CN104415762B - A kind of method of phenol type substances ortho-methylation catalyst and preparation method thereof and synthesis ortho-methylated phenol compounds - Google Patents
A kind of method of phenol type substances ortho-methylation catalyst and preparation method thereof and synthesis ortho-methylated phenol compounds Download PDFInfo
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Abstract
The method that the invention discloses a kind of phenol type substances ortho-methylation catalyst and preparation method thereof and the ortho-methylated compound of synthesizing phenol class, it is a kind of composite oxides containing ferrum, magnesium, cerium, vanadium and potassium/sodium, and each component molar is than for Fe:Mg:Ce:V:K/Na=100:(1～50): (0.5～5): (0.5～5): (0.1～0.5).Its preparation method is for being dissolved in alcohols solvent wiring solution-forming A by soluble ferric iron salt, magnesium salt in the mixing of required ratio；The ammonium metavanadate of required ratio, cerium salt and potassium/sodium compound are joined wiring solution-forming B in the strong aqua ammonia of 4～5 times of iron salt amount of substance used；Under room temperature ultrasound condition by solution A and solution B by and slowly mix in the way of flowing, continue ultrasonic 30min after adding；Gained precipitation is filtered, washs, and dries, finally roasting 8 hours at 450 DEG C；By finely ground for the solid after roasting, compression molding is catalyst.Catalyst activity of the present invention is high, prepare simple, nontoxic, good stability, long service life, and ortho selectivity is high, and by-product is few.
Description
Technical field
The present invention relates to a kind of phenol type substances ortho-methylation catalyst and preparation method thereof and the method using this catalyst synthesis ortho-methylated phenol compounds.
Background technology
The ortho-methylated product of phenol type substances include orthoresol, 2,6-xylenols, 2,5-xylenols, 2,4-xylenol, 2,3-xylenols, 2,3,4-tri-cresol, 2,3,5-tri-cresol, 2,3,6-tri-cresol, 2,4,5-tri-cresol, 2,4,6-tri-cresol etc., they are all important fine-chemical intermediates.
The ortho-methylated product of phenol type substances is to be obtained by reacting by phenol compound and methanol vapor phase ortho-alkylating.Reaction used catalyst can be generally divided into two big classes: i.e. molecular sieve and metal oxide catalyst.Owing to being easily simultaneously generated O-alkylation and C-alkylate when molecular sieve makees catalyst, therefore all there is the problem such as selectivity and less stable in this catalyst system, and this reaction is shown good catalytic performance by the catalyst such as metal-oxide and spinel oxide.
Use Al the earliest2O3, its catalysis activity and selectivity is low, and by-product is many, separation difficulty, is replaced by MgO series catalysts gradually.The catalysis activity of MgO series catalysts and ortho selectivity compare Al2O3Height, but required reaction temperature is high, and energy consumption is big, poor stability.Reaction temperature needed for the Fe-series catalyst of the eighties exploitation is substantially reduced, and catalysis activity is high.Patent about Fe-series catalyst is a lot.
A kind of alkalescence Fe/Mg/M composite oxide catalysts disclosed in CN101513614A, CN101514144A and CN101514145A.This catalyst preparing is simple, and nontoxic, desired reaction temperature is relatively low, and orthoresol selectivity is higher.But the activity of catalyst and stability need to be improved further.
Summary of the invention
It is an object of the invention to provide a kind of catalyst activity and the high Catalysts and its preparation method for the synthesizing phenol ortho-methylated compound of class material of stability.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of catalyst synthesizing ortho phenol compounds, it is a kind of composite oxides containing ferrum, magnesium, cerium, vanadium and potassium/sodium, and each component molar is than for Fe:Mg:Ce:V:K/Na=100:(1～50): (0.5～5): (0.5～5): (0.1～0.5).
The preparation method of described catalyst comprises the following steps:
1. soluble ferric iron salt, magnesium salt are dissolved in alcohols solvent wiring solution-forming A in the mixing of required ratio；
2. the ammonium metavanadate of required ratio, cerium salt and potassium (sodium) compound are joined wiring solution-forming B in the strong aqua ammonia of 4～5 times of iron salt amount of substance used；
3. under room temperature ultrasound condition by solution A and solution B by and slowly mix in the way of flowing, continue ultrasonic 30min after adding；
4. gained precipitation is filtered, washs, and dries, finally roasting 8 hours at 450 DEG C；
5. by finely ground for the solid after roasting, compression molding is catalyst.
Iron salt used by the present invention is Fe (OAc)2OH、FeCl3、Fe(NO3)3、Fe2(SO4)3Deng；Magnesium salt is Mg (OAc)2、Mg(NO3)2、MgCl2Deng；Cerium salt is Ce (OAc)3、CeCl3、Ce(NO3)3Deng；It is KOH, K containing potassium (or sodium) compound2CO3、KNO3、KCl、NaOH、Na2CO3、NaNO3, NaCl etc.；Alcohols solvent is the lower alcohols such as methanol, ethanol, propanol；Strong aqua ammonia (concentration is 25%～28%) is as precipitant.
The main physical property of described catalyst: specific surface 150～180m2/ g, pore volume 0.50～0.80mL/g, bulk density 1.00～1.20g/mL, intensity 20～40N/ grain.
The present invention also provides for a kind of method synthesizing ortho phenol compounds: mix with carrier gas after ortho position has at least the gasification of the phenol type substances of a hydrogen atom, methanol, water mixed solution, by the fixed bed reactors equipped with above-mentioned catalyst, carry out vapor phase alkylation and synthesize ortho-methylated product.
Described ortho position has at least the phenol type substances of a hydrogen atom to be phenol, orthoresol, paracresol, metacresol, 2,3-xylenols, 2,4-xylenols, 2,5-xylenols, 3,4-xylenols, 3,5-xylenols etc.；Carrier gas is noble gas；Reaction temperature 310～360 DEG C, pressure is normal pressure～2.0MPa.
The present invention can be used for manufacture include orthoresol, 2,6-xylenols, 2,5-xylenols, 2,4-xylenols, 2,3-xylenols, 2,3,4-tri-cresol, 2,3,5-tri-cresol, 2,3, the ortho-methylated phenol compounds such as 6-tri-cresol, 2,4,5-tri-cresol, 2,4,6-tri-cresol.
The invention have the advantage that catalyst preparing is simple, activity is high, good stability, catalyst can one way more than stable operation 2000h；Phenol type substances conversion ratio is more than 50%, and ortho selectivity is high, reaches more than 99%, and by-product is few, is with a wide range of applications.
Detailed description of the invention
Below according to specific embodiment, the invention will be further described:
Embodiment 1
Weigh 404.0gFe (NO3)3·9H2O、2.56gMg(NO3)2·6H2O and 1.63gCe (NO3)3·6H2O mixing is dissolved in 1000mL ethanol, then weighs 0.59g ammonium metavanadate and 0.08g sodium nitrate mixing is dissolved in the strong aqua ammonia of 700mL28%, under room temperature ultrasound condition by two kinds of solution by and slowly mix in the way of flowing, continue ultrasonic 30min after adding；Gained precipitation is filtered, washs, and dries, finally roasting 8 hours at 450 DEG C；By finely ground for the solid after roasting, compression molding is Fe100Mg1Ce0.5V0.5Na0.1Catalyst.
By above-mentioned for 40mL Catalyst packing in rustless steel fixed bed reactors, raw material is phenol: methanol: water=1:3:1(mol ratio), control reaction temperature between 320～350 DEG C, normal pressure, mass space velocity is 1.0hr-1, carrier gas is N2Its flow velocity is 20mL/min, catalyst one way stable operation 2000h, phenol average conversion 54.85%, orthoresol average selectivity 90.45%, total ortho selectivity 99.17%.
Embodiment 2
Weigh Fe (OAc)2OH190.94g、MgCl2·6H2O50.83g、CeCl3·7H2O9.31g mixing is dissolved in 800mL methanol, then weighs 3.51g ammonium metavanadate and the mixing of 0.28g potassium carbonate is dissolved in the strong aqua ammonia of 800mL25%, and other operation, with embodiment 1, obtains catalyst Fe100Mg25Ce2.5V3.0K0.2。
By above-mentioned for 40mL Catalyst packing in rustless steel fixed bed reactors, raw material is phenol: methanol: water=1:5:1(mol ratio), reaction temperature 330～360 DEG C, pressure 0.2MPa, mass space velocity is 0.5hr-1, catalyst one way stable operation 2000h, phenol average conversion 99.30%, 2,6-xylenol average selectivity > 85%, total ortho position selection rate > 98%.
Embodiment 3
Weigh FeCl3·6H2O270.30g、Mg(OAc)2·4H2O107.24g, cerous acetate 15.86g mixing is dissolved in 800mL propanol, then weighs 5.85g ammonium metavanadate and the mixing of 0.29g sodium chloride is dissolved in the strong aqua ammonia of 800mL25%, and other operation, with embodiment 1, obtains catalyst Fe100Mg50Ce5V5Na0.5。
By above-mentioned for 40mL Catalyst packing in rustless steel fixed bed reactors, raw material is paracresol: methanol: water=1:5:1(mol ratio), reaction temperature 340～360 DEG C, pressure 0.5MPa, during liquid, mass space velocity is 0.5hr-1, catalyst one way stable operation 2000h, metacresol average conversion 99.10%, 2,4,6-tri-cresol average selectivity 91.30%, total ortho position average selectivity 99.18%.
Embodiment 4
Weigh 200gFe2(SO4)3、25.64gMg(NO3)2·6H2O and Ce (NO3)3·6H2O6.52g mixing is dissolved in 1000mL ethanol, then weighs 3.51g ammonium metavanadate and the mixing of 0.51g potassium nitrate is dissolved in the strong aqua ammonia of 730mL26%, and other operation, with embodiment 1, obtains catalyst Fe100Mg10Ce2V3K0.5。
By above-mentioned for 40mL Catalyst packing in rustless steel fixed bed reactors, raw material is 2,4-xylenols: methanol: water=1:3:1(mol ratio), reaction temperature 310～340 DEG C, pressure 1.0MPa, mass space velocity is 1.5hr-1, carrier gas is N2Its flow velocity is 20mL/min, catalyst one way stable operation 2000h, 2,4-xylenol average conversion 99.05%, 2,4,6-tri-cresol average selectivity 99.15%.
Embodiment 5
Weigh 404.0gFe (NO3)3·9H2O、102.56gMg(NO3)2·6H2O and 9.51gCe (NO3)3·6H2O mixing is dissolved in 1200mL ethanol, then weighs 2.34g ammonium metavanadate and the mixing of 0.20g sodium hydroxide is dissolved in the strong aqua ammonia of 700mL28%, and other operation, with embodiment 1, obtains Fe100Mg40Ce3V2Na0.5Catalyst.
By above-mentioned for 40mL Catalyst packing in rustless steel fixed bed reactors, raw material is 3,5-xylenols: methanol: water=1:3:2(mol ratio), reaction temperature 310～340 DEG C, pressure 2.0MPa, mass space velocity is 1.0hr-1, carrier gas is N2Its flow velocity is 20mL/min, catalyst one way stable operation 2000h, 3,5-xylenol average conversion 51.30%, 2,3,5-tri-cresol average selectivity 91.40%.
Claims (6)
1. a phenol type substances ortho-methylation catalyst, it is characterized in that: be a kind of composite oxides containing ferrum, magnesium, cerium, vanadium and potassium/sodium, each component molar is than for Fe:Mg:Ce:V:K/Na=100:(1～50): (0.5～5): (0.5～5): (0.1～0.5).
2. the preparation method of catalyst described in a claim 1, it is characterised in that: comprise the following steps:
1. soluble ferric iron salt, magnesium salt are dissolved in alcohols solvent wiring solution-forming A in the mixing of required ratio；
2. the ammonium metavanadate of required ratio, cerium salt and potassium/sodium compound are joined wiring solution-forming B in the strong aqua ammonia of 4-5 times of iron salt amount of substance used；
3. under room temperature ultrasound condition by solution A and solution B by and slowly mix in the way of flowing, continue ultrasonic 30min after adding；
4. gained precipitation is filtered, washs, and dries, finally roasting 8 hours at 450 DEG C；
5. by finely ground for the solid after roasting, compression molding is described catalyst.
3. preparation method according to claim 2, it is characterised in that: iron salt is Fe (OAc)2OH、FeCl3、Fe(NO3)3、Fe2(SO4)3In one；Alcohols solvent is the one in methanol, ethanol, propanol；Magnesium salt is Mg (OAc)2、Mg(NO3)2、MgCl2In one；Cerium salt is Ce (OAc)3、CeCl3、Ce(NO3)3In one；It is KOH, K containing potassium/sodium compound2CO3、KNO3、KCl、NaOH、Na2CO3、NaNO3, one in NaCl.
4. the method synthesizing ortho phenol compounds, it is characterized in that: include that ortho position has at least the phenol type substances of a hydrogen atom, methanol, water mixed solution mix with carrier gas after gasifying, by the fixed bed reactors equipped with catalyst, carrying out vapor phase alkylation synthesis ortho phenol compounds, wherein said catalyst is the catalyst described in claim 1.
5. method according to claim 4, it is characterised in that: ortho position have at least the phenol type substances of a hydrogen atom be phenol, 2-sylvan, 4-sylvan, 3-sylvan, 2,3-xylenols, 2,4-xylenol, 2, one in 5-xylenol, 3,4-xylenols, 3,5-xylenols.
6. method according to claim 4, it is characterised in that: described vapor phase alkylation reaction temperature 310～360 DEG C, pressure is normal pressure～2.0MPa.
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| CN104725195A (en) * | 2015-04-13 | 2015-06-24 | 江苏三吉利化工股份有限公司 | Method for preparing o-cresol and 2, 6-xylenol by catalysis of heteropolyacid |
| CN109833878A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of alkylation of phenol catalyst and its synthetic method of production and 2,6- xylenol |
| CN109939708A (en) * | 2019-04-03 | 2019-06-28 | 衷晟 | A kind of methyl phenolic compounds manufacturing method |
| CN111170833A (en) * | 2020-02-18 | 2020-05-19 | 大连中沐化工有限公司 | Method for inhibiting generation of aryl methyl ether through phenol ortho-methylation reaction |
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| CN101513614A (en) * | 2009-04-05 | 2009-08-26 | 湖南长岭石化科技开发有限公司 | Phenol ortho-methylation catalyst and preparation method thereof |
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