CN102974354B - Catalyst for synthesizing 2,3,6-trimethylphenol and preparation method thereof - Google Patents

Catalyst for synthesizing 2,3,6-trimethylphenol and preparation method thereof Download PDF

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CN102974354B
CN102974354B CN201210488177.1A CN201210488177A CN102974354B CN 102974354 B CN102974354 B CN 102974354B CN 201210488177 A CN201210488177 A CN 201210488177A CN 102974354 B CN102974354 B CN 102974354B
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catalyst
alkali metal
trimethylphenol
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solid
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CN102974354A (en
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肖国民
李遵陕
姜枫
牛磊
熊振
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Southeast University
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Abstract

The invention discloses a method for preparing 2,3,6-trimethylphenol, and the 2,3,6-trimethylphenol is an important intermediate of vitamin E. The method comprises the following steps of: enabling a mixture of metacresol, methanol and water to pass a fixed bed reactor containing an o-position methylation catalyst in a liquid space velocity of 0.4-10 h<-1>, and preparing the 2,3,6-trimethylphenol by carrying out a gas solid phase catalytic reaction under a temperature of 280-450 DEG C and a pressure of 0-10 MPa, wherein the o-position methylation catalyst consists of iron oxide, silicon dioxide and alkali metal oxide, and in the oxides, the metal ion molar ratio of iron, silicon, aluminum and alkali metal is equal to 100:(0.1-10):(0.2-5):(0-1). According to a catalyst for synthesizing the 2,3,6-trimethylphenol and a preparation method thereof, the conversion rate of the metacresol for compounding the 2,3,6-trimethylphenol is 100%, the yield of the 2,3,6-trimethylphenol is above 99.9%, and the service life of the catalyst is longer than 3000 hours.

Description

A kind of method of preparing in order to the catalyst of synthetic 2,3,6-TMP
Technical field
The invention belongs to solid catalyst technical field, relate to a kind of catalyst of vitamin E important intermediate 2,3,6-TMP, and the preparation method of this catalyst.
Background technology
2,3,6-TMP has another name called pseudocuminol, 1-hydroxyl-2,3,6-TMP, 3-hydroxyl pseudocumene, and white or light yellow crystal have strong phenol taste, water insoluble, in alcohol, have good solubility.Basic organic chemical industry raw material 2,3,6-pseudocuminol application is more extensive, except being applied to vitamin E main ring synthetic, also as producing the monomer of heat resistant poly phenylate engineering plastics and the raw material of plastic alloy, this material has good anti-oxidation function simultaneously, be widely used in food additives, feed addictive and cosmetics, and in the production of this external some agricultural chemicals, disinfectant and organic chemical reactions, be also indispensable intermediate and medium.
The preparation method of 2,3,6-TMP mainly contains phynol method at present, caproic acid (4-methyl-3-carbonyl) the own fat method of-6-, and dimethylamino-ethenyl methyl ketone, metacetone method, metacetone, Beta-methyl acryladehyde method, and metacresol method etc.Wherein metacresol method technique have flow process simple, pollute little, side reaction is few, yield is compared with high, is the focus of research always.The key of this production technology is the exploitation of high activity, high selectivity, long life catalytic agent.
The activated aluminum catalyst of previous exploitation, although have the advantages that reaction temperature is low, selectively low, side reaction is more, as Japan Patent JP7853627, UK717588; The second generation magnesia catalyst occurring afterwards, it is active good to have, selective high feature, but reaction temperature too high (600 DEG C), energy consumption is high, easily tie carbon, catalyst life is shorter, as patents such as US4041085, US3446856, US4554267, US4201880.Although the third generation iron of exploitation is that composite catalyst has been obtained certain progress in recent years, but in the catalyst of good catalytic activity, relate to the use of rare precious metals or toxic metals, cause existing potential safety hazard in the higher or Catalyst Production process of Catalyst Production cost, and the preparation of such catalyst and reaction condition require harsh, the service life of catalyst is shorter, its industrial applications is still not ideal enough, as patent US4227024, US4024195, US3716589, EP19476 etc.
Summary of the invention
Technical problem: the object of the invention is to solve 2,3, the 6-pseudocuminol problem that catalyst service life is short, expensive and toxic metals uses in producing, a kind of method of preparing in order to the catalyst of synthetic 2,3,6-TMP is provided, can prepare the catalyst of cheapness, environmental protection, more than this catalyst activity is high, the selective height to 2,3,6-TMP, service life can reach 3000h.
Technical scheme: the present invention prepare in order to synthetic 2,3, the catalyst of 6-pseudocuminol, ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide that the ratio that comprises the amount of substance of nominal price ion is 100:0.1～10:0.2～5:0.01～1.
Wherein, ferriferous oxide can be FeO, Fe 3o 4, Fe 2o 3in any, the combination of any two kinds or three's combination.
Alkali metal oxide can be K 2o, Na 2any of O or both combinations.
Catalyst of the present invention is to prepare by the initial raw materials of each constituent in catalyst is carried out to the steps such as co-precipitation, oven dry, calcining, grinding, dipping, oven dry, calcining.Concrete preparation process is:
1) according to said components proportioning, the presoma of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is dissolved in deionized water, be made into the solution that total concentration is 0.4～0.6mol/L, at room temperature in solution, add precipitating reagent to pH value to be 5-10, aging under stirring condition;
2) solution in step 1) is precipitated to thing after suction filtration, washing precipitate is removed after nitrate ion, under 50～200 DEG C of conditions, dries, and in 350～600 DEG C of calcining 3～10h, obtains blocks of solid;
3) by step 2) in gained blocks of solid be ground into 10～80 object particles, then the alkali metal salt soln that adopts equi-volume impregnating that the solid particle obtaining is put into 0.12mol/L～12.38mol/L floods 10～48h, the volume ratio of alkali metal salt soln and solid particle is 0.5～1, then the solid particle after dipping is dried at 50～200 DEG C, in 350～600 DEG C of calcining 3～10h, the granular disintegration obtaining is catalyst.
Above-mentioned steps 1) in, the presoma of ferriferous oxide is molysite, can be Fe (OAc) 3, FeCl 3, Fe (NO 3) 3, FeSO 4, Fe 2(SO 4) 3, Fe (NO 3) 2, FeC 2o 42H 2a kind of or several combination arbitrarily in O, optimal selection is Fe (NO 3) 3.; The presoma of silica can be a kind of of Ludox, sodium metasilicate and silica gel or several combination arbitrarily, and optimal selection is sodium metasilicate; The presoma of alundum (Al2O3) is aluminium salt, can be Al (OAc) 3, AlCl 3and Al (NO 3) 3a kind of or arbitrarily several combination, optimal selection is Al (NO 3) 3; ; The presoma of alkali metal oxide can be K 2cO 3, Na 2cO 3, KOH, NaOH a kind of or several combination arbitrarily, optimal selection is K 2cO 3
The precipitating reagent using in step 1) can be a kind of or several combination arbitrarily of urea, ammoniacal liquor, NaOH, potassium hydroxide, and optimal selection is ammoniacal liquor.
With the reaction condition of the suitable synthetic 2,3,6-TMP of above-mentioned catalyst be: the reaction temperature of fixed bed reactors is controlled at 280～400 DEG C, particularly 330～380 DEG C, and reaction pressure is 0～10MPa; Reactant is with metacresol: methyl alcohol: the mol ratio of water=1:2～10:0～5 is by fixed bed reactors, especially with metacresol: methyl alcohol: water=1:4～7:1～3 the best; The liquid air speed of reaction mass is 0.4～10h -1, wherein the best is 0.7～2.5h -1.
For ensureing that reaction mass directly enters fixed bed reactor catalyst bed with the temperature requiring, before reactor, set gradually preheater, vaporizer, wherein the temperature of preheater is controlled at 50～180 DEG C, the temperature of vaporizer and is controlled at 180～280 DEG C.What after reacting from fixed bed reactors, flow out is the crude product of 2,3,6-TMP, and crude product, successively through separating methanol, dehydration, then process rectification under vacuum purification, is obtained to purified product.
Beneficial effect: the relative prior art of the present invention, has the following advantages:
First, the main component of catalyst of the present invention is the oxide of iron, aluminium, silicon and alkali metallic sodium or potassium, has avoided the use of rare precious metals and toxic metals, not only environmental protection but also significantly reduced production cost; This catalyst has had to have significantly improved service life, more than reaching 3000h, avoided the frequent production efficiency that more catalyst changeout causes under, significantly improved production efficiency; The conversion ratio of stock yard cresols reaches 100%, and the productive rate of 2,3,6-TMP reaches more than 99.9%, has higher catalytic efficiency.
Secondly, in method for preparing catalyst of the present invention, alkali metal oxide adopts the carrying method of incipient impregnation, has saved adhesives such as utilizing graphite and has made shaping of catalyst technique, has avoided the waste of alkali metal salt; In the forming process of catalyst, avoid the use of the adhesives such as graphite, be dried rear dinectly bruning, grind to form required granular size; Preparation condition is not harsh, more easily realizes; Raw materials is wide in range, and the presoma of each component is comparatively extensive, can select flexibly according to the market price.
Finally, 2,3,6-TMP prepared by the present invention, than commercially available 2,3,6-TMP faint yellow solid, this product is white solid, product has better outward appearance, higher product purity.
Above advantage, has reduced the production cost of 2,3,6-TMP, has improved industrial production efficiency, and has further improved the purity of product, makes product have better exterior appearance, thereby has the higher market competitiveness.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1:
1) accurately take Fe (NO 3) 39H 2o20g, FeCl 310g, Al (NO 3) 39H 2o0.1g, AlCl 30.16g, Al (OAC) 30.22g and Na 2sO 49H 2o0.06g, is dissolved in the deionized water of 350ml, then under room temperature, stirring condition, slowly drips concentration and be the ammonia spirit of 1:1 to pH=6, and time for adding is about 1h, continues to stir 2h and carried out aging under room temperature;
2) then will precipitate suction filtration, washing three times, in the baking oven under 110 DEG C of conditions, dry 24h, to remove wherein moisture, finally in Muffle furnace, under 500 DEG C of conditions, calcine 5h, obtain blocks of solid;
3) gained blocks of solid is ground to 10～80 orders, the impregnated with particles that grinding is completed is in containing 0.014g Na 2cO 3the deionized water solution of 7mL in, dipping 24h is then dried the solid particle after dipping under 110 DEG C of conditions, under 500 DEG C of conditions, calcines 3h.Obtain catalyst Fe 2o 3-SiO 2-Al 2o 3-K 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:0.1:0.2:0.01.
Embodiment 2:
1) accurately take Fe (NO 3) 220g, Fe (C 2h 4) 15g, FeSO 410g, Al (NO 3) 39H 2o1.0g, AlCl 31.20g and Na 2sO 49H 2o6.99g, is dissolved in the deionized water of 350ml, and then, under room temperature, stirring condition, slowly dripping mol ratio is NaOH: ammoniacal liquor=1:1, and the solution that quality total concentration is 30%, to pH=7, continues to stir 2h and carried out aging under room temperature;
2) then will precipitate suction filtration, washing three times, under 110 DEG C of conditions, dry 24h, under 500 DEG C of conditions, calcine 5h, obtain blocks of solid;
3) gained blocks of solid is ground to 10～80 orders, the impregnated with particles that grinding is completed is in containing 1.10g Na 2cO 3, 0.41g KOH the deionized water solution of 8mL in, dipping 24h is then dried under 110 DEG C of conditions, under 500 DEG C of conditions, calcines 3h, obtains catalyst Fe O-SiO 2-Al 2o 3-K 2o, the wherein nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide-the ratio of amount of substance be 100:10:5:1.
Embodiment 3:
1) accurately take Fe (NO 3) 39H 2o15g, Fe 2(SO 4) 310g, Fe (NO 3) 212g, FeSO 410gAl (NO 3) 39H 2o0.4g, AlCl 36H 2o0.25g, Al (OH) C 4h 6o 40.26g and Na 2sO 49H 2o1.5g, silica gel 0.27g, be dissolved in the water of 350ml, and then, under stirring condition, slowly dripping mol ratio is NaOH:KOH=1:3, and the solution that total mass concentration is 30%, to pH=5, continues to stir 2h under room temperature;
2) then will precipitate suction filtration, washing three times, under 110 DEG C of conditions, dry 24h, under 500 DEG C of conditions, calcine 5h, obtain blocks of solid;
3) gained blocks of solid is ground to 10～80 orders ,-the impregnated with particles of having ground is in containing 0.012g Na 2cO 3, 0.05g K 2cO 36.7mL deionized water solution in, dipping 24h, then under 110 DEG C of conditions, dry, under 500 DEG C of conditions, calcine 3h, obtain catalyst Fe 2o 3-FeO-SiO 2-Al 2o 3-K 2o-Na 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:5:2:0.5.
Embodiment 4:
1) take Fe (NO 3) 39H 2o30g, FeSO 420.64g, Al (NO 3) 39H 2o2.79g and Na 2sO 49H 2o0.45g ,-be dissolved in the deionized water of 350ml, then under stirring condition, slowly drip concentration and be 30% sodium hydroxide solution to pH=8, under-room temperature, continue to stir 2h;
2) then will precipitate suction filtration, washing three times, under 60 DEG C of conditions, dry 24h, under-480 DEG C of conditions, calcine 5h, obtain blocks of solid;
3) blocks of solid is ground to 10～80 orders.The impregnated with particles that grinding is completed is in containing 0.05gNa 2cO 3the deionized water solution of 5mL in, dipping 24h is then dried under 110 DEG C of conditions, under 500 DEG C of conditions, calcines 3h.Obtain catalyst Fe 3o 4-SiO 2-Al 2o 3-Na 2o, wherein the ratio of the amount of substance of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide nominal price ion is 100:1:5:0.5.
Embodiment 5:
1) take Fe (NO 3) 39H 2o70g, Al (NO 3) 39H 2o1.30g and Na 2sO 49H 2o1.23g, is dissolved in the deionized water of 350ml, then under stirring condition, slowly drips concentration and be 30% ammonia spirit to pH=7, continues to stir 2h under-room temperature;
2) then will precipitate suction filtration, washing three times, under 110 DEG C of conditions, dry 24h, under-600 DEG C of conditions, calcine 5h, obtain blocks of solid;
3) gained blocks of solid is ground to 10～80 orders.-the impregnated with particles of having ground is in containing 0.108g K 2cO 37mL deionized water solution in, dipping 24h, then under 110 DEG C of conditions, dry, under 500 DEG C of conditions, calcine 3h, obtain catalyst Fe 2o 3-SiO 2-Al 2o 3-K 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:2.5:2:0.9.
Embodiment 6:
1) accurately take FeCl 330g, Fe (NO 3) 216g, AlCl 39H 2o0.20g, Al (OH) C 4h 6o 40.26g and Na 2sO 49H 2o0.62g, Ludox 0.2g, be dissolved in the deionized water of 400mL, under room temperature, stirring condition, is titrated to pH=6 with the urea liquid that concentration is 35%, continues to stir aging 4h;
2) gained is precipitated to suction filtration, washing three times, under 80 DEG C of conditions, dry, calcine 6h at 350 DEG C, obtain blocks of solid;
3) estimate to be ground to 10-80 order by block gained, the impregnated with particles of having ground in the deionized water solution of the 6.5mL that contains 0.4g NaOH, dipping 8h, then in 80 DEG C dried, 350 DEG C calcine 5h, obtain Fe 3o 4-Fe 2o 3-SiO 2-Al 2o 3-Na 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:2.7:0.9:1.
Embodiment 7:
1) accurately take Fe (OAc) 315g, FeSO 431.6g, Al (OAc) 30.82g and Ludox 0.6g, be dissolved in the deionized water solution of 360mL, under room temperature, stirring condition, with amount of substance ratio be urea: KOH=3:1, the solution that total mass concentration is 50% is titrated to pH=9, under room temperature condition continue stir aging 5h;
2) gained is precipitated to suction filtration, washing three times, under dry at 90 DEG C, 450 DEG C of conditions, calcine 2h, obtain blocks of solid;
3) gained blocks of solid is ground to 10-80 order, the graininess of having ground impregnated in and contains 0.106gNa 2cO 3the deionized aqueous solution of 7mL in, dipping 3h calcines 4h under 120 DEG C of dry, 390 DEG C of conditions, obtains Fe 3o 4-FeO-SiO 2-Al 2o 3-Na 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:5:2:0.5.
Embodiment 8:
1) accurately take FeSO 455.6g, Al (OAc) 30.408g, Al (NO 3) 39H 2o0.75g and silica gel 0.2g, Ludox 0.1g, be dissolved in 380mL deionized water solution, under room temperature, stirring condition, with amount of substance ratio be NaOH:KOH: ammoniacal liquor=1:1:1, total concentration is that 30% solution is titrated to pH=5.5, continues to stir aging 1h under room temperature;
2) by gained sediment suction filtration, washing three times, in 100 DEG C of oven dry, under 420 DEG C of conditions, calcine 7h, obtain blocks of solid;
3) gained blocks of solid is ground to 10-80 order, the graininess of having ground impregnated in and contains 0.106gNa 2cO 3, 0.138g K 2cO 3the deionized aqueous solution of 7mL in, dipping 7h calcines 4h under 120 DEG C of dry, 420 DEG C of conditions, obtains FeO-SiO 2-Al 2o 3-Na 2o-K 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:6:2:1.
Embodiment 9:
1) accurately take FeCl 39g, Fe (NO 3) 39H 2o13.5g, FeSO 49.3g, Fe 2(SO 4) 36.67g, Fe (NO 3) 26g, FeC 2o 45.8g, AlCl 39H 2o3.75g and Na 2sO 49H 2o3.6g, is dissolved in the deionized water solution of 360mL, and the urea liquid with 35% under room temperature, stirring condition is precipitated to pH=6, continues aging 6h under stirring condition;
2) by gained sediment suction filtration, washing three times, in 100 DEG C of oven dry, under 420 DEG C of conditions, calcine 7h, obtain blocks of solid;
3) gained blocks of solid is ground to 10-80 order, the graininess of having ground impregnated in the deionized aqueous solution of the 6mL that contains 0.112g KOH, and dipping 7h calcines 4h under 120 DEG C of dry, 420 DEG C of conditions, obtains Fe 2o 3-FeO-SiO 2-Al 2o 3-Na 2o-K 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:3:5:1.
Embodiment 10:
1) accurately take FeCl 39g, Fe (NO 3) 39H 2o13.5g, FeSO 49.3g, Fe 2(SO 4) 33.35g, Al (OAc) 31.3g, AlCl 30.80g, AlCl 39H 2o2.2g and Na 2sO 49H 2o1.2g, is dissolved in the deionized water solution of 320mL, and the ammonia spirit with 35% under room temperature, stirring condition is precipitated to pH=6, continues aging 6h under stirring condition;
2) by gained sediment suction filtration, washing three times, in 100 DEG C of oven dry, under 480 DEG C of conditions, calcine 4h, obtain blocks of solid;
3) gained blocks of solid is ground to 10-80 order, the graininess of having ground impregnated in and contains 0.166g K 2cO 3the deionized aqueous solution of 6mL in, dipping 7h calcines 4h under 120 DEG C of dry, 480 DEG C of conditions, obtains Fe 3o 4-Fe 2o 3-FeO-SiO 2-Al 2o 3-Na 2o-K 2o, wherein the ratio of the amount of substance of the nominal price ion of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is 100:3:4.5:0.6.
Utilize above-mentioned catalyst to prepare 2,3, the method of 6-pseudocuminol, be reaction mass that metacresol, first alcohol and water are mixed by the fixed bed reactors of ortho-methylation catalyst are housed, be 280～450 DEG C, the liquid air speed 0.4～10h of pressure 0～10MPa, reaction mass in temperature -1condition under carry out gas-solid phase reaction, catalyze and synthesize 2,3,6-TMP.The ratio of the molal quantity of reaction mass is metacresol: methyl alcohol: water=1:2～10:0～5, and taking metacresol: methyl alcohol: water=1:4～7:1～3 are as good.The liquid air speed of reaction mass is with 0.7～2.5h -1for good.The product crude product obtaining after fixed bed reactors reaction through separating methanol, dehydration, then process rectification under vacuum purification, obtains purified product successively.

Claims (3)

1. prepare the method in order to the catalyst of synthetic 2,3,6-TMP, it is characterized in that, the method comprises the following steps:
1) according to following component proportion: ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide that the ratio of the amount of substance of nominal price ion is 100:0.1～10:0.2～5:0.01～1, the presoma of ferriferous oxide, silica, alundum (Al2O3) and alkali metal oxide is dissolved in deionized water, be made into the solution that total concentration is 0.4～0.6mol/L, at room temperature in described solution, add precipitating reagent to pH value to be 5-10, aging under stirring condition;
2) solution in described step 1) is precipitated to thing after suction filtration, washs described sediment and remove after nitrate ion, under 50～200 DEG C of conditions, dry, in 350～600 DEG C of calcining 3～10h, obtain blocks of solid;
3) by described step 2) in gained blocks of solid be ground into 10～80 object particles, then adopt equi-volume impregnating, the alkali metal salt soln of the solid particle obtaining being put into 0.12mol/L～12.38mol/L floods 10～48h, the volume ratio of described alkali metal salt soln and solid particle is 0.5～1, then the solid particle after dipping is dried at 50～200 DEG C, in 350～600 DEG C of calcining 3～10h, the granular disintegration obtaining is catalyst.
2. prepare according to claim 1 the method in order to the catalyst of synthetic 2,3,6-TMP, it is characterized in that, in described step 1), the presoma of ferriferous oxide is Fe (OAc) 3, FeCl 3, Fe (NO 3) 3, FeSO 4, Fe 2(SO 4) 3, Fe (NO 3) 2and FeC 2o 42H 2a kind of or several combination arbitrarily in O, the presoma of silica is a kind of or several combination arbitrarily in Ludox, sodium metasilicate and silica gel, the presoma of alundum (Al2O3) is Al (OAc) 3, AlCl 3and Al (NO 3) 3a kind of or arbitrarily several combination, the presoma of alkali metal oxide is K 2cO 3, Na 2cO 3, KOH and NaOH a kind of or several combination arbitrarily.
3., it is characterized in that in order to the method for the catalyst of synthetic 2,3,6-TMP according to preparation described in claim 1 or 2, in described step 1), precipitating reagent is a kind of or several combination arbitrarily of urea, ammoniacal liquor, NaOH, potassium hydroxide.
CN201210488177.1A 2012-11-26 2012-11-26 Catalyst for synthesizing 2,3,6-trimethylphenol and preparation method thereof Expired - Fee Related CN102974354B (en)

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