CN1485131A - Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof - Google Patents
Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof Download PDFInfo
- Publication number
- CN1485131A CN1485131A CNA021433615A CN02143361A CN1485131A CN 1485131 A CN1485131 A CN 1485131A CN A021433615 A CNA021433615 A CN A021433615A CN 02143361 A CN02143361 A CN 02143361A CN 1485131 A CN1485131 A CN 1485131A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active component
- total content
- reaction
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
A catalyst of synthesizing benzaldehyde and benzyl alcohol by methylbenzene, its manufacturing method and application. The active component is zirconium, or transit metals, alkaline metal, alkaline-earth metals, metals of IIIA, IVA and VA Group in the Periodic Table. The method comprises solving a zirconium compound or a zirconium compound and a compound of an element as the active component, adding a precipitator; drying, burning, pulverizing to particles. In reactions, a gas containing oxygen is the oxygen source, such as oxygen and air, an organic solution wouldn't be used. The catalyzing reaction is 180-195 degree C, the pressure is 0.8-1.2Mpa. when the conversion rate of methylbenzene is 13.0&, the total selectivity of benzaldehyde and benzyl alcohol is 86.6%. In the method, the catalyst is easy to be separated and could be recyclable, the reaction condition is mild.
Description
Technical field
The present invention relates to a kind of catalyst that is used for direct catalytic oxidation toluene synthesizing benzaldehyde and phenmethylol.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of above-mentioned catalyst in catalytic oxidation toluene synthesizing benzaldehyde and phenmethylol.
Background technology
Benzaldehyde and phenmethylol are important fine-chemical intermediates, are widely used in fields such as medicine, agricultural chemicals, food.The production of benzaldehyde and phenmethylol can be adopted the method for chlorination toluene-hydrolysis; But this method equipment corrosion is serious, produces the chlorine-contained wastewater contaminated environment, is mingled with the difficult separation of a small amount of chloride impurity in the product, can not reach the requirement of fields such as medicine, food to the raw material quality.
Document (J.Mol.Cat., 176,79-86,2001; J.Mol.Cat., 176,19-22,2001) etc. report be oxidant with the peroxide, with vanadium base heteropoly acid and manganese base complex catalyst, the method for oxidation toluene synthesizing benzaldehyde, the conversion ratio of this method toluene is less than 1.7%, the utilization rate of peroxide is not high.
With oxygen or air is oxygen source, and the report of direct oxidation toluene synthesizing benzaldehyde is more.Rhone-Poulenc company (US 3387036,1968) has reported with oxygen to be oxygen source, the method for non-catalyst oxidation toluene synthesizing benzaldehyde and phenmethylol; Toluene conversion is less than 10%, and the overall selectivity of benzaldehyde and phenmethylol is less than 50%.Document (J.Cat., 188,154-164,1999; US 6281378,2001; CN 92107558.8,1996) etc. be reported under the effect of catalytic component based on vanadium, conversion ratio was less than 16% o'clock, the overall selectivity of benzaldehyde and phenmethylol is less than 50%.Reaction condition is: temperature 200-400 ℃, and pressure 1.5-2.5MPa.Under this reaction condition, side reactions such as the easy initial ring oxidation of toluene, decarboxylation and open loop, poor selectivity, Atom economy is low.
(WO 9520560,1995 for patent; CN 1296937A, 2001; JP 2001097913,2001) etc. report be solvent with acetate, propiolic acid etc., air is an oxygen source, adopting slaines such as Fe, Co, Mn, Mo, Ni is catalyst, the interpolation bromide is an auxiliary agent, and toluene conversion is 10% o'clock, the overall selectivity 65.7% of benzaldehyde and phenmethylol.Reaction condition is: temperature 60-200 ℃, and pressure 1.0-5.0MPa.This reaction condition is gentle, and selectivity is higher, but is to use homogeneous catalyst, is difficult for recycling; Use solvent and additive, increased separating difficulty.
Summary of the invention
The object of the present invention is to provide a kind of catalyst that is used for direct catalytic oxidation toluene synthesizing benzaldehyde and phenmethylol.
Another purpose of the present invention is to provide above-mentioned Preparation of catalysts method.
Another object of the present invention is to provide the application of above-mentioned catalyst in directly catalytic oxidation toluene synthesizing benzaldehyde and phenmethylol react.
Catalyst provided by the invention is an oxygen source with oxygen-containing gas such as oxygen or air, not with an organic solvent; It is easily separated and can be recycled to have catalyst, the reaction condition gentleness, the selectivity height, pollute little, characteristics such as environmental friendliness
According to the present invention, the activity of such catalysts component is zirconium or main group metal elements such as transition metal, alkali metal or alkali earth metal, IIIA, IVA and VA is adsorbed on the zirconium; The mol ratio of zr element and active component element total content is 1.0-15, and preferable mol ratio is 1.1-8, and optimum mole ratio is 1.2-3.0.
According to the present invention, the activity of such catalysts component comprises transition metal, and such metal cation d electronic shell loses or obtain electronics easily, has stronger redox property; Out orbit can carry out electrical feedback to the reactant unoccupied orbital, weakens the chemical bond of reaction molecular, helps molecule activation.Transition metal is one or more among Zn, Cu, Ag, Ni, Pd, Co, Rh, Fe, Ru, Mn, Cr, Mo, W, V, Ti, Hf, Ce, the Sm etc. in the active component, preferable element is one or more among Zn, Cu, Ag, Co, the Ce etc., and best element is Co and Cu; Molar content with zr element is 1, and the mole total content of this dvielement is 0-0.9, and preferable content is 0.2-0.8, and optimum content is 0.4-0.6.
According to the present invention, the activity of such catalysts component comprises main group metal elements such as IIIA, IVA and VA, and the cation of this metalloid can strengthen the acidity of catalyst, perhaps weakens its alkalescence, promotes the activation of reaction molecular, improves catalyst activity.Main group metal elements such as IIIA, IVA and VA are one or more among Al, Ga, Ge, Sn, Pb, Sb, the Bi etc. in the active component, and preferable element is one or more among Al, Sn, the Bi etc., and best element is Al; Molar content with zr element is 1, and the mole total content of this dvielement is 0～0.3, and preferable content is 0.05～0.2, and optimum content is 0.1-0.2.
According to the present invention, the activity of such catalysts component comprises elements such as alkali metal or alkaline-earth metal, and the cation of this metalloid can weaken the acidity of catalyst, perhaps increases its alkalescence, influence the stability of reaction intermediate, reaction is carried out towards the direction that requires selectively at catalyst surface.Alkali metal or alkali earth metal are one or more among Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, the Ba etc. in the active component, and preferable element is one or more among Na, K, the Ca etc., and best element is Ca; Molar content with zr element is 1, and the mole total content of this dvielement is 0-0.2, and preferable content is 0.01-0.15, and optimum content is 0.05-0.1.
According to the present invention, methods such as the synthetic employing dipping of solid catalyst or precipitation make catalyst precarsor, and this precursor drying is removed and desolvated, calcination settles out active component, be ground into thinner particle, sieving obtains required steps such as granular size, obtains catalyst of the present invention.For the synthetic catalyst of precipitation, before calcination, need washing to remove impurity.
According to the present invention, the Preparation of catalysts method is: arise from 40-80 ℃ of dissolving with zirconia or with zirconia and active component element one, add precipitating reagents such as NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium, urea or ammoniacal liquor, the solution endpoint pH is 6-7, washing precipitation, 80-140 ℃ the oven dry 6-20 hour, 450-1000 ℃ calcination 1-8 hour, grind to form 80-100 purpose particle, obtain catalyst.
According to the present invention, the preparation method can also be: the zirconia that will not grind placed active component solution dipping 12-40 hour, again in 80-140 ℃ of oven dry 6-20 hour, 450-1000 ℃ calcination 1-8 hour, grind to form 80-100 purpose particle, obtain catalyst.
According to the present invention, the catalyst activity component derives from bromide, chloride, fluoride, iodide, carbonate, nitrate, nitrite, sulfate, acetate, oxalates, hydroxide, oxide of this element etc.The foreign ion of this compound can or add thermal decomposition through washing leaves away, and the activity of such catalysts component mutually combines with forms such as oxide or slaines and settles out.
According to the present invention, precipitating reagent has appreciable impact to the crystal formation of precipitation: adopt the precipitating reagent of salt to help forming crystalline precipitate, and adopt the precipitating reagent of bases easily to form amorphous precipitation; Crystalline precipitation helps washes clean, and the amorphous precipitated washes clean that is unfavorable for.Being used for precipitating reagent of the present invention can be NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium, urea, ammoniacal liquor etc.
According to the present invention, the toluene catalytic oxidation reaction belongs to consecutive reaction, and when conversion ratio was higher, product was based on products such as benzoic acid, decarboxylation, open loops, and the selectivity of benzaldehyde and phenmethylol is lower.In order to realize higher one way efficient and selectivity of product, the conversion ratio of toluene is controlled at 4-15%, and the overall selectivity of benzaldehyde and phenmethylol is 60-94%.
According to the present invention, reaction is an oxidant with oxygen-containing gas such as oxygen or air.Oxygen-containing gas has characteristics such as cheap, nontoxic pollution-free, environmental friendliness as oxidant.The oxygen-containing gas that reaction is used can be oxygen, air etc.The volume content of oxygen is 0.1-100% in the oxygen-containing gas, and preferable content is 10-100%, optimum content 20-100%.
According to the present invention, reaction temperature and reaction pressure are influential to the result of catalytic reaction.Improve reaction temperature, help the activation of reaction molecular, improve reactivity; Reaction temperature is too high, the aggravation of product deep oxidation, and side reactions such as initial ring oxidation, decarboxylation and open loop, reaction selectivity reduces.Increase reaction pressure, help oxygen and in liquid phase and solid phase duct, spread, reduce mass transport affects; Reaction pressure is too high, has increased operation easier and equipment input, and the excessive concentration of catalyst surface active oxygen is unfavorable for the selection activation of reactant simultaneously.The reaction temperature of method of the present invention is 100-250 ℃, and preferred temperature is 140-210 ℃, and optimum temperature is 180-195 ℃; Reaction pressure is 0.1-2.0MPa, and preferable pressure is 0.5-1.5MPa, and optimum pressure is 0.8-1.2MPa.
According to the present invention, after reaction finished, solid catalyst separated with unreacted raw material with product after filtration.This solid catalyst can recycle; Catalyst circulation is used can reduce the wasting of resources, saves production cost; Catalyst circulation operation instruction active component does not run off in course of reaction, does not influence product purity.Activity of such catalysts that recycles and selectivity change little.
The specific embodiment
Be described in detail the present invention below by embodiment.
Embodiment 1
With 177.3gZrOCl
28H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+Molar concentration is 1.1mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 210mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.At 100 ℃ of oven dry 12h, 650 ℃ of calcination 3h cool off, and are weighed as 60g then.Porphyrize sieves, and gets 80-100 order size particles and carries out reaction evaluating.The catalyst label is Cat-01.
Toluene oxidation is reflected in the 1.0L reactor and carries out, and adds 60g toluene and 1.6g catalyst Cat-01; Still is pushed up airtight, stir 800 rev/mins, be heated to 180 ℃, logical oxygen reacts, and reaction temperature rises to 190 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction time is 120min.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sample analysis.Benzaldehyde and phenmethylol product analysis adopt internal standard method to finish on the HP4890 gas chromatograph, and benzoic acid adopts Acid and Alkali Titration Analysis.Reaction result sees Table 1.
Embodiment 2
With 177.3gZrOCl
28H
2O and 89.3gFeCl
36H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+And Fe
3+Molar concentration is respectively 1.1mol/L and 0.66mol/L), heat while stirring, temperature remains on about 75 ℃, and 390mL sodium hydroxide solution (5.5mol/L) is added drop-wise in the above-mentioned solution, and the solution endpoint pH remains 7.After precipitation finished, suction filtration went out precipitation, removed Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.At 110 ℃ of oven dry 12h, 650 ℃ of calcination 3h cool off then, and porphyrize sieves, and gets 80-100 order size particles and carries out reaction evaluating.The catalyst label is Cat-02.The proportion of composing of active component (mol/mol) Fe: Zr=0.6: 1.Except that using Cat-02 catalyst and reaction pressure as the 0.1MPa, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 3
With 177.3gZrOCl
28H
2O and 109.6gCo (CH
3COO)
24H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+And Co
2+Molar concentration is respectively 1.1mol/L and 0.44mol/L), heat while stirring, temperature remains on about 50 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 370mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.At 120 ℃ of oven dry 12h, 550 ℃ of calcination 3h cool off then, and porphyrize sieves, and gets 80-100 order size particles and carries out reaction evaluating.The catalyst label is Cat-03, the proportion of composing of active component (mol/mol): Co: Zr=0.8: 1.Except that using Cat-03 catalyst and reaction pressure as the 1.8MPa, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 4
With 177.3gZrOCl
28H
2O and 35g urea are dissolved in and are made into 500mL solution (ZrO in the deionized water
2+Molar concentration is 1.1mol/L).Heat while stirring, temperature rises to 90 ℃, and the slow hydrolysis of urea produces precipitation, and the solution endpoint pH remains 7.After hydrolysis finished, suction filtration went out precipitation, removed Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.At 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h cool off, and are weighed as 63g then.
With 11.8gCo (NO
3)
26H
2O and 0.96gCa (NO
3)
24H
2O is dissolved in and is made into 60mL solution (Co in the deionized water
2+And Ca
2+Concentration is respectively 0.68mol/L and 0.068mol/L), the synthetic ZrO of dipping said method
250g places 24h behind the mixing, then at 120 ℃ of oven dry 12h, and 650 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-04, the ratio of active component (mol/mol): Co: Ca: Zr=0.1: 0.01: 1.Except that using the Cat-04 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 5
With 11.8gCo (NO
3)
26H
2O and 9.8gCu (NO
3)
23H
2O is dissolved in and is made into 60mL solution (Co in the deionized water
2+And Cu
2+Concentration be 0.68mol/L), dipping adopts the synthetic ZrO of method among the embodiment 1
250g places 24h behind the mixing, then at 120 ℃ of oven dry 12h, and 850 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-05, the proportion of composing of active component (mol/mol): Co: Cu: Zr=0.1: 0.1: 1.Except that using the Cat-05 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 6
With 177.3gZrOCl
28H
2O and 54.8gCo (CH
3COO)
24H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+And Co
2+Molar concentration be respectively 1.1mol/L and 0.44mol/L).Heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 290mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize.1.23gKOH is dissolved in deionized water is made into 60mL solution (K
+Concentration is 0.37mol/L), with the above-mentioned catalyst of this solution impregnation, place 24h behind the mixing, then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-06, the proportion of composing of active component (mol/mol): Co: K: Zr=0.4: 0.04: 1.Except that using the Cat-06 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 7
With 177.3gZrOCl
28H
2O and 20.6gAl (NO
3)
39H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+And Al
3+Molar concentration be respectively 1.1mol/L and 0.11mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 240mL concentration, produces precipitation, the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.At 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h cool off then, and porphyrize sieves, and gets 80～100 order size particles and carries out reaction evaluating.The catalyst label is Cat-07, the proportion of composing of active component (mol/mol): Al: Zr=0.1: 1.Except that using the Cat-07 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 8
With 177.3gZrOCl
28H
2O, 82.2gCo (CH
3COO)
24H
2O and 20.6gAl (NO
3)
39H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+, Co
2+And Al
3+Molar concentration be respectively 1.1mol/L, 0.44mol/L and 0.11mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produce precipitation, the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.At 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h cool off then, and porphyrize is with 2.0gCa (OH)
2Be dissolved in and be made into 80mL solution (Ca in the deionized water
2+Concentration be 0.34mol/L), the catalyst that the dipping said method is synthetic is placed 24h behind the mixing, then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize sieves, the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-08, the proportion of composing of active component (mol/mol): Co: Al: Ca: Zr=0.6: 0.1: 0.05: 1.Except that using the Cat-08 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 9
With 177.3gZrOCl
28H
2O, 54.8gCo (CH
3COO)
24H
2O, 18.8gCuCl
22H
2O and 20.6gAl (NO
3)
39H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+, Co
2+, Cu
2+, Al
3+Molar concentration be respectively 1.1mol/L, 0.44 mol/L, 0.22mol/L and 0.11mol/L).Heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize.With 2.0gCa (OH)
2Be dissolved in and be made into 80mL solution (Ca in the deionized water
2+Concentration is 0.34mol/L), the synthetic catalyst of dipping said method is placed 24h behind the mixing, then at 90 ℃ of oven dry 12h, 900 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-09, the proportion of composing of active component (mol/mol): Co: Cu: Al: Ca: Zr=0.4: 0.2: 0.1: 0.05: 1.Except that using the Cat-09 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 10
With 177.3gZrOCl
28H
2O, 54.8gCo (CH
3COO)
24H
2O, 4.7gCuCl
22H
2O and 20.6gAl (NO
3)
39H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+, Co
2+, Cu
2+, Al
3+Molar concentration be respectively 1.1mol/L, 0.44mol/L, 0.055mol/L and 0.11mol/L).Heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with silver nitrate (0.1mol/L) solution
-Ion.Then at 130 ℃ of oven dry 8h, 650 ℃ of calcination 8h, cooling, porphyrize.With 2.0gCa (OH)
2Be dissolved in and be made into 80mL solution (Ca in the deionized water
2+Concentration is 0.34mol/L), the synthetic catalyst of dipping said method is placed 24h behind the mixing, then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-10, the proportion of composing of active component (mol/mol): Co: Cu: Al: Ca: Zr=0.4: 0.05: 0.1: 0.05: 1.Except that using Cat-10 catalyst and reaction temperature is 210 ℃, and other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 11
With 177.3gZrOCl
28H
2O, 54.8gCo (CH
3COO)
24H
2O, 18.8gCuCl
22H
2O and 20.6gAl (NO
3)
39H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+, Co
2+, Cu
2+, Al
3+Molar concentration be respectively 1.1mol/L, 0.44mol/L, 0.22mol/L and 0.11mol/L).Heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with silver nitrate (0.1mol/L) solution
-Ion.Then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize.With 1.2gCa (OH)
2Be dissolved in and be made into 80mL solution (Ca in the deionized water
2+Concentration is 0.21mol/L), the synthetic catalyst of dipping said method is placed 24h behind the mixing, then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-11, the proportion of composing of active component (mol/mol): Co: Cu: Al: Ca: Zr=0.4: 0.2: 0.1: 0.03: 1.Except that using the Cat-11 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 12
With 177.3gZrOCl
28H
2O, 54.8gCo (CH
3COO)
24H
2O, 18.75gCuCl
22H
2O and 10.32gAl (NO
3)
39H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+, Co
2+, Cu
2+, Al
3+Molar concentration be respectively 1.1mol/L, 0.44mol/L, 0.22mol/L and 0.055mol/L).Heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling, porphyrize.With 2.0gCa (OH)
2Be dissolved in and be made into 80mL solution (Ca in the deionized water
2+Concentration is 0.34mol/L), the synthetic catalyst of dipping said method is placed 24h behind the mixing, then at 120 ℃ of oven dry 12h, 850 ℃ of calcination 2h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-12, the proportion of composing of active component (mol/mol): Co: Cu: Al: Ca: Zr=0.4: 0.2: 0.05: 0.05: 1.Except that using the Cat-12 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 13
With 177.3gZrOCl
28H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+Molar concentration is 1.1mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sal volatile of 2.8mol/L is added drop-wise in the above-mentioned solution with 210mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 125 ℃ of oven dry 20h, 750 ℃ of calcination 1h, cooling, porphyrize.With 96.0gNi (NO
3)
26H
2O, 27.0gMn (CH
3COO)
24H
2O and 3.2gMg (OH)
2Be dissolved in and be made into 80mL solution in the deionized water, the synthetic catalyst of dipping said method is placed 40h behind the mixing, then at 90 ℃ of oven dry 12h, and 900 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-13, the proportion of composing of active component (mol/mol): Ni: Mn: Mg: Zr=0.6: 0.2: 0.1: 1.Except that using the Cat-13 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 14
With 177.3gZrOCl
28H
2O, 24.8gSnCl
22H
2O, 12.1gZn (CH
3COO)
22H
2O and 41.1gCo (CH
3COO)
24H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+, Sn
2+, Zn
2+, Co
2+Molar concentration be respectively 1.1mol/L, 0.22mol/L, 0.11mol/L and 0.33mol/L).Heat while stirring, temperature remains on about 60 ℃, is that the solution of potassium carbonate of 2.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with silver nitrate (0.1mol/L) solution
-Ion.At 120 ℃ of oven dry 5h, 750 ℃ of calcination 6h cool off then, and porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-14, the proportion of composing of active component (mol/mol): Sn: Zn: Co: Zr=0.2: 0.1: 0.3: 1.Except that using the Cat-14 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 15
With 177.3gZrOCl
28H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+Molar concentration is 1.1mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 125 ℃ of oven dry 14h, 750 ℃ of calcination 5h, cooling, porphyrize.With gCe (NO
3)
36H
2O, gNH
4VO
3And gBa (OH)
2Be dissolved in and be made into 80mL solution in the deionized water, the synthetic catalyst of dipping said method is placed 40h behind the mixing, then at 120 ℃ of oven dry 12h, and 900 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-15, the proportion of composing of active component (mol/mol): Ce: V: Ba: Zr=0.1: 0.05: 0.05: 1.Except that using the Cat-15 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 16
With 177.3gZrOCl
28H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+Molar concentration is 1.1mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 125 ℃ of oven dry 14h, 750 ℃ of calcination 5h, cooling, porphyrize.With 0.57g RuCl
3, 27.4gCo (CH
3COO)
24H
2O and gBi (NO
3)
2Be dissolved in and be made into 80mL solution in the deionized water, the synthetic catalyst of dipping said method is placed 12h behind the mixing, then at 110 ℃ of oven dry 12h, and 900 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-16, the proportion of composing of active component (mol/mol): Ru: Co: Bi: Zr=0.005: 0.2: 0.02: 1.Except that using the Cat-16 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 17
With 177.3gZrOCl
28H
2O is dissolved in and is made into 500mL solution (ZrO in the deionized water
2+Molar concentration is 1.1mol/L), heat while stirring, temperature remains on about 60 ℃, is that the sodium hydroxide solution of 5.5mol/L is added drop-wise in the above-mentioned solution with 360mL concentration, produces precipitation, and the solution endpoint pH remains 7.After dropwising, suction filtration goes out precipitation, removes Cl 6 times with 300mL deionized water making beating washing respectively
-Ion detects Cl with liquor argenti nitratis ophthalmicus (0.1mol/L)
-Ion.Then at 125 ℃ of oven dry 14h, 750 ℃ of calcination 5h, cooling, porphyrize.With 6.8g (NH
4)
6Mo
7O
244H
2O, 6.4gNH
4VO
3And 3.1gBe (NO
3)
23H
2O is dissolved in and is made into 80mL solution in the deionized water, and the synthetic catalyst of dipping said method is placed 36h behind the mixing, then at 120 ℃ of oven dry 12h, and 700 ℃ of calcination 3h, cooling, porphyrize sieves, and the catalyst granules of getting 80-100 order size carries out reaction evaluating.The catalyst label is Cat-17, the proportion of composing of active component (mol/mol): Mo: V: Be: Zr=0.01: 0.1: 0.03: 1.Except that using the Cat-17 catalyst, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 18
Toluene oxidation is reflected in the 1.0L reactor and carries out, and adds 60g toluene and 1.6g catalyst (Cat-12); Still is pushed up airtight, stir 800 rev/mins, be heated to 150 ℃, logical oxygen reacts, and reaction temperature rises to 160 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction time is 120Min.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sample analysis.Benzaldehyde and phenmethylol product analysis adopt internal standard method to finish on the HP4890 gas chromatograph, and benzoic acid adopts Acid and Alkali Titration Analysis.Reaction result sees Table 2.
Embodiment 19
Toluene oxidation is reflected in the 1.0L reactor and carries out, and adds 60g toluene and 1.6g catalyst (Cat-12); Still is pushed up airtight, stir 800 rev/mins, be heated to 150 ℃, logical oxygen reacts, and reaction temperature rises to 160 ℃ and be controlled at this thermotonus, and reaction pressure is 2.0MPa, and the reaction time is 120Min.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sample analysis.Benzaldehyde and phenmethylol product analysis adopt internal standard method to finish on the HP4890 gas chromatograph, and benzoic acid adopts Acid and Alkali Titration Analysis.Reaction result sees Table 2.
Embodiment 20
Toluene oxidation is reflected in the 1.0L reactor and carries out, and adds 60g toluene and 1.6g catalyst (Cat-12); Still is pushed up airtight, stir 800 rev/mins, be heated to 150 ℃, blowing air reacts, and reaction temperature rises to 160 ℃ and be controlled at this thermotonus, and reaction pressure is 1.0MPa, and the reaction time is 120Min.Reaction is reduced to room temperature with reaction system after finishing, and opens kettle cover, sample analysis.Benzaldehyde and phenmethylol product analysis adopt internal standard method to finish on the HP4890 gas chromatograph, and benzoic acid adopts Acid and Alkali Titration Analysis.Reaction result sees Table 2.
Embodiment 21
With embodiment 12 post reaction mixture, filter to isolate catalyst, 120 ℃ of oven dry 12h, 650 ℃ of calcination 3h, cooling joins among the unreacted raw material toluene 60g and reacts, and other reaction controlled condition and analytical method are with embodiment 1.Reaction result sees Table 2.
According to above embodiment as can be seen, method of the present invention has following characteristics:
1, the method for a kind of direct catalytic oxidation toluene synthesizing benzaldehyde and phenmethylol;
2, catalyst is a solid, can recycle;
3, be oxidant with oxygen-containing gas such as oxygen or air;
4, reaction condition gentleness: temperature is 180-195 ℃, and pressure is 0.8-1.2MPa;
5, toluene conversion is 13.0% o'clock, and the overall selectivity of benzaldehyde and phenmethylol is 86.6%;
6, benzoic selectivity can reach 35.9%;
7, do not use solvent;
8, do not use additive;
9, environmental friendliness.
Table 1
| Embodiment | Catalyst | Conversion ratio (%) | Aldehyde (alcohol) overall selectivity (%) | Product distribution (%) | |||
| Benzaldehyde | Phenmethylol | Benzoic acid | Other | ||||
| ????1 | ??Cat-01 | ????0.3 | ????59.6 | ????59.6 | ????0.0 | ????0.0 | ????40.4 |
| ????2 | ??Cat-02 | ????0.9 | ????98.9 | ????85.8 | ????13.0 | ????0.7 | ????0.4 |
| ????3 | ??Cat-03 | ????2.2 | ????94.1 | ????71.2 | ????23.0 | ????3.4 | ????2.5 |
| ????4 | ??Cat-04 | ????3.6 | ????96.0 | ????65.2 | ????30.8 | ????3.0 | ????1.0 |
| ????5 | ??Cat-05 | ????4.0 | ????86.6 | ????64.1 | ????22.6 | ????11.7 | ????1.7 |
| ????6 | ??Cat-06 | ????2.8 | ????98.8 | ????78.9 | ????20.0 | ????0.0 | ????1.2 |
| ????7 | ??Cat-07 | ????7.1 | ????73.5 | ????48.3 | ????25.3 | ????21.8 | ????4.7 |
| ????8 | ??Cat-08 | ????6.2 | ????84.3 | ????51.1 | ????33.2 | ????12.8 | ????2.9 |
| ????9 | ??Cat-09 | ????7.4 | ????74.3 | ????43.4 | ????30.9 | ????20.4 | ????5.3 |
| ????10 | ??Cat-10 | ????15.9 | ????59.1 | ????38.6 | ????20.5 | ????35.9 | ????5.0 |
| ????11 | ??Cat-11 | ????9.3 | ????72.2 | ????45.1 | ????27.0 | ????25.0 | ????2.8 |
| ????12 | ??Cat-12 | ????13.0 | ????87.0 | ????56.8 | ????30.2 | ????8.6 | ????4.4 |
| ????13 | ??Cat-13 | ????6.8 | ????82.3 | ????49.1 | ????33.2 | ????15.8 | ????1.9 |
| ????14 | ??Cat-14 | ????5.9 | ????84.3 | ????52.4 | ????31.9 | ????7.4 | ????8.3 |
| ????15 | ??Cat-15 | ????11.9 | ????68.7 | ????38.6 | ????30.1 | ????25.9 | ????5.4 |
| ????16 | ??Cat-16 | ????10.8 | ????83.6 | ????53.8 | ????29.8 | ????11.9 | ????4.5 |
| ????17 | ??Cat-17 | ????4.5 | ????72.1 | ????50.8 | ????21.3 | ????19.9 | ????8.0 |
Table 2
| Embodiment | Catalyst | Conversion ratio (%) | Aldehyde (alcohol) overall selectivity (%) | Product distribution (%) | |||
| Benzaldehyde | Phenmethylol | Benzoic acid | Other | ||||
| ????18 | ??Cat-12 | ????0.6 | ????98.0 | ????90.4 | ????7.6 | ????2.0 | ????0.0 |
| ????19 | ??Cat-12 | ????13.2 | ????63.5 | ????31.1 | ????32.4 | ????22.1 | ????14.4 |
| ????20 | ??Cat-12 | ????8.9 | ????83.6 | ????46.4 | ????37.2 | ????11.0 | ????5.4 |
| ????21 | ??Cat-12 | ????12.3 | ????84.1 | ????63.6 | ????20.5 | ????10.0 | ????5.9 |
Claims (13)
1, a kind of catalyst that is used for toluene synthesizing benzaldehyde and phenmethylol, be active constituent with the zirconium or be carrier with the zirconia, active component is one or more among Zn, Cu, Ag, Ni, Pd, Co, Rh, Fe, Ru, Mn, Cr, Mo, W, V, Ti, Hf, Ce, Sm, Al, Ga, Ge, Sn, Pb, Sb, Bi, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and the Ba, and the mol ratio of zr element and active component total content is 1.0-15; Wherein:
Active component Zn, Cu, Ag, Ni, Pd, Co, Rh, Fe, Ru, Mn, Cr, Mo, W, V, Ti, Hf, Ce are or/and the mole total content of Sm is 0-0.9;
Active component Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr are or/and the mole total content of Ba is 0-0.2;
Active component A l, Ga, Ge, Sn, Pb, Sb are or/and the mole total content of Bi is 0-0.3.
2, catalyst as claimed in claim 1 is characterized in that, described active component Zn, Cu, Ag, Ni, Pd, Co, Rh, Fe, Ru, Mn, Cr, Mo, W, V, Ti, Hf, Ce are or/and the mole total content of Sm is 0.2-0.8;
Active component Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr are or/and the mole total content of Ba is 0.01-0.15;
Active component A l, Ga, Ge, Sn, Pb, Sb are or/and the mole total content of Bi is 0.05-0.2.
3, catalyst as claimed in claim 1 or 2 is characterized in that, described active component Zn, Cu, Ag, Ni, Pd, Co, Rh, Fe, Ru, Mn, Cr, Mo, W, V, Ti, Hf, Ce are or/and the mole total content of Sm is 0.4-0.6;
Active component Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr are or/and the mole total content of Ba is 0.05-0.1;
Active component A l, Ga, Ge, Sn, Pb, Sb are or/and the mole total content of Bi is 0.1-0.2.
As each described catalyst of claim 1-3, it is characterized in that 4, described active component is one or more among Zn, Cu, Ag, Co, Ce, Al, Sn, Bi, Na, K and the Ca.
As each described catalyst of claim 1-4, it is characterized in that 5, described active component is one or more among Co, Cu, Al and the Ca.
6, catalyst as claimed in claim 1 is characterized in that, the mol ratio of described zr element and active component element total content is 1.1-8.
As claim 1 or 6 described catalyst, it is characterized in that 7, the mol ratio of described zr element and active component element total content is 1.2-3.0.
8, a kind of method for preparing the described catalyst of claim 1 in 40-80 ℃ of dissolving, adds precipitating reagent with zirconium compounds, the solution endpoint pH is 6-7, and washing precipitation was 80-140 ℃ of oven dry 6-20 hour, 450-1000 ℃ calcination 1-8 hour, grind to form 80-100 purpose particle, obtain catalyst.
9, preparation method as claimed in claim 8 is characterized in that, described precipitating reagent is NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate, carbonic hydroammonium, urea or ammoniacal liquor.
10, preparation method as claimed in claim 8 is characterized in that, zirconium compounds and active component element are prepared catalyst by the described method of claim 8 together.
11, preparation method as claimed in claim 8 is characterized in that, with zirconium compounds in 40-80 ℃ of dissolving, add precipitating reagent, the solution endpoint pH is 6-7, and washing precipitation was 80-140 ℃ of oven dry 6-20 hour, 450-1000 ℃ calcination 1-8 hour, placed active component solution dipping 12-40 hour, again in 80-140 ℃ of oven dry 6-20 hour, 450-1000 ℃ calcination 1-8 hour, grind to form 80-100 purpose particle, obtain catalyst.
12, as claim 8,10 or 11 described preparation methods, it is characterized in that described catalyst activity component derives from bromide, chloride, fluoride, iodide, carbonate, nitrate, nitrite, sulfate, acetate, oxalates, hydroxide or the oxide of this element.
13, the application of catalyst as claimed in claim 1 in directly catalytic oxidation toluene synthesizing benzaldehyde and phenmethylol react.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021433615A CN1485131A (en) | 2002-09-26 | 2002-09-26 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021433615A CN1485131A (en) | 2002-09-26 | 2002-09-26 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1485131A true CN1485131A (en) | 2004-03-31 |
Family
ID=34148244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021433615A Pending CN1485131A (en) | 2002-09-26 | 2002-09-26 | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1485131A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218326A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Oxide catalyst for producing Alpha-Alpha-dimethylphenyl carbinol and preparation method thereof |
| CN102964230A (en) * | 2012-11-20 | 2013-03-13 | 东南大学 | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation |
| CN103772152A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of terephthalyl alcohol |
| CN105126860A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Toluene direct oxidation catalyst and preparation method thereof |
| CN105664926A (en) * | 2016-03-09 | 2016-06-15 | 广东工业大学 | Catalyst for preparing benzaldehyde through selective oxidation of phenylcarbinol and preparing method thereof |
| CN107056594A (en) * | 2017-03-29 | 2017-08-18 | 钦州学院 | Preparation method of benzaldehyde |
| CN108440263A (en) * | 2018-03-22 | 2018-08-24 | 南京大学盐城环保技术与工程研究院 | A kind of method that p-tert-butyltoluene liquid phase oxidation prepares p-t-Butylbenzaldehyde |
| CN108499614A (en) * | 2018-04-28 | 2018-09-07 | 丛茜 | A kind of method that modified nickel catalytic material prepares central nervous system pharmaceutical intermediate |
| CN111250116A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Catalyst, and preparation method and application thereof |
| CN116328779A (en) * | 2021-12-15 | 2023-06-27 | 中国科学院大连化学物理研究所 | Liquid state sunlight zero carbon emission methanol synthesis catalyst and preparation method and application thereof |
-
2002
- 2002-09-26 CN CNA021433615A patent/CN1485131A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218326A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Oxide catalyst for producing Alpha-Alpha-dimethylphenyl carbinol and preparation method thereof |
| CN102218326B (en) * | 2010-04-15 | 2013-01-09 | 中国石油化工股份有限公司 | Oxide catalyst for producing Alpha-Alpha-dimethylphenyl carbinol and preparation method thereof |
| CN103772152A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of terephthalyl alcohol |
| CN103772152B (en) * | 2012-10-25 | 2015-10-21 | 中国石油化工股份有限公司 | The preparation method of terephthalyl alcohol |
| CN102964230A (en) * | 2012-11-20 | 2013-03-13 | 东南大学 | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation |
| CN102964230B (en) * | 2012-11-20 | 2014-11-12 | 东南大学 | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation |
| CN105126860A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Toluene direct oxidation catalyst and preparation method thereof |
| CN105664926A (en) * | 2016-03-09 | 2016-06-15 | 广东工业大学 | Catalyst for preparing benzaldehyde through selective oxidation of phenylcarbinol and preparing method thereof |
| CN107056594A (en) * | 2017-03-29 | 2017-08-18 | 钦州学院 | Preparation method of benzaldehyde |
| CN107056594B (en) * | 2017-03-29 | 2020-07-28 | 钦州学院 | Preparation method of benzaldehyde |
| CN108440263A (en) * | 2018-03-22 | 2018-08-24 | 南京大学盐城环保技术与工程研究院 | A kind of method that p-tert-butyltoluene liquid phase oxidation prepares p-t-Butylbenzaldehyde |
| CN108440263B (en) * | 2018-03-22 | 2021-09-28 | 南京大学盐城环保技术与工程研究院 | Method for preparing p-tert-butyl benzaldehyde by liquid-phase oxidation of p-tert-butyl toluene |
| CN108499614A (en) * | 2018-04-28 | 2018-09-07 | 丛茜 | A kind of method that modified nickel catalytic material prepares central nervous system pharmaceutical intermediate |
| CN108499614B (en) * | 2018-04-28 | 2021-06-04 | 西南医科大学附属医院 | Method for preparing drug intermediate for central nervous system from modified nickel catalytic material |
| CN111250116A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Catalyst, and preparation method and application thereof |
| CN116328779A (en) * | 2021-12-15 | 2023-06-27 | 中国科学院大连化学物理研究所 | Liquid state sunlight zero carbon emission methanol synthesis catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1021638C (en) | Fluidized catalyst for acrylonitrile | |
| CN1933904A (en) | Catalyst composition for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof | |
| CN1764500A (en) | Catalyst for partial oxidation and preparation method thereof | |
| CN1054972A (en) | Method for producing propenoic acid | |
| CN1485131A (en) | Catalyst for synthesizing benzaldehyde and benzyl alcohol from toluol, the preparation process and application thereof | |
| CN1241164A (en) | Method of hydrocarbon reforming and catalyst and catalyst precursor therefor | |
| CN114957192B (en) | Method for preparing cyclic carbonate by catalyzing carbon dioxide with cerium-based catalyst | |
| CN86108970A (en) | The catalyst of alkanolamine vapour phase molecule inner dewatering reaction | |
| CN1859972A (en) | Catalyst for gaseous partial oxidation of propylene and its preparing method | |
| CN1101728C (en) | Catalyst based on palladium, gold, alkali, and lanthanoid, and method for producing vinyl acetate | |
| CN114602530A (en) | Catalyst for synthesizing dimethyl carbonate by oxidative carbonylation of methanol, preparation method and application thereof | |
| CN102936297B (en) | Porous chitosan metal porphyrin composite and preparation method and application thereof | |
| CN107096540A (en) | A kind of metal composite oxide and its preparation method and application | |
| CN104368329B (en) | A kind of cerium niobium zirconium mixed oxide catalyst, preparation method and its usage | |
| CN102671702A (en) | Method for preparing zinc oxide ionic bond grafting and coordination supported tetra(4-carboxyl phenyl) metalloporphyrin catalyst | |
| CN1502406A (en) | Catalyst for synthesizing para-hydroxybenzenemethylal by using paracresol, preparation and use | |
| CN1947836A (en) | Catalyst for preparing cyclenes and preparing method of cyclenes | |
| CN1257462A (en) | Process for the production of hexaammine cobalt nitrate | |
| CN1172915C (en) | Method for preparing pyridine alkalis | |
| CN112156797B (en) | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof | |
| CN113731394A (en) | Preparation method of cerium dioxide-carbon nitride composite material with high photocatalytic performance | |
| CN106669697A (en) | Copper-bismuth catalyst for synthesizing 1,4-butynediol as well as preparation method and application thereof | |
| CN1172691A (en) | Acrylonitrile fluidized bed lithium containing catalyst | |
| CN106669698A (en) | Copper-bismuth catalyst for synthesizing 1,4-butynediol and preparation method thereof | |
| CN1043316A (en) | Produce the method for ethylenediamines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |