CN107866284A - Methylbenzene selective carbonylating catalyst - Google Patents
Methylbenzene selective carbonylating catalyst Download PDFInfo
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- CN107866284A CN107866284A CN201610851907.8A CN201610851907A CN107866284A CN 107866284 A CN107866284 A CN 107866284A CN 201610851907 A CN201610851907 A CN 201610851907A CN 107866284 A CN107866284 A CN 107866284A
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- tolyl aldehyde
- toluene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
Abstract
The present invention relates to methylbenzene selective carbonylating catalyst.Mainly solving the problems, such as that p-tolyl aldehyde present in prior art is selectively low, the present invention includes the active component of compound shown in following Formula I by using methylbenzene selective carbonylating catalyst, wherein, R1And R2C1~C10 alkyl is independently selected from, M includes being selected from least one of Al or Ferrious material, and X and Y are independently selected from chlorine or bromine, a is the absolute value of M chemical valence, n is more than 1 and less than 5 technical scheme, the technical problem is preferably resolved, available in the industrial production of p-tolyl aldehyde.
Description
Technical field
The present invention relates to for toluene and CO selectivity carbonyl compound into the catalyst of p-tolyl aldehyde, preparation method with
And the synthetic method of p-tolyl aldehyde.
Background technology
P-tolyl aldehyde, i.e. 4- tolyl aldehydes (p-Tolualdehyde, abbreviation PTAL), are colourless or faint yellow
Prescribed liquid, there are the fragrance of a flower and almond fragrance of tenderness, there is certain excitant to eyes and skin.P-tolyl aldehyde can Gao Xuan
Selecting property ground oxidative synthesis terephthalic acid (TPA), while be also a kind of important organic synthesis intermediate, led in fine chemistry industry and medicine
Domain is widely used.
PTAL synthetic method mainly has direct high-temperature oxidation, indirect electrosynthesis method and carbonylation method.
Direct high-temperature oxidation is using paraxylene as raw material, is mixed through light bromination, basic hydrolysis, hydrogen peroxide/hydrobromic acid
PTAL is made in liquid oxidation.Although the technique raw material is easy to get, is simple to operate, aromatic hydrocarbons utilization rate is low, technique is cumbersome, total conversion
Relatively low (26.7%) (bear is normal, Jin Ningren, Hu Weixiao, waits study on the synthesis [J] the Zhejiang Polytechnical University of p-tolyl aldehydes to learn
Report, 1999,27 (4):334-337.).
Indirect electrosynthesis method is that catalysis oxidation paraxylene prepares PTAL in electrolytic cell, this method is simple, yield is higher,
Side reaction is few, blowdown is few, environmentally friendly and economize on resources, but because its used catalyst is expensive, equipment is complicated, constrains it
Industrialization development (the work of the outer formula of Tang Duo, Wang Caihong, Li Yan prestige grooves ultrasonic indirect electrosynthesis benzaldehyde/p-tolyl aldehyde online
Skill improves [J] Institutes Of Technology Of Taiyuan journal, 2015,46 (1):6-10.).
Carbonylation method is that toluene and CO catalysis of carbonyl are combined into PTAL.For the technique using CO as carbonylation agent, B-L is compound
One kind in liquid acid catalyst, solid super strong acids catalyst and ionic liquid class catalyst is catalyst, and it reacts real
Matter is that to the electrophilic substitution reaction of toluene, referred to as Jia Teman-kock (Gattermann-Koch) synthesizes anti-CO under acid catalysis
Should.This method atom utilization is high, technique is simple, raw material CO costs are low, has good market prospects.Du pont company,
Mitsubishi gas company, Exxon Mobil company etc. have successively carried out research to the technique.With B-L composite fluids acid
Class, solid super strong acids catalyst are compared, the catalytic activity of ionic liquid-catalyzed toluene and CO selective carbonylation
It is obviously improved.Saleh is with [emim] Cl/AlCl3(xAlCl3=0.75) it is catalyst, the mass ratio of IL/ toluene is 8.5/
1.8, at room temperature, CO partial pressure 8.2Mpa are kept, react 1h, realize 66% toluene conversion and 89.1% PTAL selection rates
(Saleh RY,Rouge B.Process for making aromatic aldehydes using ionic liquids
[P].US:6320083,2001-11-20.).Its further application is the oxidized synthesis pair of PTAL that will be isolated to
Phthalic acid, used in the production of industrial polyester as monomer, demand is larger.
The content of the invention
One of technical problems to be solved by the invention are the problem of p-tolyl aldehyde are selectively low, there is provided a kind of new
Methylbenzene selective carbonylating catalyst, the catalyst have the characteristics of p-tolyl aldehyde is selectively high.
The two of the technical problems to be solved by the invention are using the catalyst synthesis pair described in one of above-mentioned technical problem
The method of tolyl aldehyde.
In order to one of solve the above problems, the technical solution adopted by the present invention is as follows：
Methylbenzene selective carbonylating catalyst, include the active component of compound shown in Formula I：
Formula I；
Wherein, R1And R2C1~C10 alkyl is independently selected from, M includes being selected from least one of Al or Ferrious material, X and Y
Chlorine or bromine is independently selected from, a is the absolute value of M chemical valence, and n is more than 1 and less than 5.
In above-mentioned technical proposal, the Ferrious material preferably is selected from least one of Fe, Co and Ni.
In above-mentioned technical proposal, R1And R2In at least one alkyl be preferably methyl, more preferably simultaneously be methyl.
In above-mentioned technical proposal, n preferably 1.5~3, more preferably 1.5~2.5.
In above-mentioned technical proposal, the active component, which can use, to be included between halogenated alkyl imidazole salts and metal halide instead
Should the step of obtain.
Although the reactant used in the preparation reaction of active component of the present invention is solid, but the production obtained after reacting
Thing normal temperature is but liquid, therefore is reacted with or without solvent.As long as reaction temperature is it is not also specifically limited, make reacted
System maintains liquid.As non-restrictive, when not using solvent to prepare active component, reaction temperature is preferably 20
~50 DEG C, the reaction time is preferably 1~8h.
It is related to the preparation reaction of active component of the present invention, the middle halogenated alkyl imidazole salts that feed intake and the mol ratio of metal halide
It need to only form and be fed intake according to active component, the reaction can be completed according to the stoichiometry that active component is limited.
The preparation reaction of active component is carried out preferably in inert atmosphere, and the inert atmosphere for example can be nitrogen, helium
At least one of gas and argon gas.
As halogenated alkyl imidazole salts described in non-restrictive can be 1- octyl group -3- methylimidazolium chlorides, 1- nonyls -
3- methylimidazolium chlorides, 1- butyl -3- methylimidazolium chlorides, 1- n-propyl -3- methylimidazolium chlorides, 1- ethyl -3- methyl chlorides
Change imidazoles, N, one kind in N- dimethylammonium chloride imidazoles.More preferably described haloalkyl imidazoles is N, N- dimethylammonium chloride imidazoles.
It should be readily apparent to one skilled in the art that MXaIt is the rational formula of metal halide, M can be single metal, can also
It is the average composition of various metals, X can be that single-element in chlorine or bromine or chlorine and bromine are formed with arbitrary atom ratio
Complex element.As non-restrictive, it can be AlCl that those, which form simple metal halide,3、AlBr3、FeCl3、
CoCl2、NiCl2Deng.
In above-mentioned technical proposal, preferably M includes Al and selected from least one of Ferrious material, now Al and Ferrious material
There is synergy in terms of p-tolyl aldehyde selectivity is improved；The further preferred Formula I, which is taken, has followingization
Learn Formulas I a form：
Formula Ia；
Wherein, m is more than 0 and is iron series element less than 1, B, and b is the atomicity of iron series element, and a=3m+b × iron system is first
The absolute value of the chemical valence of element.
Still more preferably M includes Al and Ferrious material, and includes Fe and Co, Fe and Co simultaneously and improving to methylbenzene
Formaldehyde selectivity aspect has synergy；Most preferably described Formula Ia takes the form with following Formula I b：
Formula I b；
C is Fe atomicity, and Fe chemical valence is+3；D is Co atomicity, and Co chemical valence is+2；Therefore accord with
Conjunction and a=3m+3c+2d；Still more preferably c/d is 2~5.
In order to solve the above problems two, the technical solution adopted by the present invention is as follows：
The synthetic method of p-tolyl aldehyde, it is included in catalyst any one of the technical scheme of one of technical problem
Toluene be present and carry out carbonylation acquisition p-tolyl aldehyde with CO.
The key problem in technology of the present invention is the selection of catalyst, and under catalysts conditions of the present invention, those skilled in the art know
How road determines to synthesize other process conditions of p-tolyl aldehyde, as non-restrictive, such as catalyst and toluene
Mol ratio be preferably 0.1~5；Reaction temperature is preferably 30~100 DEG C；Reaction pressure is preferably 1~8MPa；Reaction time is excellent
Elect 1~12h as.
Synthesizing the specific steps of p-tolyl aldehyde can be：
(1) catalyst and toluene are added in autoclave；
(2) air CO gas displacements in kettle；
(3) it is warming up to reaction temperature, keeps constant reaction pressure, stirring, is reacted, obtained containing product to methylbenzene
The mixture of formaldehyde；
Sample treatment and analysis method are as follows：
With the frozen water washed product mixture of 2 times of above-mentioned product mixtures volumes, aqueous phase discarded, by organic phase ether
Three times, the ether that extraction uses every time is equal with organic phase volume for extraction.Ether extraction liquid it will merge three times, revolving, residue
As p-tolyl aldehyde crude product, this crude product is subjected to gas chromatographic analysis, according to Analysis result calculation to methylbenzene first
For aldehyde relative to the selectivity of total tolyl aldehyde, calculation formula is as follows：
After technical scheme, p-tolyl aldehyde selectively up to 94.1%, beneficial technology is achieved
Effect, in the production that p-tolyl aldehyde is prepared available for methylbenzene selective carbonylation.
Embodiment
【Embodiment 1】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(40.0g, 0.3mol) is slowly added into N, N- dimethylammonium chlorides
In imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, described catalyst is obtained.Elementary analysis：Calculated value C,
15.04；H, 2.27；N, 7.02.Experiment value C, 15.07；H, 2.28；N, 7.01.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (79.9g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 2】
Catalyst preparation：Under nitrogen atmosphere, by FeCl3(48.6g, 0.3mol) is slowly added into N, N- dimethylammonium chlorides
In imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, described catalyst is obtained.Elementary analysis：Calculated value C,
13.14；H, 1.98；N, 6.13.Experiment value C, 13.11；H, 1.99；N, 6.12.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (91.4g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 3】
Catalyst preparation：Under nitrogen atmosphere, by CoCl2(39.0g, 0.3mol) is slowly added into N, N- dimethylammonium chlorides
In imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, described catalyst is obtained.Elementary analysis：Calculated value C,
15.31；H, 2.31；N, 7.14.Experiment value C, 15.27；H, 2.32；N, 7.16.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (78.5g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 4】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(32.0g, 0.24mol) and FeCl3(9.7g, 0.06mol) according to
It is secondary to be slowly added into N, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described urge
Agent.Elementary analysis：Calculated value C, 14.62；H, 2.21；N, 6.82.Experiment value C, 14.58；H, 2.20；N, 6.84.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (82.2g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 5】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(32.0g, 0.24mol) and CoCl2(7.8g, 0.06mol) according to
It is secondary to be slowly added into N, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described urge
Agent.Elementary analysis：Calculated value C, 15.09；H, 2.28；N, 7.04.Experiment value C, 15.05；H, 2.27；N, 7.05.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (79.6g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 6】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(32.0g, 0.24mol), FeCl3(7.3g, 0.045mol) and
CoCl2(1.9g, 0.015mol) is slowly added into N successively, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), at 40 DEG C
Stirring reaction 4h, obtain described catalyst.Elementary analysis：Calculated value C, 14.73；H, 2.23；N, 6.87.Experiment value C,
14.70；H, 2.22；N, 6.88.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (81.5g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Comparative example 1】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(20.0g, 0.15mol) is slowly added into N, N- dimethyl chlorides
Change in imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described catalyst.Elementary analysis：Calculated value
C, 22.58；H, 3.41；N, 10.53.Experiment value C, 22.60；H, 3.40；N, 10.51.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (53.2g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 7】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(30.0g, 0.225mol) is slowly added into N, N- dimethyl chlorides
Change in imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described catalyst.Elementary analysis：Calculated value
C, 18.06；H, 2.73；N, 8.42.Experiment value C, 18.01；H, 2.72；N, 8.41.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (66.5g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 8】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(24.0g, 0.18mol) and FeCl3(7.3g, 0.045mol) according to
It is secondary to be slowly added into N, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described urge
Agent.Elementary analysis：Calculated value C, 17.60；H, 2.66；N, 8.21.Experiment value C, 17.63；H, 2.65；N, 8.19.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (68.2g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 9】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(24.0g, 0.18mol) and CoCl2(5.8g, 0.045mol) according to
It is secondary to be slowly added into N, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described urge
Agent.Elementary analysis：Calculated value C, 18.11；H, 2.74；N, 8.45.Experiment value C, 18.06；H, 2.73；N, 8.47.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (66.3g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 10】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(24.0g, 0.18mol), FeCl3(5.5g, 0.034mol) and
CoCl2(1.5g, 0.011mol) is slowly added into N successively, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), at 40 DEG C
Stirring reaction 4h, obtain described catalyst.Elementary analysis：Calculated value C, 17.72；H, 2.68；N, 8.27.Experiment value C,
17.68；H, 2.69；N, 8.25.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (67.8g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 11】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(50.0g, 0.375mol) is slowly added into N, N- dimethyl chlorides
Change in imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described catalyst.Elementary analysis：Calculated value
C, 12.89；H, 1.95；N, 6.01.Experiment value C, 12.91；H, 1.94；N, 5.99.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (93.2g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 12】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(30.0g, 0.3mol) and FeCl3(12.2g, 0.075mol) according to
It is secondary to be slowly added into N, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described urge
Agent.Elementary analysis：Calculated value C, 12.50；H, 1.89；N, 5.83.Experiment value C, 12.47；H, 1.88；N, 5.82.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (96.1g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 13】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(30.0g, 0.3mol) and CoCl2(9.7g, 0.075mol) according to
It is secondary to be slowly added into N, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), in 40 DEG C of stirring reaction 4h, obtain described urge
Agent.Elementary analysis：Calculated value C, 12.94；H, 1.95；N, 6.04.Experiment value C, 12.90；H, 1.96；N, 6.02.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (92.8g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
【Embodiment 14】
Catalyst preparation：Under nitrogen atmosphere, by AlCl3(30.0g, 0.3mol), FeCl3(9.1g, 0.056mol) and
CoCl2(2.4g, 0.019mol) is slowly added into N successively, in N- dimethylammonium chlorides imidazoles (26.2g, 0.15mol), at 40 DEG C
Stirring reaction 4h, obtain described catalyst.Elementary analysis：Calculated value C, 12.61；H, 1.90；N, 5.88.Experiment value C,
12.64；H, 1.91；N, 5.86.
Carbonylation：Added in 250ml autoclaves above-mentioned catalyst (95.3g, 0.2mol) and toluene (9.2g,
0.1mol)；Air CO gas displacements in kettle；It is warming up to 50 DEG C, keeps reaction pressure 4.0MPa, 800rpm stirring, reacts 5h,
The product mixtures of p-tolyl aldehyde must be contained.
For the ease of comparing and illustrating, by composition parameter in catalyst activity component and corresponding p-tolyl aldehyde
Selectivity be listed in Table 1 below.
Table 1
Claims (9)
1. methylbenzene selective carbonylating catalyst, include the active component of compound shown in Formula I：
Wherein, R1And R2C1~C10 alkyl is independently selected from, M includes being selected from least one of Al or Ferrious material, and X and Y are independent
Selected from chlorine or bromine, a is the absolute value of M chemical valence, and n is more than 1 and less than 5.
2. catalyst according to claim 1, it is characterized in that the Ferrious material in Fe, Co and Ni at least one
Kind.
3. catalyst according to claim 1, it is characterized in that R1And R2In at least one alkyl be methyl.
4. catalyst according to claim 1, it is characterized in that n is 1.5~3.
5. catalyst any one of Claims 1 to 4, it is characterized in that the active component, which uses, includes halogenated alkyl imidazoles
The step of being reacted between salt and metal halide obtains.
6. the synthetic method of p-tolyl aldehyde, be included in catalyst any one of Claims 1 to 5 exist Toluene with
CO carries out carbonylation and obtains p-tolyl aldehyde.
7. according to the method for claim 6, it is characterized in that described reaction temperature is 30~100 DEG C.
8. according to the method for claim 6, it is characterized in that described reaction pressure is 1~8MPa.
9. according to the method for claim 6, it is characterized in that the described reaction time is 1~12h.
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