CN110963896B - Method for producing aromatic aldehyde ketone through gas phase oxidation reaction - Google Patents

Method for producing aromatic aldehyde ketone through gas phase oxidation reaction Download PDF

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CN110963896B
CN110963896B CN201910019247.0A CN201910019247A CN110963896B CN 110963896 B CN110963896 B CN 110963896B CN 201910019247 A CN201910019247 A CN 201910019247A CN 110963896 B CN110963896 B CN 110963896B
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absorption
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aromatic
aldehyde ketone
aromatic aldehyde
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CN110963896A (en
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刘经伟
徐骏
李泽壮
邢跃军
廉勇
卞伯同
杨爱武
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The invention relates to a method for producing aromatic aldehyde ketone by gas phase oxidation reaction, comprising the following steps: (1) Mixing the branched aromatic compound with oxygen-containing gas, and oxidizing the mixture to generate aldehyde ketone under the action of a catalyst; (2) Carrying out primary or multistage absorption on the reaction product by using a solvent to realize product trapping; (3) The trapped product is subjected to desolventizing to obtain aromatic aldehyde ketone. The aromatic aldehyde ketone produced by the method has the characteristics of good yield and high purity.

Description

Method for producing aromatic aldehyde ketone through gas phase oxidation reaction
Technical Field
The invention relates to a method for producing aromatic aldehyde ketone by gas phase oxidation reaction. More particularly, the present invention relates to a method for capturing a product using one or more stages of absorption during oxidation of an aromatic compound or branched heterocyclic compound, and obtaining an aromatic aldehyde ketone from the captured product by means of desolvation.
Background
Aromatic aldehyde ketones are important fine chemicals downstream of aromatic hydrocarbons. Generally, aromatic aldehyde is obtained by reacting aromatic hydrocarbon with chlorine and then oxidizing under the action of a catalyst such as nitric acid, and the whole process involves corrosive chlorine, strong acid and strong alkali, so that the process is not environment-friendly and is subject to elimination danger. Taking paraxylene downstream derivatives paraphthalaldehyde and paramethylbenzaldehyde as examples, the paraphthalaldehyde is generated by adopting paraxylene and chlorine to react under illumination to generate a chloro-hexachloro substituted compound, and then the paraphthalaldehyde is generated by adopting nitric acid oxidation and sodium hydroxide alkali neutralization, wherein about 10 tons of hydrochloric acid and 0.2 ton of paraaldehyde benzoic acid are produced as byproducts for each 1 ton of paraphthalaldehyde, and a large amount of NOx is discharged; toluene is used as a raw material for the p-methylbenzaldehyde, and the p-methylbenzaldehyde is obtained by chloridizing (bromine) and then by a Sommelet reaction method, wherein halogen and strong acid are also involved in the process.
Along with the increasing stricter environmental protection requirements at home and abroad, the generation of terephthalaldehyde by one-step oxidation of paraxylene as a raw material is widely paid attention to academia and industry at home and abroad. Foreign companies such as Eastman, nippon, BASF and LG have been conducting many years of research work on paraxylylene oxide to terephthalaldehyde. For example, eastman corporation in U.S. Pat. No. 3,182 describes the production of terephthalaldehyde by air oxidation of paraxylene, the catalyst being chosen from tungsten oxide or a multicomponent system of silicotungstic acid and aluminum oxide, bismuth oxide, the conversion of paraxylene and the yield of terephthalaldehyde being up to 41% and 54% at a reaction temperature of 550 ℃. In US6458737 patent by Nippon company, oxides of antimony, iron and tungsten are supported on alumina as catalysts, oxidized with air, and the conversion of paraxylene is 90.9% and the yield of paraphthalaldehyde is 62.6% at a reaction temperature of 550 ℃. The BASF corporation describes in EP0621352 a process for the electrochemical oxidation of paraxylene to terephthalaldehyde. Yoo et al prepared Fe-Mo catalysts by chemical vapor deposition, characterized these catalysts by XRD, TEM, XPS, etc., and examined their performance in the oxidation of paraxylene to terephthalaldehyde (Applied Catalysis A,1996, pages 29-51, applied Catalysis A,1993, 105, 83-105, applied Catalysis A,1993, 106, 259-273). In 2006, LG chemical company developed a process for producing Terephthalaldehyde (TPAL) by a direct oxidation method, which adopts tungsten-containing metal composite oxide as a catalyst, and in a multitubular fixed bed reactor with a shell-and-tube configuration, the conversion rate of paraxylene is 70-78% and the selectivity of terephthalaldehyde is 70-80% under the conditions of 550-600 ℃ and normal pressure. According to the introduction of LG chemical company, the new technology can greatly reduce the production cost, and similar o-phthalaldehyde can also be produced by the selective oxidation of o-xylene.
Fe-Mo metal oxide catalyst prepared by sol-gel method in Guangzhou university Liu Zili subject group, wherein the reaction temperature is 550 ℃, the flow rate of reaction gas is 1000mL/min, and the mass space velocity of paraxylene is 0.48 h -1 Under the conditions of (1) the conversion of paraxylene was 86% and the selectivity to terephthalaldehyde was 50%. Fe-Mo-W metal oxide catalyst prepared by Guangxi university Qin Zu gift and the like, the reaction gas flow rate is controlled at 1000mL/min at the reaction temperature of 500 ℃ and the paraxylene mass airspeed is 2 h -1 Under the conditions of 99.5% conversion of paraxylene and 7% selectivity to terephthalaldehyde4% (Chemical Engineering Journal,2014, 242, pages 414-421). However, both of these reported reaction results have serious drawbacks, mainly in that the reaction process only analyzes liquid and solid products, and does not analyze products of deep oxidation of xylene into CO and CO2, resulting in a high calculation result of selectivity to terephthalaldehyde.
The catalysts or preparation methods disclosed in the above background art, mainly for the oxidation of aromatic hydrocarbons to aromatic aldehydes, have disclosed in CN200680051149.6 a method for preparing aromatic dialdehydes, which comprises a reaction step for producing aromatic dialdehydes by gas phase oxidation of xylenes, a step for recovering crude aromatic dialdehydes in the melt phase and a step for purifying the aromatic dialdehydes. In the process, the aromatic dialdehyde is captured in a molten state into a collecting container, and then impurities are removed through a light and heavy removal tower, so that the aromatic dialdehyde is obtained, however, the low-boiling monoaldehyde chemical cannot be captured by adopting a melting mode, and the monoaldehyde chemical usually enters an incineration system along with tail gas, so that the effective product is difficult to realize complete capture.
Disclosure of Invention
The present inventors have made intensive studies on the basis of the prior art and have found that the present invention has been completed by a method of adding one or more stages of absorbers to the reaction product after the system and then obtaining high-purity aromatic aldehyde ketone by rectification.
The invention provides a method for producing aromatic aldehyde ketone by gas phase oxidation reaction, which comprises the following steps: (1) Mixing the branched aromatic compound with oxygen-containing gas, and oxidizing to produce aldehyde ketone with high selectivity under the action of catalyst to produce acid and alcohol with less side product; (2) The generated product of the reaction is absorbed by one stage or multiple stages, so that the product is trapped; (3) The trapped product is subjected to desolventizing to obtain aromatic aldehyde ketone.
The present invention provides a process for producing aromatic aldehyde ketones by gas phase oxidation, in one embodiment, the catalyst has one of the following general formulae (I), (II), (III), (iv), (v), (vi):
Mo a R b M c Od（I）
wherein b/a=0.02 to 1.5, c/a=0.05 to 6, d is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), R is a rare earth element selected from at least one of La, ce and Nd, M is an auxiliary agent and at least one element selected from Li, na, K, rb, cs, mg, ca, sr, ba, ti, zr, nb, cr, mn, re, fe, ru, co, ni, pd, pt, cu, au, zn, cd, al, ga, in, sn, pb, sb, bi, si;
Ag a1 V b1 Mo c1 M1 d1 O e1 （II）
wherein b 1/a1=1.0 to 2.5, c 1/a1=0.05 to 1.1, d 1/a1=0.01 to 0.58, e1 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), M1 is an auxiliary agent and is at least one metal selected from Li, na, K, rb, cs, mg, ca, sr, ba, ti, zr, nb, cr, W, mn, re, fe, ru, co, ni, pd, pt, cu, au, zn, cd, al, ga, in, sn, pb, sb, bi, la, ce, nd;
Ag a2 V b2 Ni c2 M2 d2 O e2 （III）
wherein b 2/a2=1.0-2.5, c 2/a2=0.05-1.2, d 2/a2=0.01-0.58, e2 is a value required for satisfying the valence of an element other than an oxygen atom in the general formula (I), M2 is an auxiliary agent and is at least one metal selected from Li, na, K, rb, cs, mg, ca, sr, ba, ti, zr, nb, cr, W, mn, re, fe, ru, co, pd, pt, cu, au, zn, cd, al, ga, in, sn, pb, sb, bi, la, ce, nd;
Ag a3 V b3 Si c3 M3 d3 O e3 （Ⅳ）
wherein b 3/a3=1.0 to 2.5, c 3/a3=0.05 to 0.8, d 3/a3=0.01 to 0.58, e3 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), M3 is an auxiliary agent and is at least one metal selected from Li, na, K, rb, cs, mg, ca, sr, ba, ti, zr, nb, cr, W, mn, re, fe, ru, co, ni, pd, pt, cu, au, zn, cd, al, ga, in, sn, pb, sb, bi, la, ce, nd, mo;
W a4 X b4 Y c4 O d4 （Ⅴ）
wherein b 4/a4=0.1 to 1.3, c 4/a4=0.05 to 0.8, d4 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), W is tungsten, X is selected from P, sb, bi and Si, and Y is at least one metal selected from Fe, co, ni, mn, re, cr, V, nb, ti, zr, zn, cd, Y, la, ce, B, al, tl, sn, mg, ca, sr, ba, li, na, K, rb, cs;
W a5 X' b5 Y' c5 O d5 （Ⅵ）
wherein b 5/a5=0.1 to 1.3, c 5/a5=0.05 to 1.2, d5 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), W is tungsten, X 'is selected from Li, na, K, rb and Cs, and Y' is at least one metal selected from Fe, co, ni, cu, mn, re, cr, V, nb, ti, zr, zn, cd, Y, la, ce, B, al, sn, mg, ca, sr and Ba;
Ag a6 V b6 W c6 M4 d6 O e6 （Ⅶ）
wherein b6/a6 is more than 1.0, c6/a6=0.05-1.5, d 6/a6=0.01-0.58, e6 is a value determined by the valence and frequency of elements except oxygen atoms in the general formula (I), and the auxiliary agent M4 is at least one metal or P alkali metal selected from Li, na, K, rb, cs, mg, ca, sr, ba, ti, zr, nb, cr, mo, mn, re, fe, ru, co, ni, pd, pt, cu, au, zn, cd, al, ga, in, sn, pb, sb, bi, la, ce, nd.
According to the present invention, the conditions for the catalytic oxidation reaction include: the hot spot temperature is 200-550 ℃, preferably 240-540 ℃, the pressure is normal pressure to 5MPa, preferably normal pressure to 0.2MPa, and the feeding concentration is 15-150 gm -3 Preferably 15 to 100gm -3 Airspeed of 1000-60000 h -1 Preferably 2000 to 60000h -1 。
If desired, the branched aromatic compound or branched heterocyclic compound or the mixture may be preheated to 100 to 500 ℃, preferably 200 to 450 ℃, prior to contact with the catalyst.
According to the present invention, the branched aromatic compound means a compound in which one or more hydrogens on the aromatic ring are substituted with one or more C1-C12 alkanyl groups, preferably C1-C6 alkanes, and examples thereof include methane, ethane, propane, n-butane, isobutane, tert-butane, n-pentane, isopentane, and n-hexane. The branched aromatic compound is preferably toluene, paraxylene, o-xylene, m-xylene, mesitylene, meta-trimethylbenzene, durene.
According to the present invention, the branched heterocyclic compound means a compound in which one or more hydrogens on the heterocycle are substituted with one or more C1 to C12 alkanyl groups, preferably C1 to C6 alkanes, and examples thereof include alkyl compounds such as methane, ethane, propane, n-butane, isobutane, t-butane, n-pentane, isopentane, and n-hexane. The branched heterocyclic compound is preferably picoline, lutidine, collidine.
The heterocyclic compound is a compound in which one or more carbons in the cyclic carbon compound are replaced with oxygen, nitrogen, or sulfur, and may be, for example, pyridine, thiophene, or the like.
According to the invention, the catalytic oxidative dehydrogenation takes place when the branched aromatic compound or branched heterocyclic compound has only one C1-C12 alkanyl group. When the branched aromatic compound or branched heterocyclic compound has a plurality of C1-C12 alkyl groups, it is desirable that at least one of the C1-C12 alkyl groups undergoes the catalytic oxidation reaction, but it is not required that all of the C1-C12 alkyl groups be capable of undergoing the catalytic oxidation reaction, although it is sometimes desirable according to actual needs.
According to the invention, the one or more stage absorption is preferably a multistage absorption, for example a 2-10 stage absorption, for example a2, 3, 4, 5 or 6 stage absorption.
According to the present invention, the solvent used in the one or more stages of absorption includes an organic solvent such as an aromatic compound, a hetero atom compound, a paraffin compound, or water.
According to the present invention, when multi-stage absorption is employed, it is preferable to employ an organic solvent in the first-stage absorption. In one embodiment, the organic solvent used in the first stage absorption is preferably an aromatic compound or a heteroatom compound.
According to the present invention, the aromatic compound in the solvent used in the one or more stages of absorption includes aromatic hydrocarbon, aromatic alcohol, aromatic aldehyde, aromatic acid, aromatic ester, for example, toluene, xylene, trimethylbenzene, tetramethylbenzene, benzyl alcohol, benzaldehyde, p-methylbenzaldehyde, dibutyl phthalate, dioctyl phthalate, preferably aromatic ester, further preferably dimethyl phthalate, dibutyl phthalate, dioctyl phthalate.
The heteroatom compounds used in the one or more stage absorption according to the present invention include cyclic compounds containing oxygen, nitrogen, sulfur, and chain compounds such as dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, tetrahydrofuran, delta-butyrolactone, N-methylpyrrolidone, tributyl phosphate, and the like.
According to the invention, the paraffin compounds mentioned are compounds on which one or more hydrogens, one or more carbons replaced by heteroatoms, preferably alkanes having a carbon number higher than 7 and lower than 16, more preferably alkanes having a carbon number higher than 8 and lower than 14, are also included on linear or branched alkanes, such as octane, dioxane, decane, 1, 2-dichlorooctane, etc.
According to the invention, the ratio of the total mass of the solvent to the total mass of the reaction product adopted in the one-stage or multi-stage absorption is 0.01-0.1:1.
According to the invention, the one-stage or multistage absorption is carried out in an absorption column.
According to the invention, the absorption column temperature at which the one-stage or multistage absorption is carried out is 20-160 ℃. In order to ensure the absorption temperature, the materials generated by the oxidation reaction need to undergo one-stage or multi-stage heat exchange, and the temperature of the materials is reduced to 30-170 ℃.
According to the invention, the product after trapping is subjected to solvent removal to obtain aromatic aldehyde ketone, for example, by adopting a rectification mode, and the temperature of the tower bottom of the rectification tower is 100-300 ℃. In order to ensure an effective separation of the absorption solvent from the aromatic aldehyde, the rectification column is usually operated under a negative pressure, with an absolute pressure of 10 to 80kPa.
According to the invention, the collected product is subjected to a desolventizing mode to obtain aromatic aldehyde ketone, and the specific mode is that a rectification mode is adopted, when the boiling point of the solvent for absorption is higher than that of the aromatic aldehyde ketone product, the aromatic aldehyde ketone is discharged from the top of the rectification tower or a side line of the tower; when the boiling point of the absorption solvent is lower than that of the aromatic aldehyde ketone product, the aromatic aldehyde ketone is discharged from the bottom of the tower.
According to the invention, the trapped product is subjected to solvent removal to obtain aromatic aldehyde ketone, specifically, a rectification mode is adopted, and alkali washing and water washing are optionally added before and after a rectification tower to remove aromatic acid.
According to the invention, recovery rate means that (1) the generated product of the reaction is subjected to one-stage or multi-stage absorption by a solvent to realize product trapping; (2) The trapped product is desolvated, and then the ratio of the total amount of the obtained aromatic aldehyde ketone to the total amount of the aldehyde ketone actually generated by the reaction is obtained.
Compared with the prior art, such as the comparative patent CN200680051149.6, the invention not only can collect the high-boiling point polysubstituted aromatic ketone and aromatic aldehyde, but also has good collecting effect on the low-boiling point monoaldehyde monoketone, the recovery rate of the aldehyde ketone in the oxidation reaction product can reach more than 99%, and the purity of the single aldehyde ketone can reach more than 99%.
Detailed Description
The invention is further illustrated by the following examples:
example 1
10.0g of ammonium molybdate heptahydrate was dissolved in 100ml of water to prepare a molybdenum solution, and 0.5mol L of Mo was added in a mass ratio of Ce: ti=1.0:0.1:0.08 -1 Aqueous cerium nitrate solution and 0.1mol L -1 Mixing thoroughly, adding 28% ammonia water solution to adjust pH=13, adding monoethanolamine according to the mass ratio of ammonia water to monoethanolamine of 70:1, precipitating, crystallizing at 130deg.C, filtering, and roasting at 500deg.C for 3 hr to obtain Mo 1 Ce 0.1 Ti 0.08 Ox catalyst, catalyst surface area measured to be 4m 2 g -1 . At a reaction hot spot temperature of 350 ℃, the toluene concentration is 55gm -3 Air space velocity is 45000h -1 Toluene conversion was 10.5%, benzaldehyde selectivity was 92.8%, benzoic acid selectivity was6.4% and COx selectivity of 0.3%.
Example 2
10.0g of ammonium molybdate heptahydrate was dissolved in 100ml of water to prepare a molybdenum solution, and 0.5mol L of Mo: la: mn=1.0:0.1:0.19 was added in terms of mass ratio -1 Aqueous lanthanum nitrate solution and 0.1mol L -1 After fully mixing, adding 28% ammonia water solution to adjust the pH value to be=13, adding monoethanolamine according to the mass ratio of ammonia water to monoethanolamine of 70:1, precipitating, crystallizing at 130 ℃, filtering, roasting at 500 ℃ for 3 hours, and obtaining Mo 1 La 0.1 Mn 0.19 Ox catalyst, catalyst surface area measured to be 4m 2 g -1 . At a reaction hot spot temperature of 510 ℃, the para-xylene concentration was 55gm -3 Air space velocity of 40000h -1 The conversion of paraxylene was 12.4%, the selectivity to terephthalaldehyde and paramethylbenzaldehyde was 97.3%, and the selectivity to COx was 0.4%.
Example 3
10.0g of ammonium metavanadate is dissolved in hydrogen peroxide with the mass fraction of 20% and salicylic acid solution with the mass fraction of 5% to prepare a vanadium solution, and 0.5mol L is added according to the mass ratio V of Ag to Si, pt=1.2:1.0:0.6:0.13 -1 Silver nitrate aqueous solution and SiO with mass fraction of 10% 2 Hydrosol and 0.1mol L -1 After fully mixing, adding 28% ammonia water solution to adjust the pH to be 13, wherein the mass ratio of the ammonia water to the adipic acid is 50:1, crystallizing the precipitate at 130 ℃, filtering, and roasting at 550 ℃ for 3 hours to obtain Ag 1 V 1.2 Si 0.6 Pt 0.13 O x Catalyst, surface area of catalyst was measured to be 13m 2 g -1 . At a reaction hot spot temperature of 520℃and a metaxylene concentration of 40gm -3 Space velocity of 35000h -1 The conversion of meta-xylene was 14.1%, the selectivity of isophthalaldehyde and meta-methylbenzaldehyde was 88.5% and the selectivity of COx was 7.9%.
Example 4
10.0g of ammonium metavanadate is dissolved in 10% of hydrogen peroxide solution and 5% of citric acid solution to prepare a vanadium solution, wherein the ratio of the mass of V to Ag to Mo is Mn=1.5:1.0:1.0:014 adding 0.5mol L -1 Silver nitrate aqueous solution, 0.4mol L -1 Ammonium molybdate heptahydrate aqueous solution and 0.1mol L -1 After fully mixing, adding 28% ammonia water solution to adjust the pH to be=13, crystallizing the precipitate at 150 ℃, filtering, and roasting at 530 ℃ for 3 hours to prepare Ag 1 V 1.5 Mo 1 Mn 0.14 Ox catalyst, catalyst surface area 5m 2 g -1 The dispersity of vanadium was 17%. At a reaction hot spot temperature of 510 ℃, the para-xylene concentration is 60 gm -3 Space velocity of 43000h -1 The conversion of p-xylene was 13.3%, the selectivity to terephthalaldehyde and p-methylbenzaldehyde was 98.4%, and the selectivity to COx was 0.2%.
Example 5
10.0g of ammonium metavanadate is dissolved in hydrogen peroxide with the mass fraction of 20% and tartaric acid solution with the mass fraction of 5% to prepare a vanadium solution, and 0.5mol L is added according to the mass ratio V of Ag to Ni to Cd=1.2 to 1.0 to 0.33 to 0.11 -1 Silver nitrate aqueous solution, 0.4mol L -1 And 0.1mol L of nickel nitrate aqueous solution -1 After fully mixing, adding 28% ammonia water solution to adjust the pH to be=13, adding cyclohexylamine according to the mass ratio of ammonia water to ethanolamine of 45:1, precipitating, crystallizing at 130 ℃, filtering, and roasting at 550 ℃ for 3 hours to obtain Ag 1 V 1.2 Ni 0.33 Cd 0.11 Ox catalyst, catalyst surface area 15m 2 g -1 The dispersity of vanadium was 15%. At a reaction hot spot temperature of 510 ℃, the concentration of mesitylene is 40gm -3 Space velocity of 40000h -1 The mesitylene conversion was 14.1%, the total selectivity of monomethyl dialdehyde, dimethyl monoaldehyde and trimesic aldehyde was 95.1%, and the selectivity of COx was 0.7%.
Example 6
The reaction products of examples 1 to 5 were subjected to 2-stage absorption in an absorption column using, as absorbents, respectively, pseudocumene (A), sulfolane (B), N, N-dimethylformamide (C), tetrahydrofuran (D), dimethyl sulfoxide (E), n-octane (F) and water (G). The temperature of the absorption tower kettle is 70 ℃. And obtaining aldehyde products by adopting a rectification mode after absorption, wherein the temperature of a tower bottom of a rectification tower is 130 ℃ and the pressure is 20kPa.
The recovery of aldehydes in each example is shown in Table 1.
Although the invention is described in detail herein with reference to the exemplary embodiments, it should be understood that the invention is not limited to the embodiments. Those having ordinary skill in the art and access to the teachings herein will recognize additional variations, modifications, and embodiments that are within the scope thereof. Accordingly, the invention is to be construed broadly in accordance with the appended claims.

Claims (7)

1. A method for producing aromatic aldehydes by gas phase oxidation, comprising: (1) Mixing branched aromatic compounds with an oxygen-containing gas, and oxidizing the mixture to form aldehyde under the action of a catalyst; (2) The generated product of the reaction is absorbed by a solvent for 2-10 levels, so as to realize the trapping of the product; (3) The trapped product is subjected to solvent removal to obtain aromatic aldehyde; wherein the solvent used in the absorption of the first to penultimate stages is selected from the group consisting of toluene, xylene, trimethylbenzene, tetramethylbenzene, benzyl alcohol, benzaldehyde, p-methylbenzaldehyde, a combination of one or more of dibutyl phthalate, dioctyl phthalate, dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, tetrahydrofuran, delta-butyrolactone, N-methylpyrrolidone, tributyl phosphate, the solvent used in the absorption of the last stage is selected from the group consisting of one or more of dimethyl sulfoxide, sulfolane and water,
the branched aromatic compound is at least one selected from toluene, paraxylene, o-xylene, m-xylene, mesitylene, meta-trimethylbenzene, durene,
the catalyst is a combination of one or more of the following general formulas (I), (II), (III), (IV):
Mo a R b M c Od(I)
wherein b/a=0.02 to 1.5 and c/a=005 to 6, d is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), R is a rare earth element selected from at least one of La and Ce, M is an auxiliary agent and at least one element selected from Ti and Mn; ag (silver) a1 V b1 Mo c1 M1 d1 O e1 (II)
Wherein, b 1/a1=1.0-2.5, c 1/a1=0.05-1.1, d 1/a1=0.01-0.58, e1 is a value required for satisfying the valence of the element except the oxygen atom in the general formula (I), M1 is an auxiliary agent and is selected from Mn;
Ag a2 V b2 Ni c2 M2 d2 O e2 (III)
wherein b 2/a2=1.0-2.5, c 2/a2=0.05-1.2, d 2/a2=0.01-0.58, e2 is a value required for satisfying the valence of an element other than an oxygen atom in the general formula (I), M2 is an auxiliary agent and is selected from Cd;
Ag a3 V b3 Si c3 M3 d3 O e3 (Ⅳ)
wherein b 3/a3=1.0 to 2.5, c 3/a3=0.05 to 0.8, d 3/a3=0.01 to 0.58, e3 is a value required to satisfy the valence of an element other than an oxygen atom in the general formula (I), and M3 is an auxiliary agent and is selected from Pt.
2. The process according to claim 1, wherein the oxidation reaction hot spot temperature is 200 to 550 ℃, the pressure is normal pressure to 5MPa, and the feed concentration is 15 to 150gm -3 Air airspeed of 1000-60000 h -1 。
3. The process according to claim 1, wherein the oxidation reaction hot spot temperature is 240 to 500 ℃, the pressure is normal pressure to 0.2MPa, and the feed concentration is 15 to 100gm -3 Air airspeed of 2000-60000 h -1 。
4. The method according to claim 1, characterized in that a2, 3, 4, 5 or 6 stage absorption is used.
5. The process according to claim 4, wherein the solvent used in the first stage absorption is dimethyl phthalate, dibutyl phthalate, or dioctyl phthalate.
6. The process according to claim 1, wherein the ratio of the total mass of solvent to the total mass of reaction product employed in the one or more stages of absorption is from 0.01 to 0.1:1, the absorption being carried out at a temperature of from 20 to 160 ℃.
7. The method according to claim 1, wherein the collected product is desolventized to obtain aromatic aldehyde, in particular by rectification.
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US3946067A (en) * 1972-08-29 1976-03-23 National Distillers And Chemical Corporation Process for the preparation of aromatic aldehydes
CN101360702A (en) * 2005-12-14 2009-02-04 Lg化学株式会社 A method for preparing an aromatic dialdehyde and a manufacturing system for the same
CN103012028A (en) * 2012-12-19 2013-04-03 湖南大学 Method for preparing aromatic aldehyde through catalytic oxidation of toluene compound
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