CN1663941A - Process for synthesizing benzaldehyde by selective oxidation of toluene - Google Patents
Process for synthesizing benzaldehyde by selective oxidation of toluene Download PDFInfo
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Abstract
Disclosed is a process for synthesizing benzaldehyde by selective oxidation of toluene, wherein the catalyst mainly comprises manganese, copper, cobalt, ferrum, nickel, zirconium, zinc, Argentine or/and halides of sodium, calcium, potassium, nitrates, sulfates, acetates, benzoates. The preparing process comprises letting in oxygen at the presence of the catalyst. When the conversion rate of toluene is 10%, the selectivity of benzaldehyde is 62%, the selectivity of benzoic alcohol is 14%, the selectivity of benzene carbonic acid is 22%, when the conversion rate of toluene is 39%, the selectivity of benzaldehyde is 20%, the selectivity of benzoic alcohol is 5%, the selectivity of benzene carbonic acid is 73%.
Description
Technical field
The present invention relates to the method for selective oxidation toluene synthesizing benzaldehyde under a kind of mild conditions.
Background technology
Phenyl aldehyde and phenylformic acid all are important chemical material.Phenyl aldehyde is the important intermediate of important foodstuff additive, synthetic drugs and spices etc.Phenylformic acid is the important intermediate of synthesis of caprolactam.
The method of benzoic preparation has the chlorination toluene hydrolysis method, and (US 4229379; US 4450298), toluene electrochemical oxidation process and toluene catalytic oxidation method etc., wherein maximum with the research of toluene catalytic oxidation method.Cobalt is added in industrial many employings and bromide is a catalyzer, and temperature of reaction is 160 ℃, and catalyst concn is 60-100ppm, and toluene conversion 15%, benzoic selectivity are 90%, and the selectivity of phenyl aldehyde is 3-5%.This method runs into problems such as catalyzer blocking pipe in process of production, influences production equipment and runs well; Phenyl aldehyde proportion in products distribution is less, and compares with phenylformic acid, and phenyl aldehyde has higher market value.Compare with existing chlorination toluene hydrolysis method, the phenyl aldehyde that adopts catalytic oxidation to produce, the quality product height is suitable in sector applications such as medicine, spices, food.Therefore, under the situation that does not change existing equipment, improve the content of phenyl aldehyde in product by changing catalyzer, or the modulation products distribution is one of important method of research and development at present.
Patent US 3387036 adopts the non-catalyst oxidation method, and temperature of reaction 170-220 ℃, toluene conversion is 7-10%, the selectivity 19-32% of phenyl aldehyde, and the selectivity of phenylcarbinol is 30-38%, benzoic selectivity is 10-16%.
Patent US 3579589, US 3989674, US 4137259 etc. adopt the method for catalytic gas phase oxidation toluene, temperature of reaction 250-600 ℃, pressure 1.0-10.0MPa.This method temperature of reaction and reaction pressure are all higher; Only under lower toluene conversion (less than 4%) situation, just can obtain the phenyl aldehyde (about 70%) of highly selective.Patent EP 1088810, it is catalyzer that EP 1348687 adopts metal ions such as iron and cobalt, the catalyzed reaction temperature is 60-130 ℃, the catalyzer usage quantity is the 0.07-0.28% (mol ratio) of toluene consumption, bromide is an additive, usage quantity is 0.14-1.14% (mol ratio), and acetate etc. are solvent, and usage quantity is the 30-50% (volume ratio) of toluene consumption.The transformation efficiency of toluene is less than 25%, and the phenyl aldehyde selectivity is 30-50%, and benzyl alcohol selective is 5-15%, and the phenylformic acid selectivity is 45-55%.This method toluene conversion and selectivity of product are all higher, but the consumption of catalyzer and solvent is all bigger.
Patent CN 02143361.5 adopts the soild oxide catalyzer, has realized heterogeneous catalytic oxidation toluene synthesizing benzaldehyde.In toluene conversion is 10% o'clock, and the overall selectivity of phenyl aldehyde and phenylcarbinol reaches 86%, wherein the selectivity 56.8% of phenyl aldehyde.The catalyzer that this method adopts is a solid state, is easy to after the reaction reclaim and recycling.But there are problems such as the even mass transfer difficulty of skewness in solid catalyst in reactor
Summary of the invention
The object of the present invention is to provide the method for selective oxidation toluene synthesizing benzaldehyde under a kind of mild conditions.
The condition that method of the present invention is used is: temperature of reaction is 90-160 ℃, reaction times 30-600 minute, and reaction pressure 0.5-1.5Mpa.
The catalytic oxidation of hydro carbons is commonly considered as free radical reaction, experience single electron transfer course.Reaction process is through initiation, transmission and the destruction three phases of free radical.The initiation of free radical has different modes, as heat, light, metal ion etc.The method of toluene autocatalyzed oxidation is to rely on heat or reactor wall initiation reaction, need comparatively high temps, and product selectivity is poor.By adding catalyzer, can play the effect of initiation reaction.Catalyzer can reduce the activation energy of reaction simultaneously, reduces temperature of reaction, improves product selectivity.Metal ion has variable valence state, betatopic is easier, by with the molecular oxygen effect, realize that the oxygen species are by the transfer of molecular oxygen to the product molecule.The ability difference of different metal ion transfer of molecules oxygen is bigger, and it is also bigger to show corresponding oxidation capacity difference, and the metal ion synergistic effect by two or more sometimes forms redox circulation.Halogen ion or acid ion with metal ion uses simultaneously also play an important role.As the halogen ion, lose an electronics with metal ion, form free radical, can initiation reaction, typical ion such as bromine, iodine etc.; Acetate ion formed oxonium ion easily, also had initiation.Liquid-phase catalysis selective oxidation catalyzer provided by the invention, mainly by transition metal such as manganese, copper, cobalt, iron, nickel, zirconium, zinc, silver or/and the halogenide of basic metal such as sodium, calcium, alkaline-earth metal, nitrate, vitriol, acetate, benzoate etc. form.
Change the usage quantity of catalyzer, can influence the turnover number of catalytic oxidation; Because the reaction of toluene oxidation is consecutive reaction, the distribution of the usage quantity modulation product by changing catalyzer is to change optionally one of approach of toluene conversion and phenyl aldehyde.As will improving the phenyl aldehyde selectivity, catalyst levels 0.0005-0.25% (weight ratio of metal ion and toluene), preferable consumption is 0.001-0.15%, optimum amount is 0.003-0.01%.Realize that toluene conversion is at 10% o'clock, the phenyl aldehyde selectivity is 62%, and the phenylformic acid selectivity is 22%.As will obtaining higher toluene conversion, catalyst levels 0.001-0.35% (weight ratio of metal ion and toluene), preferable consumption is 0.01-0.3%, optimum amount is 0.1-0.28%.Realize that toluene conversion is at 39% o'clock, the phenyl aldehyde selectivity is 20%, and the phenylformic acid selectivity is 73%.
Reaction process need add additive, and the additive of adding has following effect: at first, additive can mix catalyzer better with raw material toluene, reduces the negative effect that mass transfer brings; Secondly, additive may be again the initiator of reaction, produces radical initiation reaction, reduces the high temperature of reaction needed or the catalyzer of high density greatly; Once more, the use of additive can change products distribution, owing to the use of additive, has changed the acid-basicity or the polarity of reaction system, and also corresponding the obtaining of products distribution changes; At last, additive plays the effect of stablizing intermediate product in reaction process.The additive that the present invention adopts comprises acetate, phenylformic acid, water, methyl alcohol, ethanol, tributyl phosphate etc.But the use meeting of additive is had relatively high expectations to conversion unit.The usage quantity of additive is 0-30% (with the weight ratio of toluene), and preferable consumption is 1-20%, and optimum amount is 5-15%.
Embodiment
Be described in detail the present invention below by embodiment.
Embodiment 1: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.85g Manganese dibromide, 0.7g four water cobaltous acetates and 42g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 240 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Product analysis adopts marker method once to finish on HP 4890 gas chromatographs.Reaction result sees Table one.
Embodiment 2: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.85g cobaltous bromide, 0.7g four water manganous acetates and 42g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 3: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.45g sodium-chlor, 0.7g cobaltous bromide, 0.1g nitrate trihydrate copper and 14g phenylformic acid, still is pushed up airtight, be heated to 140 ℃, logical oxygen reacts, temperature of reaction rises to 150 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 4: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.2g iron bromide, 0.1g cobalt nitrate hexahydrate, 0.15g four water manganous acetates and 7g glacial acetic acid, still is pushed up airtight, be heated to 130 ℃, blowing air reacts, temperature of reaction rises to 140 ℃ and be controlled at this thermotonus, and reaction pressure is 1.5MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 5: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.4g Manganese dibromide, 0.2g four water cobaltous acetates, 0.2g eight water zirconium oxychlorides and 28g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, blowing air reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 6: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.05g zinc bromide, 0.02g cobalt nitrate hexahydrate, 0.01g nine water iron nitrates and 21g methyl alcohol, still is pushed up airtight, be heated to 110 ℃, logical oxygen reacts, temperature of reaction rises to 120 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 7: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.001g ferrous bromide, 0.001g four water manganous acetates, 0.001g four water cobaltous acetates and 21g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 120 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 8: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.001g Potassium Bromide, 0.02g CoCL2,0.02g four water manganous acetates and 14g glacial acetic acid, still is pushed up airtight, be heated to 100 ℃, blowing air reacts, temperature of reaction rises to 110 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 9: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.001g Manganese dibromide, 0.001g cobaltous benzoate and 14g glacial acetic acid, still is pushed up airtight, be heated to 90 ℃, logical oxygen reacts, temperature of reaction rises to 100 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 10: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.65g Manganese dibromide and 0.07g cupric benzoate, still is pushed up airtight, be heated to 80 ℃, logical oxygen reacts, temperature of reaction rises to 90 ℃ and be controlled at this thermotonus, and reaction pressure is 0.5MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 11: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.3g nickelous bromide and 0.7g CoCL2,0.001g Silver Nitrate and 10g water, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 12: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.85g Manganese dibromide and 0.35g four water cobaltous acetates, 0.02g six water nickelous nitrates, 13g water and 7g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 13: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.85g Manganese dibromide, 0.01g two water Calcium Bromides and 0.3g four water cobaltous acetates and 7g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 30 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 14: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.01g Manganese dibromide, 0.001g potassiumiodide and 0.3g four water cobaltous acetates and 1.4g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 15: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.001g Manganese dibromide and 0.02g four water cobaltous acetates and 2.8g tributyl phosphate, still is pushed up airtight, be heated to 140 ℃, logical oxygen reacts, temperature of reaction rises to 150 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 60 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 16: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene and 0.3g cupric bromide and 0.7g cobaltous benzoate, still is pushed up airtight, be heated to 150 ℃, logical oxygen reacts, temperature of reaction rises to 160 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 600 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 17: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.1g Sodium Bromide and 0.3g cupric sulfate pentahydrate, still is pushed up airtight, be heated to 150 ℃, logical oxygen reacts, temperature of reaction rises to 160 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 600 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 18: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.03g cupric bromide, 0.2g four water manganous acetates and 0.97g dehydrated alcohol, still is pushed up airtight, be heated to 150 ℃, logical oxygen reacts, temperature of reaction rises to 160 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 600 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 19: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.85g Manganese dibromide, 0.03g cupric bromide, 0.05g four water cobaltous acetates and 42g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 240 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Analytical procedure is with embodiment 1.Reaction result sees Table one.
Embodiment 20: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 0.85g Manganese dibromide, 0.7g four water cobaltous acetates and 42g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 30 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Product analysis adopts marker method once to finish on HP 4890 gas chromatographs.Reaction result sees Table one.
Embodiment 21: toluene oxidation is reflected in the 500mL reactor and carries out, add 140g toluene, 1.05g Manganese dibromide, 1.0g four water cobaltous acetates and 42g glacial acetic acid, still is pushed up airtight, be heated to 120 ℃, logical oxygen reacts, temperature of reaction rises to 130 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction times is 240 minutes.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sampling analysis.Product analysis adopts marker method once to finish on HP 4890 gas chromatographs.Reaction result sees Table one.
Table one, reaction result
| Embodiment | Metal ion total amount/toluene (wt.%) | Additive/toluene (wt.%) | Transformation efficiency (mol%) | Products distribution (mol%) | ||||
| Aldehyde | Alcohol | Acid | Ester | Unknown | ||||
| ????1 | ????0.27 | ????30 | ????39.40 | ?20.39 | ??5.3 | ?73.09 | ??0 | ????1.22 |
| ????2 | ????0.28 | ????30 | ????21.00 | ?30.72 | ??2.94 | ?60.66 | ??0 | ????5.68 |
| ????3 | ????0.28 | ????10 | ????29.66 | ?17.63 | ??4.27 | ?76.10 | ??0 | ????2 |
| ????4 | ????0.065 | ????5 | ????26.97 | ?12.93 | ??2.96 | ?82.31 | ??0 | ????1.00 |
| ????5 | ????0.15 | ????20 | ????17.26 | ?31.42 | ??0.98 | ?66.24 | ??0 | ????1.37 |
| ????6 | ????0.014 | ????15 | ????37.68 | ?13.33 | ??2.21 | ?83.40 | ??0 | ????1.06 |
| ????7 | ????0.0005 | ????15 | ????13.61 | ?42.81 | ??0.28 | ?56.91 | ??0 | ????0 |
| ????8 | ????0.0072 | ????10 | ????7.87 | ?54.46 | ??7.49 | ?35.40 | ??0 | ????2.65 |
| ????9 | ????0.0020 | ????10 | ????3.27 | ?58.32 | ??35.45 | ?6.23 | ??0 | ????0 |
| ????10 | ????0.13 | ????0 | ????0.38 | ?38.94 | ??38.45 | ?22.61 | ??0 | ????0 |
| ????11 | ????0.18 | ????7.1 | ????0 | ?0 | ??0 | ?0 | ??0 | ????0 |
| ????12 | ????0.22 | ????14.3 | ????0.1 | ?0 | ??0 | ?0 | ??0 | ????100 |
| ????13 | ????0.21 | ????5 | ????8.36 | ?51.22 | ??15.06 | ?33.72 | ??0 | ????0 |
| ????14 | ????0.053 | ????1 | ????8.32 | ?40.71 | ??11.72 | ?42.63 | ??0 | ????4.95 |
| ????15 | ????0.0036 | ????2 | ????10.71 | ?62.37 | ??13.77 | ?22.25 | ??0 | ????1.60 |
| ????16 | ????0.16 | ????0 | ????22.72 | ?12.39 | ??6.47 | ?67.17 | ??2.74 | ????11.23 |
| ????17 | ????0.07 | ????0 | ????7.85 | ?29.96 | ??19.11 | ?29.33 | ??3.81 | ????17.80 |
| ????18 | ????0.038 | ????0.7 | ????3.51 | ?40.33 | ??25.93 | ?17.58 | ??4.47 | ????11.70 |
| ????19 | ????0.17 | ????30 | ????15.43 | ?12.12 | ??9.66 | ?61.30 | ??9.09 | ????7.83 |
| ????20 | ????0.15 | ????30 | ????4.34 | ?51.23 | ??32.59 | ?16.18 | ??0 | ????0 |
| ????21 | ????0.35 | ????30 | ????19.51 | ?15.3 | ??5.0 | ?60.8 | ??3.0 | ????15.9 |
Annotate: aldehyde is meant phenyl aldehyde; Alcohol is meant phenylcarbinol; Acid is meant phenylformic acid; Ester is meant peruscabin
Claims (7)
1. the method for a selective oxidation toluene synthesizing benzaldehyde, catalyzer mainly by manganese, copper, cobalt, iron, nickel, zirconium, zinc, silver or/and the halogenide of sodium, calcium, potassium, nitrate, vitriol, acetate, benzoate are formed, the total consumption of catalyzer is counted 0.0005-0.35% by the weight ratio of metal ion and toluene; Under the effect of catalyzer, be oxygen source with the molecular oxygen, temperature of reaction is 90-160 ℃, reaction times 30-600 minute, reaction pressure 0.5-1.5Mpa.
2. the method for claim 1 is characterized in that, adds acetate, phenylformic acid, water, methyl alcohol, ethanol or tributyl phosphate in the reaction as additive, and addition is by counting 0-30% with the weight ratio of toluene.
3. the method for claim 1 is characterized in that, improves the phenyl aldehyde selectivity, and catalyst levels is counted 0.001-0.25% by the weight ratio of metal ion and toluene.
4. as claim 1 or 3 described methods, it is characterized in that improve the phenyl aldehyde selectivity, catalyst levels is counted 0.003-0.01% by the weight ratio of metal ion and toluene.
5. the method for claim 1 is characterized in that, improves toluene conversion, and catalyst levels is counted 0.001-0.35% by the weight ratio of metal ion and toluene.
6. as claim 1 or 5 described methods, it is characterized in that improve toluene conversion, catalyst levels is counted 0.1-0.28% by the weight ratio of metal ion and toluene.
7. the method for claim 1 is characterized in that, the addition of described additive is by counting 5-15% with the weight ratio of toluene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786947A (en) * | 2010-03-18 | 2010-07-28 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN103265416A (en) * | 2013-05-23 | 2013-08-28 | 南京大学 | Method for preparing benzaldehyde from methylbenzene with high selectivity |
| CN105085214A (en) * | 2014-08-29 | 2015-11-25 | 浙江工业大学 | Benzaldehyde compound synthesis method |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
| CN107778152A (en) * | 2017-10-10 | 2018-03-09 | 重庆奥舍生物化工有限公司 | A kind of preparation method of 4 tert-butyl o phthalaldehyde |
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2004
- 2004-03-01 CN CN 200410007341 patent/CN1663941A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786947A (en) * | 2010-03-18 | 2010-07-28 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN101786947B (en) * | 2010-03-18 | 2013-05-29 | 申广照 | Method for preparing benzaldehyde by oxidizing toluene |
| CN103265416A (en) * | 2013-05-23 | 2013-08-28 | 南京大学 | Method for preparing benzaldehyde from methylbenzene with high selectivity |
| CN105085214A (en) * | 2014-08-29 | 2015-11-25 | 浙江工业大学 | Benzaldehyde compound synthesis method |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
| CN107778152A (en) * | 2017-10-10 | 2018-03-09 | 重庆奥舍生物化工有限公司 | A kind of preparation method of 4 tert-butyl o phthalaldehyde |
| CN107778152B (en) * | 2017-10-10 | 2020-10-27 | 重庆奥舍生物化工有限公司 | Preparation method of 4-tert-butyl phthalaldehyde |
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