CN103191769A - Catalyst for producing benzaldehyde through catalytic oxidation of benzyl alcohol and preparation method thereof - Google Patents
Catalyst for producing benzaldehyde through catalytic oxidation of benzyl alcohol and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of a catalyst, and particularly discloses a catalyst for producing benzaldehyde through catalytic oxidation of benzyl alcohol and a preparation method thereof. The method comprises the following steps of: dipping a carrier in a copper salt solution to load copper, wherein the copper salt content of the solution is 0.1-10wt% of the carrier (in terms of copper weight), and loading iron to obtain the catalyst. The catalyst, when used for producing benzaldehyde through catalytic oxidation of methanol, can be used for improving the conversion rate of the benzyl alcohol and selectivity of the benzaldehyde.
Description
Technical field
The present invention relates to a kind of catalyst for phenmethylol catalytic oxidation producing benzaldehyde, and this Preparation of catalysts method, catalyst technical field belonged to.
Background technology
Benzaldehyde (being commonly called as almond oil) is as a kind of important fine-chemical intermediate, it is widely used in manufacturings such as medicine, spices, agricultural chemicals, dyestuff and plastics, and along with expanding economy, China is increasing to the demand of benzaldehyde, and is also more and more higher to the requirement of its quality simultaneously.
At present, industrial common employing toluene light chlorinolysis is produced benzaldehyde, its process is the mixture that earlier toluene is obtained comprising benzyl chloride, benzal chloride and benzenyl chloride through the light chlorination, with benzyl chloride by after isolating in the mixture, add hydrolyst again in the remaining mixture and heat up, add water gradually and be hydrolyzed, hydrolysis finishes by obtaining product after neutralization, alkali cleaning, the distillation.The complex technical process of this method except containing benzaldehyde, also contains corrosive byproducts such as hydrogen chloride and benzenyl chloride in the products therefrom, easily consersion unit is caused the corrosivity infringement.
In order to overcome the existing defective of chlorination toluene Hydrolyze method, adopt toluene oxidation method, methyl benzoate catalytic hydrogenation method and benzyl alcohol oxidation method to produce at present more and do formaldehyde.But, because the toluene oxidation method is that toluene and oxidant are reacted under catalytic action, in the product except benzaldehyde, also have accessory substances such as a large amount of benzoic acid, maleic acid and hydrocarbon, selective and the yield of benzaldehyde is very low, and the employed zirconia catalyst of methyl benzoate catalytic hydrogenation method and benzene feedstock methyl formate is expensive, causes its technology cost very high, so toluene oxidation method and methyl benzoate catalytic hydrogenation method are unsuitable for large-scale promotion and use.Because the benzyl alcohol oxidation method is that phenmethylol and liquid state or gaseous oxidizer are directly prepared benzaldehyde under catalyst action, its preparation technology is simple, the selective and yield of product benzaldehyde is high, and the low price of raw material and catalyst, thereby this method is more suitable for being extensive use of.Wherein, having a kind of in the benzyl alcohol oxidation method custom catalysts is to be active component with Cu and Fe, the research of support type Cu-Fe composite oxide catalytic Oxybenzene methyl alcohol is disclosed as the 27th phase the 5th of Chinese periodical document " Harbin Teachers' Univ.'s natural science journal " 2011 volume 56-61 page or leaf, it is carrier with the MCM-49 molecular sieve, adopt co-impregnation loaded Cu-Fe oxide on carrier to prepare catalyst as active component; Use this catalyst phenmethylol and 30v%H
2O
2At 90 ℃ of oxidation reaction 5h, the conversion ratio of final phenmethylol is 87.40%, and reaction selectively is 74.46% to benzaldehyde.
Though the support type Cu-Fe catalyst of employing co-impregnation preparation has certain effect for the oxidation reaction of phenmethylol in the above-mentioned technology, but the catalytic activity of this catalyst is very low as can be known after tested, thereby cause the benzene feedstock conversion of methanol very low, the content of benzaldehyde is very low in the end product.But for the low problem of above-mentioned technology catalyst activity, those skilled in the art can not find suitable solution always.
Summary of the invention
Technical problem to be solved by this invention is that the support type Cu-Fe activity of such catalysts of available technology adopting co-impregnation preparation is low, thereby when using it for the catalytic phenylmethanol oxidation reaction, low and selectively low to benzaldehyde of conversion of raw material; And then propose a kind of for phenmethylol catalytic oxidation producing benzaldehyde and the high Preparation of catalysts method of catalytic activity.
For solving the problems of the technologies described above, the invention provides a kind of Preparation of catalysts method for phenmethylol catalytic oxidation producing benzaldehyde, it comprises the steps:
(1) with carrier impregnation in the soluble Cu salting liquid, obtain intermediate material after drying and the roasting again; Wherein, in the weight of Cu, Cu salt is the 0.1-10wt% of carrier;
(2) described intermediate material be impregnated in the solubility Fe salting liquid, the solid material that obtains of drying and roasting is the catalyst for phenmethylol catalytic oxidation producing benzaldehyde then.
In the weight of Fe, Fe salt is the 0.1-10wt% of carrier.
The dip time of described step (1) is 1-5h.
In the described step (1), baking temperature is 90-120 ℃, and be 10-24h drying time, and sintering temperature is 400-580 ℃, and roasting time is 3-6h.
Solvent in the described Cu salting liquid is the 50-1000wt% of described carrier, and the solvent in the described Fe salting liquid is the 50-1000wt% of described carrier.
In the described step (2), dip time is 1-5h, and baking temperature 90-120 ℃, be 10-24h drying time, and sintering temperature is 400-580 ℃, and roasting time is 3-6h.
Described Cu salt is one or more in copper nitrate, copper sulphate and the copper chloride; Described Fe salt is one or more in ferric nitrate, ferric sulfate and the iron chloride; Described carrier is one or more in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide.
In the described step (2), also comprise described solid material is processed into the particle that particle diameter is 0.1-380 μ m.
The catalyst that is used for phenmethylol catalytic oxidation producing benzaldehyde that described preparation method obtains, gross weight in catalyst, its component comprises, one or more 80-99% in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide
CuO 0.12-12.5%
Fe
2O
3 0.14-14.3%。
In the gross weight of catalyst, its component comprises, one or more 84-98% in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide
CuO 0.12-10.0%
Fe
2O
3 0.14-11.4%。
The present invention compares with the prior art scheme has following beneficial effect:
(1) the Preparation of catalysts method for phenmethylol catalytic oxidation producing benzaldehyde of the present invention, it comprises carrier impregnation in the soluble Cu salting liquid, obtain intermediate material after drying and the roasting again, in the weight of Cu, Cu salt is the 0.1-10wt% of carrier; Described intermediate material be impregnated in the solubility Fe salting liquid then, the solid material that obtains after drying and the roasting is the catalyst for phenmethylol catalytic oxidation producing benzaldehyde then.The Preparation of catalysts method of phenmethylol catalytic oxidation producing benzaldehyde of the present invention be earlier with carrier impregnation in copper salt solution with loaded Cu, wherein, the Cu salt content of this solution is that the 0.1-10wt%(of carrier is in Cu content), and then Fe in the load; In this course, the amorphous CuO that form to disperse at carrier surface at first, load Fe more afterwards, the Fe of generation
2O
3Be amorphous state, and the amorphous CuO formation crystalline state of seldom reuniting.Since the high adsorption capacity of the reactant of amorphous CuO, simultaneous amorphous Fe
2O
3Produced more Lattice Oxygen defective with the coexisting structure of amorphous CuO, and this Lattice Oxygen defective provides more adsorption activity position for reactant, so the activity of such catalysts height of the method for the invention preparation, the conversion ratio of phenmethylol and the yield of benzaldehyde are all very high.When having overcome the available technology adopting co-impregnation and having prepared the Cu-Fe composite oxide catalysts, active component CuO takes place easily to reunite under the effect of the iron oxide of load at the same time and forms crystalline state, the adsorption activity of crystalline state CuO is low, and the Lattice Oxygen defective that crystalline state CuO and iron oxide produce is less, thereby cause activity of such catalysts low, the conversion ratio of phenmethylol and product benzaldehyde yield be very low problem all.The applicant finds that preparation method of the present invention also can overcome when adopting first load iron back loading copper to be equipped with catalyst simultaneously, the iron oxide that is dispersed on the carrier makes the cupric oxide of back loading that reunion formation crystalline state takes place easily, thereby has reduced the problem of catalyst activity.
(2) catalyst for phenmethylol catalytic oxidation producing benzaldehyde of the present invention, described catalyst is carrier with in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide one or more, described carrier has good adsorption performance, catalytic performance and thermal stability, and its low price has reduced production cost with respect to the MCM-49 molecular sieve.
Description of drawings
For the easier quilt of content of the present invention is understood, the present invention is further detailed content of the present invention with the specific embodiment by reference to the accompanying drawings;
Fig. 1 is the XRD figure of embodiment 5 of the present invention, Comparative Examples 1 and Comparative Examples 2 prepared catalyst.
The specific embodiment
Embodiment 1
(1) takes by weighing 0.005g Gerhardite (in the weight of copper) and be dissolved in the 2.5g deionized water, take by weighing the 5gSBA-15 molecular sieve then and impregnated in 1h in the above-mentioned solution, then behind 90 ℃ of dry 24h, obtain intermediate material at 500 ℃ of roasting 3h;
(2) taking by weighing 0.025g nine nitric hydrate iron (in the weight of iron) is dissolved in the 2.5g deionized water, then intermediate material be impregnated in 1h in the above-mentioned solution, then at 90 ℃ of dry 20h, obtain solid material at 500 ℃ of roasting 3h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C1.
Described catalyst C1 contains SBA-15 molecular sieve 99wt%, CuO0.12wt%, Fe
2O
30.88wt%.
Embodiment 2
(1) takes by weighing 0.20g Gerhardite (in the weight of copper) and be dissolved in the 12.5g deionized water, take by weighing the 5gHZSM-22 molecular sieve then and impregnated in 3h in the above-mentioned solution, then behind 110 ℃ of dry 18h, obtain intermediate material at 400 ℃ of roasting 5h;
(2) taking by weighing 0.5g ferric sulfate (in the weight of iron) is dissolved in the 25g deionized water, then intermediate material be impregnated in 5h in the above-mentioned solution, then at 120 ℃ of dry 12h, obtain solid material at 580 ℃ of roasting 6h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C2.
Described catalyst C2 contains HZSM-22 molecular sieve 81wt%, CuO4.7wt%, Fe
2O
314.3wt%.
(1) takes by weighing 0.20g Gerhardite (in the weight of copper) and be dissolved in the 12.5g deionized water, take by weighing 5gY type molecular sieve then and impregnated in 5h in the above-mentioned solution, then behind 120 ℃ of dry 18h, obtain intermediate material at 580 ℃ of roasting 6h;
(2) taking by weighing 0.45g six Ferric Chloride Hydrateds (in the weight of iron) is dissolved in the 50g deionized water, then intermediate material be impregnated in 3h in the above-mentioned solution, then at 110 ℃ of dry 24h, obtain solid material at 400 ℃ of roasting 5h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C3.
Described catalyst C3 contains Y zeolite 84wt%, CuO4.6wt%, Fe
2O
311.4wt%.
Embodiment 4
(1) takes by weighing 0.10g Salzburg vitriol (in the weight of copper) and be dissolved in the 25g deionized water, take by weighing the 5gSAPO molecular sieve then and impregnated in 1h in the above-mentioned solution, then behind 90 ℃ of dry 18h, obtain intermediate material at 400 ℃ of roasting 3h;
(2) taking by weighing 0.005g nine nitric hydrate iron (in the weight of iron) is dissolved in the 12.5g deionized water, then intermediate material be impregnated in 3h in the above-mentioned solution, then at 110 ℃ of dry 10h, obtain solid material at 500 ℃ of roasting 5h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C4.
Described catalyst C4 contains SAPO molecular sieve 98wt%, CuO1.86wt%, Fe
2O
30.14wt%.
Embodiment 5
(1) takes by weighing 0.25g Copper dichloride dihydrate (in the weight of copper) and be dissolved in the 25g deionized water, take by weighing the 5g4A molecular sieve then and impregnated in 3h in the above-mentioned solution, then behind 110 ℃ of dry 18h, obtain intermediate material at 500 ℃ of roasting 5h;
(2) taking by weighing 0.35g ferric sulfate (in the weight of iron) is dissolved in the 25g deionized water, then intermediate material be impregnated in 5h in the above-mentioned solution, then at 120 ℃ of dry 24h, obtain solid material at 580 ℃ of roasting 6h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C5.
Described catalyst C5 contains 4A molecular sieve 86.6wt%, CuO5.4wt%, Fe
2O
38wt%.
Embodiment 6
(1) takes by weighing 0.4g Copper dichloride dihydrate (in the weight of copper) and be dissolved in the 50g deionized water, take by weighing the 2g silica then and the 3g aluminium oxide impregnated in 5h in the above-mentioned solution, then behind 120 ℃ of dry 10h, obtain intermediate material at 580 ℃ of roasting 6h;
(2) taking by weighing 0.35g six Ferric Chloride Hydrateds is dissolved in the 25g deionized water, then intermediate material be impregnated in 1h in the above-mentioned solution, then at 90 ℃ of dry 24h, obtain solid material at 400 ℃ of roasting 3h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C6.
Described catalyst C6 silicon oxide-containing 32wt%, aluminium oxide 50.4wt%, CuO10wt%, Fe
2O
37.6wt%.
Embodiment 7
(1) taking by weighing 0.5g Copper dichloride dihydrate (in the weight of copper) is dissolved in the 50g deionized water, take by weighing 2g HZSM-5 molecular sieve, 2g HZSM-22 molecular sieve and 1gY type molecular sieve then and impregnated in 6h in the above-mentioned solution, then behind 110 ℃ of dry 18h, obtain intermediate material at 500 ℃ of roasting 5h;
(2) taking by weighing 0.4g nine nitric hydrate iron (in the weight of iron) is dissolved in the 25g deionized water, then intermediate material be impregnated in 3h in the above-mentioned solution, then at 120 ℃ of dry 18h, obtain solid material at 580 ℃ of roasting 6h, at last solid material is pulverized and sieved, the particle that obtains particle diameter and be 0.1-380 μ m is catalyst C7.
Described catalyst C7 contains HZSM-5 molecular sieve 33.5wt%, HZSM-22 molecular sieve 31.1wt%, Y zeolite 15.4wt%, CuO12.5wt%, Fe
2O
37.5wt%.
Comparative Examples 1
Take by weighing the 0.95g Gerhardite and 1.81g nine water ferric nitrates are dissolved in the 10g deionized water, take by weighing the 5g4A molecular sieve then and impregnated in 5h in the above-mentioned solution, then behind 120 ℃ of dry 18h, obtain catalyst C01 at 580 ℃ of roasting 5h.
Comparative Examples 2
(1) takes by weighing 1.81g nine water ferric nitrates and be dissolved in the 25g deionized water, take by weighing the 5g4A molecular sieve then and impregnated in 5h in the above-mentioned solution, then behind 100 ℃ of dry 18h, obtain intermediate material at 580 ℃ of roasting 5h;
(2) take by weighing the 0.95g Gerhardite and be dissolved in the 25g deionized water, then intermediate material be impregnated in 3h in the above-mentioned solution, then at 110 ℃ of dry 12h, obtain catalyst C02 at 580 ℃ of roasting 6h.
Test case
(1) the catalyst C1-C7 in the embodiment of the invention and C01, C02 in the Comparative Examples are used for the catalytic performance of test phenmethylol catalytic oxidation producing benzaldehyde, test condition is: the mol ratio of phenmethylol and oxidant oxygen is 3, the mass ratio of phenmethylol and catalyst is 15, solvent is acetonitrile, 80 ℃ of reaction temperatures, the reaction time is 6h.The conversion ratio of final phenmethylol and the yield of benzaldehyde see Table 1.
Above-mentioned oxidant and solvent can adopt also that other are applicable to oxidant and the solvent of phenmethylol catalytic oxidation producing benzaldehyde in the prior art.
Table 1
| Catalyst | Phenmethylol conversion ratio/% | Benzaldehyde yield/% |
| C1 | 95.2 | 96 |
| C2 | 98.8 | 97.2 |
| C3 | 97.5 | 98.0 |
| C4 | 98.6 | 97.5 |
| C5 | 99.0 | 99.2 |
| C6 | 98.0 | 98.9 |
| C7 | 97.8 | 97.9 |
| C01 | 83.2 | 71.2 |
| C02 | 80.2 | 83.1 |
As can be seen from Table 1, in phenmethylol catalytic oxidation producing benzaldehyde reaction, when using prepared catalyst of the present invention, phenmethylol conversion ratio and benzaldehyde yield when the conversion ratio of phenmethylol and the yield of benzaldehyde are higher than use catalyst C01 and C02.
(2) XRD diffraction test: as shown in Figure 1, in the XRD spectra of catalyst C5, the CuO diffraction maximum is less than the CuO diffraction maximum in catalyst C01 and the C02 spectrogram, it is the crystallization degree that the crystallization degree of the CuO of catalyst C5 is lower than the CuO among catalyst C01 and the C02, it is amorphous that CuO among the C5 mostly is greatly, the adsorption activity height of amorphous CuO, so catalytic activity height of catalyst C5, be that the catalyst that the present invention prepares has advantages of high catalytic activity, when the catalyst of the present invention's preparation that the data in this and the table 1 are reacted was used for phenmethylol catalytic oxidation producing benzaldehyde, the high yield of the high conversion of phenmethylol and benzaldehyde was consistent.
Though the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it; but; those skilled in the art should be understood that any form that does not exceed the claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (10)
1. a Preparation of catalysts method that is used for phenmethylol catalytic oxidation producing benzaldehyde comprises the steps:
(1) with carrier impregnation in the soluble Cu salting liquid, obtain intermediate material after drying and the roasting again; Wherein, in the weight of Cu, Cu salt is the 0.1-10wt% of carrier;
(2) described intermediate material be impregnated in the solubility Fe salting liquid, the solid material that obtains of drying and roasting is the catalyst for phenmethylol catalytic oxidation producing benzaldehyde then.
2. preparation method according to claim 1 is characterized in that, in the weight of Fe,
Fe salt is the 0.1-10wt% of carrier.
3. preparation method according to claim 1 and 2 is characterized in that, the dip time of described step (1) is 1-5h.
4. according to the arbitrary described preparation method of claim 1-3, it is characterized in that in the described step (1), baking temperature is 90-120 ℃, be 10-24h drying time, and sintering temperature is 400-580 ℃, and roasting time is 3-6h.
5. according to the arbitrary described preparation method of claim 1-4, it is characterized in that the solvent in the described Cu salting liquid is the 50-1000wt% of described carrier, the solvent in the described Fe salting liquid is the 50-1000wt% of described carrier.
6. according to the arbitrary described preparation method of claim 1-5, it is characterized in that in the described step (2), dip time is 1-5h, baking temperature 90-120 ℃, be 10-24h drying time, and sintering temperature is 400-580 ℃, and roasting time is 3-6h.
7. according to the arbitrary described preparation method of claim 1-6, it is characterized in that described Cu salt is one or more in copper nitrate, copper sulphate and the copper chloride; Described Fe salt is one or more in ferric nitrate, ferric sulfate and the iron chloride; Described carrier is one or more in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide.
8. according to the arbitrary described preparation method of claim 1-7, it is characterized in that, in the described step (2), also comprise described solid material is treated to the particle that particle diameter is 0.1-380 μ m.
9. the catalyst that is used for phenmethylol catalytic oxidation producing benzaldehyde that the described preparation method of claim 1 obtains, in the gross weight of catalyst, its component comprises,
One or more 80-99% in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide
CuO 0.12-12.5%
Fe
2O
3 0.14-14.3%。
10. catalyst according to claim 9 is characterized in that, in the gross weight of catalyst, its component comprises,
One or more 84-98% in 4A molecular sieve, HZSM-5 molecular sieve, HZSM-22 molecular sieve, Y zeolite, SAPO molecular sieve, SBA-15 molecular sieve, silica and the aluminium oxide
CuO 0.12-10.0%
Fe
2O
3 0.14-11.4%。
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| CN103691479A (en) * | 2013-12-12 | 2014-04-02 | 大连理工大学 | Preparation method and application of composite catalyst |
| CN103962184A (en) * | 2014-04-16 | 2014-08-06 | 西北大学 | Preparation method of Cu, Fe-doped vacancy Keggin type silicon tungsten polyoxometallate catalyst |
| CN106831371A (en) * | 2016-12-29 | 2017-06-13 | 南京工业大学 | A kind of catalysis oxidation prepares benzaldehyde new method |
| CN108607557A (en) * | 2018-05-22 | 2018-10-02 | 常州大学 | A kind of preparation method and application of copper oxide clay |
| CN112588291A (en) * | 2021-01-11 | 2021-04-02 | 武汉工程大学 | Copper-doped iron oxide nanosheet three-dimensional porous material and preparation and application thereof |
| CN115819201A (en) * | 2022-11-22 | 2023-03-21 | 江苏万隆化学有限公司 | Green synthesis process of o-chlorobenzaldehyde catalyzed by titanium silicalite molecular sieve |
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| CN103691479A (en) * | 2013-12-12 | 2014-04-02 | 大连理工大学 | Preparation method and application of composite catalyst |
| CN103691479B (en) * | 2013-12-12 | 2016-04-06 | 大连理工大学 | A kind of preparation method of composite catalyst and application |
| CN103962184A (en) * | 2014-04-16 | 2014-08-06 | 西北大学 | Preparation method of Cu, Fe-doped vacancy Keggin type silicon tungsten polyoxometallate catalyst |
| CN103962184B (en) * | 2014-04-16 | 2016-04-13 | 西北大学 | A kind of preparation method of vacant Keggin-type silicon tungsten oxygen phosphate catalyst of Cu, Fe doping |
| CN106831371A (en) * | 2016-12-29 | 2017-06-13 | 南京工业大学 | A kind of catalysis oxidation prepares benzaldehyde new method |
| CN108607557A (en) * | 2018-05-22 | 2018-10-02 | 常州大学 | A kind of preparation method and application of copper oxide clay |
| CN112588291A (en) * | 2021-01-11 | 2021-04-02 | 武汉工程大学 | Copper-doped iron oxide nanosheet three-dimensional porous material and preparation and application thereof |
| CN112588291B (en) * | 2021-01-11 | 2022-07-12 | 武汉工程大学 | Copper-doped iron oxide nanosheet three-dimensional porous material and preparation and application thereof |
| CN115819201A (en) * | 2022-11-22 | 2023-03-21 | 江苏万隆化学有限公司 | Green synthesis process of o-chlorobenzaldehyde catalyzed by titanium silicalite molecular sieve |
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