CN103084213A - 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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- CN103084213A CN103084213A CN2012104613547A CN201210461354A CN103084213A CN 103084213 A CN103084213 A CN 103084213A CN 2012104613547 A CN2012104613547 A CN 2012104613547A CN 201210461354 A CN201210461354 A CN 201210461354A CN 103084213 A CN103084213 A CN 103084213A
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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 a kind of Catalysts and its preparation method of synthetic 2,6-xylenol and use this catalyst to synthesize the method for 2,6-xylenol.
Background technology
2,6-xylenol is the raw material of synthetic polyphenylene oxide resin (PPE), photograph with medicament, agricultural chemicals, medicine, polyester and polyether resin, uses very extensive.
Early stage 2, the 6-xylenol is to separate to obtain from coal tar and petroleum cracking product, yields poorly, and is of poor quality.At first N.Cullinane in 1945 etc. adopt phenol and methyl alcohol to carry out the gas phase catalysis methylation reaction, have synthesized 2, the 6-xylenol.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 that uses the earliest is Al
2O
3, catalytic activity and ortho-methylated replacement selectively very low due to it generate a large amount of contrapositions and a position methylated phenol simultaneously, as Japan Patent JP7853627, are therefore replaced by MgO is catalyst based gradually.US3446856, US4041085, US4201880, US4554267 etc. all provide MgO catalyst based.Although the catalyst based Al that compares of MgO
2O
3Catalytic activity high and the ortho position is selectively good, but required reaction temperature is very high, poor stability, thereby cause energy consumption large.Therefore MgO is catalyst based is replaced by emerging Fe-series catalyst gradually, all discloses Fe-series catalyst separately as patents such as US3716589, US3953529, US4024195, US4227024, EP19476.The catalyst that wherein especially provides with US4429171 is the most representative, this catalyst is comprised of Fe, In, Cr, Si, five kinds of elements of K, in preparation 2, after using this catalyst in the gas phase catalytic reaction of 6-xylenol, reaction temperature is down to 300 ~ 400 ℃, 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.Yet, to find in application, the preparation reappearance of this catalyst is relatively poor, is difficult to obtain the catalyst prod with stability.CN1634656A provides a kind of catalyst that is comprised of Fe, In, Cr, Si, Ca, K, seven kinds of elements of C, and during for the synthesis of 2,6-xylenol, phenol conversion can reach 99%, and the ortho position selectively reaches 97%.But this catalytic component is many, and 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 synthetic 2, the 6-xylenol of nontoxic, good stability.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of catalyst of synthetic 2,6-xylenol is a kind of Fe, Mg and heteropoly acid/salt composite oxides, and each component mol ratio is Fe:Mg: heteropoly acid/salt=1:(0.01～0.05): (0.01～0.04).
The present invention also provide a kind of synthetic 2,6-xylenol catalyst the preparation method wherein, the method comprises the following steps:
1. with 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 the polyethylene glycol consumption be in catalyst the iron oxide quality 1%～10%, the concentrated ammonia liquor consumption is 5～10 times of molysite molal quantity used;
3. under the normal temperature ultrasound condition, solution A and solution B are slowly mixed in the mode that also flows, add rear continuation and stir 30min;
4. the gained precipitation is filtered, washing, and then oven dry, then 450 ℃ of roastings 8 hours;
5. with the solid porphyrize after roasting, compressing tablet is the gained catalyst.
Heteropoly acid/salt in catalyst of the present invention has stronger acidity, can regulate the Acidity of Aikalinity of catalyst, thereby effectively improves the active and stable of catalyst, and the conversion ratio of phenol is improved, and extend the service life of catalyst.
Soluble ferric iron salt of the present invention can be Fe (NO
3)
3, FeCl
3, Fe (OAc)
3Deng; The 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.; The PEG(mean molecule quantity is 800 ~ 4000) as dispersant, concentrated ammonia liquor (concentration is 25 ~ 28%) is as precipitating reagent.
The present invention also provides a kind of method of synthetic 2,6-xylenol, is included in the reaction tube that catalyst is housed, and makes phenol, the contact of first alcohol and water, and leads to inert carrier gas in reaction tube, and it is characterized in that: described catalyst is catalyst provided by the invention.
Described contact conditions comprises that phenol, first alcohol and water mol ratio are 1:(3～5): (0.5～1), pressure are normal pressure～0.5MPa, and temperature is 330～380 ℃, air speed 0.4～2 hr
-1, the flow rate of carrier gas scope is 10～25mL/min.
Add suitable quantity of water in reaction mixture, with the diluting reaction gaseous mixture, make its reacting balance, reduce the generation of catalyst upper surface carbon deposit, thereby 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 position selective alkylation catalyst, is not only applicable to also be applicable to 2-methylphenol, 2,4, the preparation of 6-trimethylbenzene phenolic compound by phenol compound and synthetic 2, the 6-xylenol of methyl alcohol reaction.Simultaneously, also be suitable for being with a wide range of applications by phenol compound and synthetic other ortho position alkylphenol compounds of alkylol reaction.
Advantage of the present invention is: catalyst low-temperature activity is high, method for making is simple, nontoxic, stable
Good.Phenol one way average conversion is higher, reaches more than 99%, and the ortho position is selectively up to more than 99%; Catalyst is longer service life, but more than catalyst one way stable operation 2000h.
The specific embodiment
The invention will be further described according to specific embodiment for the below:
Embodiment 1
Take Fe (NO
3)
39H
2O404g, Mg (NO
3)
26H
2O12.82g and phosphotungstic acid 28.80g mixing are dissolved in 800mL ethanol, then under the normal temperature ultrasound condition with its with 28% the 700mL concentrated ammonia liquor that contains 4gPEG with and the mode of stream slowly mix, continue after adding to stir 30min, then with sedimentation and filtration, washing, dry by the fire 6h under 120 ℃.The gained solid, is broken into 10 ~ 20 purpose granules again and is gained catalyst Fe Mg at last with the solid porphyrize again at 450 ℃ of lower roasting 8h after compressing tablet
0.05PW
0.01(PW represents phosphotungstic acid).
In the stainless steel fixed bed reactors, raw material is phenol: methyl alcohol with the above-mentioned Catalyst packing of 40mL: 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, the reaction normal pressure, and 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 the normal temperature ultrasound condition with its with 28% the 700mL concentrated ammonia liquor that contains 8gPEG with and the mode of stream slowly mix, continue after adding to stir 30min, then with sedimentation and filtration, washing, dry by the fire 6h under 120 ℃.The gained solid, is broken into 10 ~ 20 purpose granules again and is gained catalyst Fe Mg at last with the solid porphyrize again at 450 ℃ of lower roasting 8h after compressing tablet
0.01SM
0.04(SM represents silicomolybdic acid).
In the stainless steel fixed bed reactors, raw material is phenol: methyl alcohol with the above-mentioned Catalyst packing of 40mL: 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 are dissolved in 800mL ethanol, then under the normal temperature ultrasound condition with its with 28% the 700mL concentrated ammonia liquor that contains 4gPEG with and the mode of stream slowly mix, continue after adding to stir 30min, then with sedimentation and filtration, washing, dry by the fire 6h under 120 ℃.The gained solid, is broken into 10 ~ 20 purpose granules again and is gained catalyst Fe Mg at last with the solid porphyrize again at 450 ℃ of lower roasting 8h after compressing tablet
0.03(PMNa)
0.02(PMNa represents sodium phosphomolybdate).
In the stainless steel fixed bed reactors, raw material is phenol: methyl alcohol with the 40mL Catalyst packing: 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 are dissolved in 800mL ethanol, then under the normal temperature ultrasound condition with its with 28% the 700mL concentrated ammonia liquor that contains 0.8gPEG with and the mode of stream slowly mix, continue after adding to stir 30min, then with sedimentation and filtration, washing, dry by the fire 6h under 120 ℃.The gained solid, is broken into 10 ~ 20 purpose granules again and is gained catalyst Fe Mg at last with the solid porphyrize again at 450 ℃ of lower roasting 8h after compressing tablet
0.04(SWNa)
0.02(SWNa represents silicotungstic sodium).
In the stainless steel fixed bed reactors, raw material is phenol: methyl alcohol with the above-mentioned Catalyst packing of 40mL: 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 synthetic 2, a 6-xylenol, it is characterized in that: be a kind of Fe, Mg and heteropoly acid/salt composite oxides, each component mol ratio is 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 a kind of in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid, sodium phosphotungstate, sodium phosphomolybdate, silicotungstic sodium, silicomolybdic acid sodium.
3. the preparation method of a claim 1,2 described catalyst is characterized in that: comprise the following steps:
1. with 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 the polyethylene glycol consumption be in catalyst the iron oxide quality 1%～10%, the concentrated ammonia liquor consumption is 5～10 times of molysite molal quantity used;
3. under the normal temperature ultrasound condition, solution A and solution B are slowly mixed in the mode that also flows, add rear continuation and stir 30min;
4. the gained precipitation is filtered, washing, and then oven dry, then 450 ℃ of roastings 8 hours;
5. with the solid porphyrize after roasting, compressing tablet is the gained catalyst.
4. one kind synthetic 2, the method of 6-xylenol is included in the reaction tube that catalyst is housed, and makes phenol, the contact of first alcohol and water, and lead to inert carrier gas in reaction tube, it is characterized in that: described catalyst is the described catalyst of any one in claim 1,2.
5. method according to claim 4, it is characterized in that: described contact conditions comprises: phenol, first alcohol and water mol ratio are 1:(3～5): (0.5～1), pressure are normal pressure～0.5MPa, and temperature is 330～380 ℃, air speed 0.4～2 hr
-1, the flow rate of carrier gas scope is 10～25mL/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108348899A (en) * | 2015-11-19 | 2018-07-31 | 国际壳牌研究有限公司 | Antigravity system for manufacturing glycol and method |
| CN109395711A (en) * | 2018-11-30 | 2019-03-01 | 中国科学院大连化学物理研究所 | A kind of preparation method of boron scandium catalyst and its application in synthesis 2,6- xylenol |
| CN109939708A (en) * | 2019-04-03 | 2019-06-28 | 衷晟 | A kind of methyl phenolic compounds manufacturing method |
| CN109970513A (en) * | 2019-03-04 | 2019-07-05 | 宝鸡文理学院 | A method of phenol in catalysis recycling methanol method synthesis methyl phenyl ethers anisole technique |
| CN115124671A (en) * | 2022-07-15 | 2022-09-30 | 山东海科创新研究院有限公司 | Preparation method of phenol phenolic resin and product obtained by preparation method |
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| JPS57112342A (en) * | 1980-11-28 | 1982-07-13 | Asahi Chem Ind Co Ltd | Preparation of ortho-methylated phenolic compound |
| 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 |
| 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108348899A (en) * | 2015-11-19 | 2018-07-31 | 国际壳牌研究有限公司 | Antigravity system for manufacturing glycol and method |
| CN109395711A (en) * | 2018-11-30 | 2019-03-01 | 中国科学院大连化学物理研究所 | A kind of preparation method of boron scandium catalyst and its application in synthesis 2,6- xylenol |
| CN109970513A (en) * | 2019-03-04 | 2019-07-05 | 宝鸡文理学院 | A method of phenol in catalysis recycling methanol method synthesis methyl phenyl ethers anisole technique |
| 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 |
| CN115124671A (en) * | 2022-07-15 | 2022-09-30 | 山东海科创新研究院有限公司 | Preparation method of phenol phenolic resin and product obtained by preparation method |
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