CN103084213B - Catalyst for synthesizing 2,6-xylenol as well as preparation method of catalyst and method for synthesizing 2,6-xylenol - Google Patents
Catalyst for synthesizing 2,6-xylenol as well as preparation method of catalyst and method for synthesizing 2,6-xylenol Download PDFInfo
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Abstract
The invention discloses a catalyst for synthesizing 2,6-xylenol as well as a preparation method of the catalyst and a method for synthesizing 2,6-xylenol. The catalyst is a composite oxide of Fe, Mg and heteropolyacid/salt with a molar ratio of 1:(0.01-0.05):(0.01-0.04). The preparation method of the catalyst comprises the following steps of: mixing and dissolving soluble iron slat, magnesium salt and heteropolyacid/salt into an alcohol solvent in proportion to obtain a solution A; adding polyethylene glycol to stronger ammonia water to obtain a solution B; slowly mixing the solution A with the solution B under a normal-temperature ultrasonic condition in a cocurrent flow mode, and continuously stirring for 30 minutes after the polyethylene glycol is added; filtering, washing and drying the obtained precipitates; and grinding and tabletting the roasted solid to obtain the catalyst. The preparation method of the catalyst disclosed by the invention is adopted, so that the phenol conversion rate is as high as 99%, the ortho-position selectivity is as high as 99%, and the service life of the catalyst is more than 2000 hours. Moreover, the catalyst is high in low-temperature activity, simple in preparation method, non-toxic and good in stability.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of a kind of synthesis 2,6-xylenol and use the method for this catalyst synthesis 2,6-xylenol.
Background technology
2,6-xylenol is the raw material synthesizing polyphenylene oxide resin (PPE), photograph with medicament, agricultural chemicals, medicine, polyester and polyether resin, applies very extensive.
Early stage 2,6-xylenols are separated to obtain from coal tar and petroleum cracking product, yields poorly, of poor quality.First N.Cullinane in 1945 etc. adopt phenol and methyl alcohol to carry out gas phase catalysis methylation reaction, have synthesized 2,6-xylenols.The synthesis of selective of 2,6-xylenol and the raising of conversion ratio depend primarily on updating of its ortho-methylation catalyst.
The phenol ortho-methylation catalyst used the earliest is Al
2o
3, due to its catalytic activity and the selective very low of ortho-methylated replacement, generate a large amount of contrapositions and a position methylated phenol simultaneously, as Japan Patent JP7853627, therefore gradually by MgO catalyst based replace.It is catalyst based that US3446856, US4041085, US4201880, US4554267 etc. all provide MgO.Although MgO is catalyst based compare Al
2o
3catalytic activity high and ortho selectivity is good, but required reaction temperature is very high, poor stability, thus causes energy consumption large.Therefore MgO catalyst based gradually replace by emerging Fe-series catalyst, as the patents such as US3716589, US3953529, US4024195, US4227024, EP19476 all disclose respective Fe-series catalyst.The catalyst most wherein especially provided with US4429171 is representative, this catalyst is made up of Fe, In, Cr, Si, K five kinds of elements, in preparation 2, after using this catalyst in the gas phase catalytic reaction of 6-xylenol, reaction temperature is down to 300 ~ 400 DEG C, reaction mixture liquid air speed 0.1 ~ 5h
-1, phenol conversion reaches as high as the selective highest order 99.6% of 100%, 2,6-xylenol.But find in the application, the preparation reappearance of this catalyst is poor, is difficult to obtain the catalyst prod with stability.CN1634656A provides a kind of catalyst be made up of Fe, In, Cr, Si, Ca, K, C seven kinds of elements, and can reach 99% for the synthesis of phenol conversion during 2,6-xylenol, ortho selectivity reaches 97%.But this catalytic component is many, preparation is complicated, and initial reaction temperature is high.
Summary of the invention
The object of the present invention is to provide that a kind of low temperature active is high, method for making is simple, the Catalysts and its preparation method of synthesis 2, the 6-xylenol of nontoxic, good stability.
To achieve these goals, the technical solution used in the present invention is as follows:
The catalyst of a kind of synthesis 2,6-xylenol is a kind of Fe, Mg and heteropoly acid/salt composite oxides, and each component molar is than being Fe:Mg: heteropoly acid/salt=1:(0.01 ~ 0.05): (0.01 ~ 0.04).
Present invention also offers the preparation method of the catalyst of a kind of synthesis 2,6-xylenol wherein, the method comprises the following steps:
1. by soluble ferric iron salt, magnesium salts and heteropoly acid/salt are dissolved in alcohols solvent wiring solution-forming A in required ratio mixing;
2. polyethylene glycol PEG is joined wiring solution-forming B in concentrated ammonia liquor, wherein polyethylene glycol consumption is 1% ~ 10% of iron oxide quality in catalyst, and concentrated ammonia liquor consumption is 5 ~ 10 times of molysite molal quantity used;
3. under normal temperature ultrasound condition, solution A and solution B are slowly mixed in the mode also flowed, add rear continuation and stir 30min;
4. gained precipitation is filtered, and washing, then dries, then 450 DEG C of roastings 8 hours;
5. by the solid porphyrize after roasting, compressing tablet is gained catalyst.
Heteropoly acid/salt in catalyst of the present invention has stronger acidity, the Acidity of Aikalinity of adjustable catalyst, thus effectively improves activity and the stability of catalyst, and the conversion ratio of phenol can be made to improve, and the service life of catalyst extends.
Soluble ferric iron salt of the present invention can be Fe (NO
3)
3, FeCl
3, Fe (OAc)
3deng; Solubility magnesium salts can be Mg (NO
3)
2, MgCl
2, Mg (OAc)
2deng; Heteropoly acid (salt) can be phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, sodium phosphotungstate, sodium phosphomolybdate, silicotungstic sodium, silicomolybdic acid sodium etc.: alcohols solvent can be methyl alcohol, ethanol or propyl alcohol etc.; PEG(mean molecule quantity is 800 ~ 4000) as dispersant, concentrated ammonia liquor (concentration is 25 ~ 28%) is as precipitating reagent.
Present invention also offers the method for a kind of synthesis 2,6-xylenol, be included in and be equipped with in the reaction tube of catalyst, phenol, first alcohol and water are contacted, and lead to inert carrier gas in reaction tube, it is characterized in that: described catalyst is catalyst provided by the invention.
Described contact conditions comprises phenol, first alcohol and water mol ratio is 1:(3 ~ 5): (0.5 ~ 1), pressure is normal pressure ~ 0.5MPa, and temperature is 330 ~ 380 DEG C, air speed 0.4 ~ 2 hr
-1, flow rate of carrier gas scope is 10 ~ 25mL/min.
Add suitable quantity of water in reaction mixture, with diluting reaction gaseous mixture, make its reacting balance, reduce the generation of catalyst upper surface carbon deposit, thus improve catalyst stability.The mol ratio of water and phenol is 0.5 ~ 1:1, and ratio is too large, can reduce reaction efficiency, increases energy consumption.
Catalyst provided by the present invention is a kind of ortho selectivity alkylation catalyst, is not only applicable to, by phenol compound and methyl alcohol Reactive Synthesis 2,6-xylenol, also be applicable to the preparation of 2-methylphenol, 2,4,6-trimethylbenzene phenolic compounds.Meanwhile, be also suitable for, by phenol compound and other ortho alkyl phenol compound of alkylol Reactive Synthesis, being with a wide range of applications.
Advantage of the present invention is: catalyst low-temperature activity is high, method for making is simple, nontoxic, stability
Good.Phenol one way average conversion is higher, reaches more than 99%, and ortho selectivity is up to more than 99%; Catalyst is longer for service life, and catalyst can one way more than stable operation 2000h.
Detailed description of the invention
According to specific embodiment, the invention will be further described below:
embodiment 1
Take Fe (NO
3)
39H
2o404g, Mg (NO
3)
26H
2o12.82g and phosphotungstic acid 28.80g mixing is dissolved in 800mL ethanol, then under normal temperature ultrasound condition by its with containing 4gPEG 28% 700mL concentrated ammonia liquor with and the mode that flows slowly mix, continue after adding to stir 30min, then by sedimentation and filtration, washing, at 120 DEG C, dry 6h.Gained solid is roasting 8h at 450 DEG C again, finally by solid porphyrize, is broken into 10 ~ 20 object granules again and is gained catalyst Fe Mg after compressing tablet
0.05pW
0.01(PW represents phosphotungstic acid).
By above-mentioned for 40mL Catalyst packing in stainless steel fixed bed reactors, raw material is phenol: methyl alcohol: water=1:5:1(mol ratio), mass space velocity is 0.4 hr
-1, carrier gas is N
2its flow velocity is 20 mL/min, and reaction normal pressure, catalyst one way stable operation 2000 h, reaction result sees the following form.
embodiment 2
Take Fe (OAc)
3233.05g, Mg (OAc)
21.42g and silicomolybdic acid 94.55g mixing is dissolved in 800mL ethanol, then under normal temperature ultrasound condition by its with containing 8gPEG 28% 700mL concentrated ammonia liquor with and the mode that flows slowly mix, continue after adding to stir 30min, then by sedimentation and filtration, washing, at 120 DEG C, dry 6h.Gained solid is roasting 8h at 450 DEG C again, finally by solid porphyrize, is broken into 10 ~ 20 object granules again and is gained catalyst Fe Mg after compressing tablet
0.01sM
0.04(SM represents silicomolybdic acid).
By above-mentioned for 40mL Catalyst packing in stainless steel fixed bed reactors, raw material is phenol: methyl alcohol: water=1:4:0.5(mol ratio), mass space velocity is 0.5 hr
-1, carrier gas is N
2its flow velocity is 15 mL/min, reaction pressure 0.2MPa, and catalyst one way stable operation 2000 h, reaction result sees the following form.
embodiment 3
Take FeCl
3162.21g, MgCl
26H
2o6.10g and sodium phosphomolybdate 37.82g mixing is dissolved in 800mL ethanol, then under normal temperature ultrasound condition by its with containing 4gPEG 28% 700mL concentrated ammonia liquor with and the mode that flows slowly mix, continue after adding to stir 30min, then by sedimentation and filtration, washing, at 120 DEG C, dry 6h.Gained solid is roasting 8h at 450 DEG C again, finally by solid porphyrize, is broken into 10 ~ 20 object granules again and is gained catalyst Fe Mg after compressing tablet
0.03(PMNa)
0.02(PMNa represents sodium phosphomolybdate).
By 40mL Catalyst packing in stainless steel fixed bed reactors, raw material is phenol: methyl alcohol: water=1:3:0.5(mol ratio), mass space velocity is 1.0 hr
-1, carrier gas is N
2its flow velocity is 10 mL/min, reaction pressure 0.2MPa, and catalyst one way stable operation 2000 h, reaction result sees the following form.
embodiment 4
Take Fe (NO
3)
39H
2o404g, Mg (NO
3)
29H
2o10.24g and silicotungstic sodium 6.60g mixing is dissolved in 800mL ethanol, then under normal temperature ultrasound condition by its with containing 0.8gPEG 28% 700mL concentrated ammonia liquor with and the mode that flows slowly mix, continue after adding to stir 30min, then by sedimentation and filtration, washing, at 120 DEG C, dry 6h.Gained solid is roasting 8h at 450 DEG C again, finally by solid porphyrize, is broken into 10 ~ 20 object granules again and is gained catalyst Fe Mg after compressing tablet
0.04(SWNa)
0.02(SWNa represents silicotungstic sodium).
By above-mentioned for 40mL Catalyst packing in stainless steel fixed bed reactors, raw material is phenol: methyl alcohol: water=1:4:0.5(mol ratio), mass space velocity is 2.0hr
-1, carrier gas is N
2its flow velocity is 25 mL/min, reaction pressure 0.5MPa, and catalyst one way stable operation 2000 h, reaction result sees the following form.
Claims (5)
1. the catalyst of synthesis 2, a 6-xylenol, is characterized in that: be a kind of Fe, Mg and heteropoly acid/salt composite oxides, and each component molar is than being Fe:Mg: heteropoly acid/salt=1:(0.01 ~ 0.05): (0.01 ~ 0.04).
2. catalyst according to claim 1, is characterized in that: heteropoly acid/salt is the one in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, sodium phosphotungstate, sodium phosphomolybdate, silicotungstic sodium, silicomolybdic acid sodium.
3. a preparation method for catalyst described in claim 1 or 2, is characterized in that: comprise the following steps:
1. by soluble ferric iron salt, magnesium salts and heteropoly acid/salt are dissolved in alcohols solvent wiring solution-forming A in required ratio mixing;
2. polyethylene glycol is joined wiring solution-forming B in concentrated ammonia liquor, wherein polyethylene glycol consumption is 1% ~ 10% of iron oxide quality in catalyst, and concentrated ammonia liquor consumption is 5 ~ 10 times of molysite molal quantity used;
3. under normal temperature ultrasound condition, solution A and solution B are slowly mixed in the mode also flowed, add rear continuation and stir 30min;
4. gained precipitation is filtered, and washing, then dries, then 450 DEG C of roastings 8 hours;
5. by the solid porphyrize after roasting, compressing tablet is gained catalyst.
4. a synthesis 2, the method of 6-xylenol, is included in and is equipped with in the reaction tube of catalyst, and phenol, first alcohol and water are contacted, and inert carrier gas is led in reaction tube, it is characterized in that: described catalyst is the catalyst in claim 1,2 described in any one.
5. method according to claim 4, is characterized in that: described contact conditions comprises: phenol, first alcohol and water mol ratio are 1:(3 ~ 5): (0.5 ~ 1), pressure is normal pressure ~ 0.5MPa, and temperature is 330 ~ 380 DEG C, air speed 0.4 ~ 2 hr
-1, flow rate of carrier gas scope is 10 ~ 25mL/min.
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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 |
| EP3377218B1 (en) * | 2015-11-19 | 2021-04-14 | Shell Internationale Research Maatschappij B.V. | Catalyst system and process for the production of glycols |
| CN109395711B (en) * | 2018-11-30 | 2020-05-19 | 中国科学院大连化学物理研究所 | Preparation method of boron-scandium catalyst and application of boron-scandium catalyst in synthesis of 2, 6-dimethylphenol |
| CN109970513B (en) * | 2019-03-04 | 2021-12-28 | 宝鸡文理学院 | Method for catalytically recovering phenol in anisole synthesis process by methanol method |
| CN109939708A (en) * | 2019-04-03 | 2019-06-28 | 衷晟 | A kind of methyl phenolic compounds manufacturing method |
| CN115124671B (en) * | 2022-07-15 | 2023-04-25 | 东营市赫邦化工有限公司 | Preparation method of phenol-formaldehyde resin and product obtained by preparation method |
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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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| JPS57112342A (en) * | 1980-11-28 | 1982-07-13 | Asahi Chem Ind Co Ltd | Preparation of ortho-methylated phenolic compound |
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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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| Title |
|---|
| "杂多酸催化剂在烷基化反应中的研究进展";申凤善等;《分子科学学报》;20060228;第22卷(第1期);第1-2节 * |
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