transition metal catalysts |
The conversion ratio of acetonitrile (%) |
The yield of 2-picoline (%) |
Embodiment 10 |
A1 |
86.7 |
80.5 |
Embodiment 11 |
A2 |
90.3 |
84.8 |
Embodiment 12 |
A3 |
91.7 |
85.3 |
Embodiment 13 |
A4 |
92.1 |
87.6 |
Embodiment 14 |
A5 |
94.5 |
90.1 |
Embodiment 15 |
A6 |
94.7 |
90.5 |
Embodiment 16 |
A7 |
93.9 |
89.3 |
Embodiment 17 |
A8 |
93.1 |
88.8 |
Embodiment 18 |
A9 |
75.3 |
58.9 |
This shows that carrier-borne transition metal catalysts provided by the invention can promote acetonitrile and acetylene reaction to make the 2-picoline effectively.Particularly, when the porous carrier in the described carrier-borne transition metal catalysts was the carrier of process dehydration and dehydroxylation processing, described carrier-borne transition metal catalysts can significantly improve the selectivity of described acetonitrile and acetylene reaction generation 2-picoline.