CN103285865A - Catalyst for synthesizing benzaldehyde by carrying out liquid-phase high-selectivity catalytic oxidation on methylbenzene - Google Patents
Catalyst for synthesizing benzaldehyde by carrying out liquid-phase high-selectivity catalytic oxidation on methylbenzene Download PDFInfo
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Abstract
The invention discloses a novel catalyst for carrying out liquid-phase high-selectivity catalytic oxidation on methylbenzene. The catalyst mainly takes an alkaline-earth metal composite oxide with high temperature stability as a carrier and metals (V, Cr, Mn, Fe, Co, Ni, Cu, Au, Pd and Pt) with high activity as catalytic oxidation active centers. The prepared catalyst shows high selectivity and activity in liquid-phase oxidation of methylbenzene. Under the conditions that the reaction temperature is 90-160 DEG C, the reaction time is 2-48 hours and the pressure of air or oxygen is 0.5-2.0MPa, the highest selectivity of benzaldehyde can be 94.0% and the highest conversion rate of methylbenzene also reaches 45.0%. Compared with the reported results, the prepared catalyst has the advantages that the catalyst still has good mesoporous structure under high temperature; in the catalysis process, the conversion rate of methylbenzene and the yield of benzaldehyde are high; and meanwhile, any solvent or organic additive is not added to a reaction system and the catalyst has the advantages of high yield, low cost, no environmental pollution, easy separation, good repeatability and the like.
Description
Technical field
The present invention relates to a kind of new catalyst for toluene liquid phase high-selectivity oxidation producing benzaldehyde and preparation method thereof.
Background technology
VOC (VOCs) is one of common waste gas, mainly comes production fields such as comfortable petrochemical industry, paint production, coated metal, printing and bag lacquer, evaporate into not only to pollute the environment in the atmosphere, also can be detrimental to health.If VOCs is converted into useful chemical products or chemical intermediate, can not only reduce discharging wastes, and can turn waste into wealth, increase economic efficiency.Toluene, this harm is maximum, pollute one of the heaviest VOCs member, can oxidized generation phenmethylol, benzaldehyde, benzoic acid, Ergol etc., these products are widely used in dyestuff, solvent, spices as general intermediate, plasticizer, dyestuff, anticorrisive agent, fields such as fire retardant.Especially in recent years along with medicine, fragrance industry increase year by year to the demand of no chlorobenzaldehyde, Benzyl Side-Chain selective oxidation producing benzaldehyde is more paid close attention to.But the present industrial technology that still adopts the sixties, reaction speed is slow, and the toluene consumption is big, and because the existence of deep oxidation and the side reaction of ring hydroxylating, selectively lower, economic benefits are poor.Therefore, research methylbenzene selective oxidation generation benzaldehyde has business development value and scientific meaning.
Air, oxygen compare with other oxidant have cheapness, environmental protection and plurality of advantages such as be easy to get, this makes molecular oxygen selective oxidation toluene have very big development prospect.Molecular oxygen selective oxidation toluene can be divided into gaseous oxidation and liquid phase oxidation.Though two kinds of catalyst system and catalyzings have all demonstrated advantages of high catalytic activity, deep oxidation takes place in reaction temperature height easily in the catalytic gas phase oxidation process, causes target product selectivity generally on the low side.Aspect liquid phase catalytic oxidation, the MC catalyst system and catalyzing is comparatively ripe, but the target product selectivity of gained still remains to be improved, catalyst, solvent, product separation difficulty simultaneously, and environmental pollution is serious, the needs of incompatibility modern chemical industry development; Recent Kesavan etc. are at Science, 2011, reported condition of no solvent under activated carbon supported Au, Pd nanometer alloy catalyst (Au-Pd/C) to the liquid phase catalytic oxidation of toluene at 331 (6014): 185～199, find when n in the catalyst (Au): n (Pd)=1: 1.85,160 ℃ are reacted 27h down, the conversion ratio of toluene is 94.4%, Ergol selectively can reach 85.5%, but benzaldehyde selectively has only 1.0%, and how optimizing catalyst system and catalyzing selectively is one of the difficult problem that needs to be resolved hurrily with what improve benzaldehyde.
Summary of the invention
1. invent the technical problem that will solve
At the problem that exists in the existing method of producing benzaldehyde, the invention provides a kind of new catalyst for toluene liquid phase high-selectivity oxidation producing benzaldehyde and preparation method thereof.
2. technical scheme
(1) a kind of new catalyst for toluene liquid phase high selectivity catalytic oxidation is characterized in that: catalyst is carrier with the alkaline-earth metal composite oxides of high-temperature stability mainly; Be the catalytic oxidation activity center with highly active metal (V, Cr, Mn, Fe, Co, Ni, Cu, Au, Pd, Pt) etc., wherein the content of responsible metallic element account for 0.03～1.0% of catalyst gross mass.
(2) preparation method who is used for the new catalyst of toluene liquid phase selective oxidation producing benzaldehyde comprises the steps:
1) mixed aqueous solution of preparation divalent alkaline-earth metal nitrate and aluminum nitrate, control alkaline earth metal cation and aluminum ions mol ratio are 2.0～5.0; Control cationic total concentration at 0.2～1.5mol/L;
2) preparation ammonium carbonate solution, the mole dosage of control ammonium carbonate and aluminum nitrate is identical, above two solution is mixed the back fully stirred 0.5 hour, and temperature is controlled at 60 ℃, utilizes NH in this process
4The pH value of OH control mixed solution is 8～11.5, and the colloid with gained filters or centrifugal dehydration then, washes to neutrality 100 ℃ of oven dry, 300～700 ℃ of following N of the solid sample of gained with water
2Calcining is 4 hours in the gas, can get corresponding composite oxide of metal;
3) the gained composite oxide of metal being placed mass percent concentration is 1～10% the halogeno-amine aqueous solution, and adds isopyknic 0.2mol/L template agent aqueous solution therein, and temperature is controlled at 60～100 ℃, and the pH value is controlled 8.0～11.5.Add transition metal nitrate or precious metal salt after 12 hours, keeping the molal quantity of transition metal nitrate is 5～20% of alkaline-earth metal molal quantity, and the noble metal molal quantity is 0.1～1.0% of alkaline-earth metal molal quantity, adds an amount of H simultaneously
2O
2, keep H
2O
2The molal quantity of molal quantity and halogeno-amine equates, stirs 24 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800～1200 ℃ of following N
2Calcine 2～10 hours required new catalysts in the gas.
Described alkaline earth nitrate can be one or both in magnesium nitrate, calcium nitrate, strontium nitrate and the barium nitrate.
Described halogeno-amine can be one or both in ammonium fluoride, ammonium chloride, ammonium bromide and the ammonium iodide.
Described template agent can be a kind of in the triblock copolymer (P123) of softex kw (CTAB), Triton X-100 (TritonX-10) and polyoxyethylene-poly-oxypropylene polyoxyethylene.
Described transition metal nitrate can be one or both in nitric acid vanadium, chromic nitrate, manganese nitrate, ferrous nitrate, cobalt nitrate, nickel nitrate, the copper nitrate, and precious metal salt can be PdCl
2, HAuCl
43H
2O and H
2PtCl
66H
2Among the O one or both.
Product analysis, chromatographic condition is as follows: (temperature programming: 50 ℃ of initial temperatures, continue 5min to Agilent 6890 gas-chromatographies by 15 ℃ of phase I/min to 220 ℃ for capillary column: 30mm * 320um * 0.25um), 50 ℃ of column temperatures.Carrier gas is N
2, flow velocity 40mL/min, the hydrogen ion flame detector, hand sampling, sample size 0.2 μ L carries out quantitative analysis by normalization method to each product.
3. beneficial effect
The present invention compares with existing catalyst has following advantage:
(1) the gained catalyst still has meso-hole structure under higher temperature, specific area is higher.
(2) in the course of reaction, the selective and yield of benzaldehyde is all higher, the reaction condition gentleness.
(3) do not add any solvent and organic additive in the reaction system, environment is not produced and pollute, and target product is easily separated, can be used for industrial production in a large number.
The specific embodiment:
Embodiment 1
With 7.2Kg Mg (NO
3)
26H
2O, 3.1Kg Ba (NO
3)
2With 7.5Kg Al (NO
3)
39H
2O is made into 200L solution with deionized water; With 2.1Kg Na
2CO
3Be made into 200L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 8.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 300 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 1% ammonium fluoride aqueous solution that the gained sample places quality 50L percent concentration, and adds the CTAB of 50L 0.2mol/L therein, and temperature is controlled at 60 ℃, utilizes NH simultaneously
4It is 8.0 that OH control mixes liquid pH value.Cu (the NO that adds 7.2Kg after 12 hours
3)
23H
2O, the 30%H of molal quantitys such as adding and amine fluoride simultaneously
2O
2The aqueous solution stirred 24 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
22 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, feed O
2To 0.5MPa, toluene 10.0Kg, catalyst amount are the 0.6%wt of reactant, when being warming up to 90 ℃, start stirring, react after 12 hours, and product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 3.0%, benzaldehyde selectively be 85%.
Embodiment 2
With 6.1Kg Mg (NO
3)
26H
2O, 1.4Kg Ca (NO
3)
24H
2O and 2.3Kg Al (NO
3)
39H
2O is made into 7.2L solution with deionized water; With 0.6Kg Na
2CO
3Be made into 7.2L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 11.5 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 700 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 10% ammonium fluoride aqueous solution that the gained sample places quality 50L percent concentration, and adds the CTAB of 50L 0.2mol/L therein, and temperature is controlled at 60 ℃, utilizes NH simultaneously
4It is 11.5 that OH control mixes liquid pH value.Cu (the NO that adds 0.87Kg after 12 hours
3)
26H
2Fe (the NO of O and 1.0Kg
3)
26H
2O, the 30%H of molal quantitys such as adding and amine fluoride simultaneously
2O
2The aqueous solution stirred 24 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 1200 ℃ of following N
210 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, and bubbling air is to 0.5MPa, toluene 10.0Kg, catalyst amount is the 0.6%wt of reactant, when being warming up to 160 ℃, starts stirring, react after 48 hours, product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 15.0%, benzaldehyde selectively be 25%.
Embodiment 3
With 6.1Kg Mg (NO
3)
26H
2O, 1.6Kg Ba (NO
3)
2With 3.8Kg Al (NO
3)
39H
2O is made into 40L solution with deionized water; With 1.1Kg Na
2CO
3Be made into 40L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 10.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 500 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 3.0% the amine bromide aqueous solution that the gained sample places quality 50L percent concentration, and adds the TritonX-10 of 50L 0.2mol/L therein, and temperature is controlled at 80 ℃, utilizes NH simultaneously
4It is 10.0 that OH control mixes liquid pH value.Cr (the NO that adds 1.4Kg after 12 hours
3)
29H
2V (the NO of O and 1.0Kg
3)
26H
2O, the 30%H of molal quantitys such as adding and amine bromide simultaneously
2O
2The aqueous solution stirred 12 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
26 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, feed O
2To 2.0MPa, toluene 10.0Kg, catalyst amount are the 0.6%wt of reactant, when being warming up to 120 ℃, start stirring, react after 24 hours, and product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 25.0%, benzaldehyde selectively be 35%.
Embodiment 4
With 11.3Kg Mg (NO
3)
26H
2O, 1.6Kg Ba (NO
3)
2With 3.8Kg Al (NO
3)
39H
2O is made into 40L solution with deionized water; With 1.0Kg Na
2CO
3Be made into 40L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 10.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 500 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 6.0% the ammonium iodide aqueous solution that the gained sample places quality 50L percent concentration, and adds the P123 of 50L 0.2mol/L therein, and temperature is controlled at 80 ℃, utilizes NH simultaneously
4It is 10.0 that OH control mixes liquid pH value.Mn (the NO that adds 0.9Kg after 12 hours
3)
26H
2Co (the NO of O and 0.9Kg
3)
26H
2O, the 30%H of molal quantitys such as adding and iodate amine simultaneously
2O
2The aqueous solution stirred 12 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
26 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, and bubbling air is to 1.5MPa, toluene 10.0Kg, catalyst amount is the 0.6%wt of reactant, when being warming up to 150 ℃, starts stirring, react after 12 hours, product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 15.0%, benzaldehyde selectively be 65%.
Embodiment 5
With 8.7Kg Mg (NO
3)
26H
2O, 1.6Kg Ba (NO
3)
2With 1.8Kg Al (NO
3)
39H
2O is made into 40L solution with deionized water; With 1.0Kg Na
2CO
3Be made into 40L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 10.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 500 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 6.0% the ammonium iodide aqueous solution that the gained sample places quality 50L percent concentration, and adds the P123 of 50L 0.2mol/L therein, and temperature is controlled at 80 ℃, utilizes NH simultaneously
4It is 10.0 that OH control mixes liquid pH value.Cu (the NO that adds 0.7Kg after 12 hours
3)
23H
2Ni (the NO of O and 0.9Kg
3)
26H
2O, the 30%H of molal quantitys such as adding and iodate amine simultaneously
2O
2The aqueous solution stirred 12 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
26 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, feed O
2To 2.0MPa, toluene 10.0Kg, catalyst amount are the 1.0%wt of reactant, when being warming up to 160 ℃, start stirring, react after 8 hours, and product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 45.0%, benzaldehyde selectively be 94%.
Embodiment 6
With 8.7Kg Mg (NO
3)
26H
2O, 1.7Kg Sr (NO
3)
24H
2O and 3.8Kg Al (NO
3)
39H
2O is made into 80L solution with deionized water; With 1.0Kg Na
2CO
3Be made into 80L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 10.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 500 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 2.0% bromize ammonium solution that the gained sample places quality 50L percent concentration, and adds the P123 of 50L 0.2mol/L therein, and temperature is controlled at 80 ℃, utilizes NH simultaneously
4It is 10.0 that OH control mixes liquid pH value.The PdCl that adds 0.7g after 12 hours
2, add the 30%H with molal quantitys such as amine bromide simultaneously
2O
2The aqueous solution stirred 12 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
26 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, feed O
2To 2.0MPa, toluene 10.0Kg, catalyst amount are the 0.5%wt of reactant, when being warming up to 160 ℃, start stirring, react after 8 hours, and product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 5.0%, benzaldehyde selectively be 76%.
Embodiment 7
With 8.7Kg Mg (NO
3)
26H
2O, 1.6Kg Ba (NO
3)
2With 3.8Kg Al (NO
3)
39H
2O is made into 80L solution with deionized water; With 1.0Kg Na
2CO
3Be made into 80L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 10.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 500 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 2.0% the ammonium iodide aqueous solution that the gained sample places quality 50L percent concentration, and adds the CTAB of 50L 0.2mol/L therein, and temperature is controlled at 80 ℃, utilizes NH simultaneously
4It is 10.0 that OH control mixes liquid pH value.The PdCl that adds 4.0g after 12 hours
2HAuCl with 8.0g
43H
2O, the 30%H of molal quantitys such as adding and iodate amine simultaneously
2O
2The aqueous solution stirred 12 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
26 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, and bubbling air is to 2.0MPa, toluene 10.0Kg, catalyst amount is the 0.5%wt of reactant, when being warming up to 160 ℃, starts stirring, react after 8 hours, product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 35.0%, benzaldehyde selectively be 86%.
Embodiment 8
With 6.1Kg Mg (NO
3)
26H
2O, 4.2Kg Ba (NO
3)
2With 3.8Kg Al (NO
3)
39H
2O is made into 80L solution with deionized water; With 1.0Kg Na
2CO
3Be made into 80L solution with deionized water, after two solution mix, 60 ℃ of following vigorous stirring 0.5 hour, and add NH
4It is 10.0 that OH control mixes liquid pH value.The colloid of gained filters or centrifugal dehydration, is washed to neutrality, after 100 ℃ of oven dry, places 500 ℃ of following N
2Calcining is 4 hours in the atmosphere, and it is 2.0% the ammonium iodide aqueous solution that the gained sample places quality 50L percent concentration, and adds the CTAB of 50L 0.2mol/L therein, and temperature is controlled at 80 ℃, utilizes NH simultaneously
4It is 10.0 that OH control mixes liquid pH value.The H that adds 4.0g after 12 hours
2PtCl
66H
2The HAuCl of O and 4.0Kg
43H
2O, the 30%H of molal quantitys such as adding and iodate amine simultaneously
2O
2The aqueous solution stirred 12 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800 ℃ of following N
26 hours required new catalysts of calcining in the gas.Toluene and catalyst are added in the 100L autoclave, feed O
2To 2.0MPa, toluene 10.0Kg, catalyst amount are the 0.5%wt of reactant, when being warming up to 160 ℃, start stirring, react after 8 hours, and product is got supernatant Agilent 6890 gas chromatographic analysis through centrifugal sedimentation.The conversion ratio of toluene is 37.0%, benzaldehyde selectively be 90%.
Claims (6)
1. new catalyst that is used for toluene liquid phase high selectivity catalytic oxidation, it is characterized in that: catalyst is carrier with the alkaline-earth metal composite oxides of high-temperature stability mainly; Be the catalytic oxidation activity center with highly active metal (V, Cr, Mn, Fe, Co, Ni, Cu, Au, Pd, Pt) etc., wherein the content of institute's carried metal element accounts for 0.03～1.0% of catalyst gross mass.
2. the preparation method who is used for toluene liquid phase selective oxidation producing benzaldehyde new catalyst comprises the steps:
(1) mixed aqueous solution of preparation divalent alkaline-earth metal nitrate and aluminum nitrate, control alkaline earth metal cation and aluminum ions mol ratio are 2.0～5.0; Control cationic total concentration at 0.2～1.5mol/L;
(2) preparation ammonium carbonate solution, the mole dosage of control ammonium carbonate and aluminum nitrate is identical, above two solution is mixed the back fully stirred 0.5 hour, and temperature is controlled at 60 ℃, utilizes NH in this process
4The pH value of OH control mixed solution is 8～11.5, and the colloid with gained filters or centrifugal dehydration then, washes to neutrality 100 ℃ of oven dry, 300～700 ℃ of following N of the solid sample of gained with water
2Calcining is 4 hours in the gas, can get corresponding composite oxide of metal;
(3) the gained composite oxide of metal being placed mass percent concentration is 1～10% the halogeno-amine aqueous solution, and adds isopyknic 0.1mol/L template agent aqueous solution therein, and temperature is controlled at 60～100 ℃, and the pH value is controlled 8.0～11.5.Add transition metal nitrate or precious metal salt after 12 hours, keeping the molal quantity of transition metal nitrate is 5～20% of alkaline-earth metal molal quantity, and the noble metal molal quantity is 0.1～1.0% of alkaline-earth metal molal quantity, adds an amount of H simultaneously
2O
2, keep H
2O
2The molal quantity of molal quantity and halogeno-amine equates, stirs 24 hours, and the colloid of gained filters or centrifugal dehydration, 100 ℃ of oven dry, 800～1200 ℃ of following N
2Calcine 2～10 hours required new catalysts in the gas.
3. alkaline earth nitrate as claimed in claim 2 can be one or both in magnesium nitrate, calcium nitrate, strontium nitrate and the barium nitrate.
4. ammonium halide as claimed in claim 2 can be one or both in ammonium fluoride, ammonium chloride, ammonium bromide and the ammonium iodide.
5. template agent as claimed in claim 2 can be a kind of in the triblock copolymer (P123) of softex kw (CTAB), Triton X-100 (TritonX-10) and polyoxyethylene-poly-oxypropylene polyoxyethylene.
6. transition metal nitrate as claimed in claim 2 can be one or both in nitric acid vanadium, chromic nitrate, manganese nitrate, ferrous nitrate, cobalt nitrate, nickel nitrate, the copper nitrate, and precious metal salt can be PdCl
2, HAuCl
43H
2O and H
2PtCl
66H
2Among the O one or both.
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| CN115715986A (en) * | 2022-11-02 | 2023-02-28 | 浙江大洋生物科技集团股份有限公司 | Preparation method of catalyst for generating benzaldehyde by catalytic oxidation of toluene at low temperature and normal pressure |
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