CN1868992A - Alkylphenol coproduction technology - Google Patents
Alkylphenol coproduction technology Download PDFInfo
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- CN1868992A CN1868992A CN 200510043676 CN200510043676A CN1868992A CN 1868992 A CN1868992 A CN 1868992A CN 200510043676 CN200510043676 CN 200510043676 CN 200510043676 A CN200510043676 A CN 200510043676A CN 1868992 A CN1868992 A CN 1868992A
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Abstract
A process for preparing multiple alkylphenol products from phenol and isobutene includes such steps as catalytic alkylating reaction to obtain alkylated liquid, deactivating the catalyst (aluminum phenolate), flash distilling, rectifying to obtain 2,6-di-tert-butyl phenol and o-tert-butyl phenol, reaction between residual bottom liquid and p-methylphenol under the action of acidic catalyst to obtain the alkylated liquid, and rectifying to obtain 2,4-di-tert-butyl phenol and o-tert-butyl p-methyl phenol.
Description
Technical field
The invention belongs to fine chemistry industry, particularly the production technique of alkylphenol.
Background technology
Alkylphenol generally, is carried out alkylated reaction and makes in the presence of catalyzer by phenol and alkylating agent (as alkene, hydrocarbon, ether, alcohol etc.).Conventional art produces 2, the 6-DI-tert-butylphenol compounds (is called for short 2,6-phenol) production technique is that employing phenol and iso-butylene are raw material, with phenol oxygen base aluminium is catalyzer, under processing condition such as certain reaction temperature, proportioning raw materials, prepare 2,6-phenol content＞75%, o-tert-butylphenol (adjacent tertiary butyl phenol) content＜10%, 2,4,6-tri-butyl-phenol (2,4,6-phenol)＜10%, the thick alkylation liquid of other by product about 5%, obtain high purity 2 by catalyst deactivation, flash distillation, rectifying separation, 6-phenol.Cat head 2, the light component before the 6-phenol boiling point returns alkylation reaction, and at the bottom of the tower 2, the heavy component after the 6-phenol is handled as the still raffinate.Production technique is single for producing 2,6 di t butyl phenol, and production technique exists material consumption, energy consumption height; The product cost height; Range of product is single.Because the heavy component of producing is many, in postorder was handled, the still raffinate of generation was many, and the equipment obstruction is serious, and the equipment cycle of operation is short.
Summary of the invention
Technical problem to be solved by this invention provides the coproduction technology of alkylphenol, prepares o-tert-butylphenol when the preparation 2,6 di t butyl phenol, improves the 2,6 di t butyl phenol device capbility; Reduce material consumption, the energy consumption of 2,6 di t butyl phenol device, reduce product cost; Reduce by product and impurity level (the residual amount of still); The prolongation equipment cycle of operation.
Alkylphenol coproduction technology of the present invention, it is characterized in that using phenol aluminium to be catalyzer, phenol and iso-butylene are at 70～150 ℃ of following alkylated reactions, and preparing the 2,6 di t butyl phenol weight content is 40-50%, o-tert-butylphenol content is at the alkylation liquid of 30-50%, through catalyst deactivation, flash distillation, enter distillation system, separate by refining, obtain 2,6 di t butyl phenol and o-tert-butylphenol.
The technical qualification of above-mentioned optimal process are:
The alkylated reaction temperature is 100-110 ℃, more preferred 110-120 ℃.
The mass ratio of catalyzer phenol aluminium and phenol is 0.009-0.47%, preferred 0.01～0.03%.
Also contain 2,4 about 6% in the alkylation liquid that alkylated reaction obtains, 6-tri-butyl-phenol (2,4,6-phenol), other by product is lower than 5%.Isolate 2 respectively through distillation system after alkylation liquid process catalyst deactivation, the flash distillation, 6-DI-tert-butylphenol compounds and o-tert-butylphenol contain 2,4 about 70% in the still raffinate, the 6-tri-butyl-phenol, under an acidic catalyst condition, with the p-methyl phenol reaction, temperature of reaction is 80～130 ℃, reaction solution passes through rectifying separation, produce 2,4-DI-tert-butylphenol compounds (2,4-phenol) and o-tert-butyl p-methyl phenol (o-tert-butyl p-cresol).Wherein the mass ratio of p-methyl phenol and heavy component material is 1: 2-4, the mass ratio of an acidic catalyst and p-methyl phenol are 10-20%.An acidic catalyst is mineral acid (as sulfuric acid, a phosphoric acid etc.), Lewis acid (as aluminum chloride, boron trifluoride etc.), acidic white earth, acidic resins etc.The preferred strong acidic ion resin that adopts.
Alkylation liquid is at first isolated overhead fraction in distillation system: 2, and the cut (front-end volatiles) before the 6-phenol boiling point, front-end volatiles separation and purification obtain purity and are not less than 99.5% adjacent tertiary butyl phenol; Component is 2 at the bottom of the tower, and the component after 6-phenol and the boiling point thereof carries out rectifying again and obtains purity and be not less than 99.5% product 2,6-phenol; Still raffinate (heavy component) enters normal-pressure reaction kettle, under an acidic catalyst condition, reacts with p-methyl phenol (p-cresol).
Advantage of the present invention: can utilize existingly 2,6-phenol device is producing 2, on the 6-phenolic group plinth, but the adjacent tertiary butyl phenol of combination producing, 2,4-phenol and o-tert-butyl p-cresol.So not only improved the production capacity of device, and reduced material consumption, energy consumption, reduced product cost, produced the impurity minimizing, alleviated the stifled phenomenon of hanging of equipment, prolonged the equipment cycle of operation Gu pay.Alkylphenol product of the present invention is used for the intermediate of oxidation inhibitor, sterilant, spices.
Table 1 per unit area yield 2,6-phenol and coproduction 2,4-phenol, adjacent tertiary butyl phenol, the contrast of o-tert-butyl p-cresol
| Sequence number | Project | Per unit area yield 2,6-phenol | Coproduction 2,4-phenol, adjacent tertiary butyl phenol, the contrast of o-tert-butyl p-cresol | |
| 1 | The consumption of ton product | Phenol, (kg/t) iso-butylene, (kg/t) aluminum shot, (kg/t) steam, (t/t), (degree/t) recirculated water, (t/t) | 530 660 0.003 2 15 200 103 | 480 575 0.0019 12 180 98 |
| 2 | Output (ton/year) | 3000 | 4000 (2,6 phenol+adjacent trimethylphenylmethane phenol+2,4 phenol+o-tert-butyl p-cresol) | |
| 3 | The residual amount of still (kg/t) | 100 | 30 | |
| 4 | Flash distillation still cleaning cycle (my god) | 7 | 12 | |
| 5 | Falling-film evaporator cleaning cycle (moon) | 2 | 5 | |
| 6 | Product purity, % | Be not less than 99.5% | Be not less than 99.5% | |
Embodiment
Embodiment and Comparative Examples further specify the present invention, but do not limit the scope of the invention.
Embodiment 1:
At 1m
3Add 400kg phenol in the reactor, the 3kg aluminum shot is under 100-120 ℃, stirring reaction 1-2h is pressed in the alkanisation still (I) after reaction finishes, and will add alkylation reaction still (I) behind the 800kg phenol alkanisation, heat temperature raising is during to 60-80 ℃, and the iso-butylene of vaporization is in advance fed alkanisation still (I) continuously, and control reaction temperature is no more than 80 ℃, behind the reaction 2h, sampling analysis, when 2,6-phenol content reaches 40-50%, adjacent tertiary butyl phenol content reaches 30-40%, stopped reaction.Thick alkylation liquid obtains smart alkylation liquid through hydrolysis, flash distillation.Smart alkylation liquid is through rectifying tower I, be-760 in vacuum tightness～-750mmHg, 160～180 ℃ of tower still temperature, 100～120 ℃ of separation of tower top temperature obtain cat head I product: 2, fraction (foreshot) before the 6-phenol boiling point, I at the bottom of the tower: comprise 2,6 phenol are at interior heavy component material, and the I material removes rectifying tower II at the bottom of the tower, be-760 in vacuum tightness～-750mmHg, 180～200 ℃ of tower still temperature, 110～130 ℃ of separation and purifications of tower top temperature, cat head II obtain purity and are not less than 99.5% product 2,6-phenol, the II heavy component enters 2m at the bottom of the tower
3Alkylation reaction still II.Cat head I foreshot enters rectifying tower III, be-760 in vacuum tightness～-750mmHg, 150～170 ℃ of tower still temperature, under 80～100 ℃ of the tower top temperatures, cat head III isolates adjacent tertiary butyl phenol boiling point fraction before, turn back to alkylation reaction still I and continue to participate in reaction, III at the bottom of the tower, fraction enters rectifying tower IV, be-760 in vacuum tightness～-750mmHg, under 160～180 ℃ of the tower still temperature, 100～120 ℃ of tower top temperatures, cat head IV obtains purity and is not less than the adjacent tertiary butyl phenol of 99.5% product, and the IV cut returns smart alkylation liquid basin and participates in rectifying continuously at the bottom of the tower.The results are shown in Table 2.
Embodiment 2
At 2m
3Among the alkylation reaction still II, II heavy component at the bottom of the adding 1600kg tower, 500kg p-methyl phenol (p-cresol), 75kg an acidic catalyst, heat temperature raising, control reaction temperature 100-110 ℃, stirring reaction 2h, sampling analysis.In alkylation liquid II, 2,4,6-phenol content＜0.5% o'clock stopped reaction.Alkylation liquid II directly enters rectifying tower V, be-760 in vacuum tightness～-750mmHg, 160～180 ℃ of tower still temperature, under 100～110 ℃ of the tower top temperatures, at first isolate o-tert-butyl p-cresol boiling point fraction before, return alkylation reaction still II, again reaction from cat head V.Be-760 in vacuum tightness～-750mmHg, under 180～190 ℃ of the tower still temperature, 110～120 ℃ of tower top temperatures, go out purity from cat head V separation and purification again and be not less than 99.5% product o-tert-butyl p-cresol.The V product enters rectifying tower VI at the bottom of the tower, be-760 in vacuum tightness～-750mmHg, under 180～210 ℃ of the tower still temperature, 120～140 ℃ of tower top temperatures, cat head is isolated high purity product 2,4-phenol, bottom product is handled as the still raffinate.The results are shown in Table 3.
Comparative Examples 1
At 1m
3Add 400kg phenol in the reactor, the 5kg aluminum shot, under 100-120 ℃, stirring reaction 1-2h is pressed into 3m after reaction finishes
3In the alkylation reaction still.800kg phenol fusing back is added in the alkylation reaction still, and heat temperature raising is during to 80-100 ℃, with the iso-butylene of vaporization in advance, feeds continuously in the alkanisation still, and control reaction temperature is no more than 100 ℃, behind the reaction 2h, and sampling analysis.When 2,6-phenol content＞75%, o-tert-butyl phenol＜10%, 2,4,6-phenol＜10% back stopped reaction.Alkylation liquid gets smart alkylation liquid through hydrolysis, flash distillation.Smart alkylation liquid enters rectifying tower I, be-760 in vacuum tightness～-750mmHg, under 160～180 ℃ of the tower still temperature, 100～120 ℃ of tower top temperatures, cat head I gets foreshot and returns alkylation reaction, the I material enters rectifying tower II at the bottom of the tower, be-760 in vacuum tightness～-750mmHg, 180～200 ℃ of tower still temperature, under 110～130 ℃ of the tower top temperatures, cat head II separation and purification gets purity and is not less than 99.5% product 2,6-phenol, and II handles as the still raffinate at the bottom of the tower.The results are shown in Table 2.
Embodiment 3
1m
3Add aluminum shot 2kg in the reactor, 100-120 ℃ of alkylation reaction temperature, other condition the results are shown in Table 2 with embodiment 1
Embodiment 4
1m
3Add aluminum shot 1kg in the reactor, 120-150 ℃ of alkylation reaction temperature, other condition the results are shown in Table 2 with embodiment 1
Embodiment 5
1m
3Add aluminum shot 5kg in the reactor, 80-100 ℃ of alkylation reaction temperature, other condition the results are shown in Table 2 with embodiment 1
Embodiment 6
At 2m
3Add the 50kg an acidic catalyst among the alkylation reaction still II, temperature of reaction 100-130 ℃, other condition the results are shown in Table 3 with embodiment 2
Embodiment 7
At 2m
3Add the 100kg an acidic catalyst among the alkylation reaction still II, temperature of reaction 90-100 ℃, all the other conditions the results are shown in Table 3 with embodiment 2
Embodiment 8
At 2m
3Add the 75kg an acidic catalyst among the alkylation reaction still II, temperature of reaction 80-100 ℃, all the other conditions the results are shown in Table 3 with embodiment 2
Table 2 reaction conditions and product test result
| Sequence number | Reaction conditions | Alkylation reaction liquid I component content (%, wt) | |||||
| Temperature of reaction, ℃ | The aluminum shot add-on, kg | Reaction times, h | 2,6 phenol | O-tert-butyl phenol | 2,4,6-phenol | Other | |
| Embodiment 1 Comparative Examples 1 embodiment 3 embodiment 4 embodiment 5 | 70-80 80-100 100-120 120-150 80-100 | 3 5 2 1 5 | 4 4 6 10 3 | 47.3 72 43.5 38.7 58.0 | 35.7 8.7 38.3 40.3 30.2 | 7.2 9.3 8.2 10.9 8.3 | 9.8 10.0 10.0 10.1 11.5 |
Table 3 reaction conditions and product tester
| Sequence number | Reaction conditions | Alkylation reaction liquid II component content (%, wt) | |||||
| Temperature of reaction, ℃ | The aluminum shot add-on, kg | Reaction times, h | 2,4 phenol | The o-tert-butyl p-cresol | 2,4,6-phenol | Other | |
| Embodiment 2 embodiment 6 embodiment 7 embodiment 8 | 100-110 110-130 90-100 80-100 | 75 50 100 75 | 4 5 3 5 | 63.1 60.5 61.4 62.3 | 30.0 29.8 30.2 30.0 | 0.21 0.43 0.32 0.28 | 6.10 9.27 8.18 7.42 |
Claims (10)
1, a kind of alkylphenol coproduction technology, it is characterized in that using phenol aluminium to be catalyzer, phenol and iso-butylene are at 70～150 ℃ of following alkylated reactions, and preparing the 2,6 di t butyl phenol weight content is 40-50%, o-tert-butylphenol content is at the alkylation liquid of 30-50%, through catalyst deactivation, flash distillation, enter distillation system, separate by refining, obtain 2,6 di t butyl phenol and o-tert-butylphenol.
2, production technique according to claim 1 is characterized in that described alkylated reaction temperature is 100-110 ℃.
3, production technique according to claim 2 is characterized in that described alkylated reaction temperature is 110-120 ℃.
4, production technique according to claim 1, the mass ratio that it is characterized in that catalyzer phenol aluminium and phenol is 0.009-0.47%.
5, production technique according to claim 4, the mass ratio that it is characterized in that catalyzer phenol aluminium and phenol is 0.01～0.03%.
6, production technique according to claim 1, it is characterized in that the still raffinate that obtains through distillation system after described alkylation liquid is through catalyst deactivation, flash distillation contains 2,4, the 6-tri-butyl-phenol under an acidic catalyst condition, reacts with p-methyl phenol, temperature of reaction is 80～130 ℃, reaction solution produces 2,4-DI-tert-butylphenol compounds and o-tert-butyl p-methyl phenol by rectifying separation.
7, production technique according to claim 1, it is characterized in that described alkylation liquid is through catalyst deactivation, after the flash distillation through rectifying, cat head isolates 2, cut before the 6-DI-tert-butylphenol compounds, be 2 at the bottom of the tower, component after 6-DI-tert-butylphenol compounds and the boiling point thereof, overhead fraction goes out o-tert-butylphenol through rectifying separation again, and component goes out 2,6 di t butyl phenol and heavy constituent still raffinate through rectifying separation at the bottom of the tower, the still raffinate is under an acidic catalyst condition, with the p-methyl phenol reaction, temperature of reaction is 80～130 ℃, and reaction solution passes through rectifying separation, produce 2,4-DI-tert-butylphenol compounds and o-tert-butyl p-methyl phenol.
8,, it is characterized in that described an acidic catalyst selection mineral acid, Lewis acid, acidic white earth or acidic resins according to claim 6 or 7 described production technique.
9, according to claim 6 or 7 described production technique, the mass ratio that it is characterized in that p-methyl phenol and heavy component material is 1: 2-4, the mass ratio of an acidic catalyst and p-methyl phenol are 10-20%.
10, production technique according to claim 8 is characterized in that described an acidic catalyst is a strong acidic ion resin.
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| CNB200510043676XA CN100387563C (en) | 2005-05-28 | 2005-05-28 | Alkylphenol coproduction technology |
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| CNB200510043676XA CN100387563C (en) | 2005-05-28 | 2005-05-28 | Alkylphenol coproduction technology |
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| CN1868992A true CN1868992A (en) | 2006-11-29 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320930A (en) * | 2011-05-30 | 2012-01-18 | 常州大学 | Method for preparing alkylphenol products and method for effectively governing wastewater |
| CN101628854B (en) * | 2009-08-18 | 2012-09-26 | 淄博科威化工有限公司 | O-tert-pentylphenol production process |
| CN108689806A (en) * | 2018-05-06 | 2018-10-23 | 陕西巴斯腾科技有限公司 | A kind of method of cresols product rectifying still raffinate recycling cresols |
| CN110746276A (en) * | 2019-12-05 | 2020-02-04 | 万华化学集团股份有限公司 | Method for producing o-tert-butylphenol and p-tert-butylphenol by rectification and crystallization |
| CN112574008A (en) * | 2020-12-25 | 2021-03-30 | 南京晶典抗氧化技术研究院有限公司 | Method for synthesizing 2, 6 di-tert-butylphenol by using environment-friendly heterogeneous catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2039062A1 (en) * | 1970-08-06 | 1972-02-10 | Hoechst Ag | Process for the preparation of 2,6-di-tert-butylphenol |
| PT66330B (en) * | 1976-03-22 | 1978-08-16 | Sterlitamaxky O Promyshlenny | Method of preparing 2,6-di-tert. butylphenol |
| CN1193007A (en) * | 1998-01-22 | 1998-09-16 | 义县精细化工总厂 | Process for synthesizing mixed tertbutyl-phenol |
-
2005
- 2005-05-28 CN CNB200510043676XA patent/CN100387563C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628854B (en) * | 2009-08-18 | 2012-09-26 | 淄博科威化工有限公司 | O-tert-pentylphenol production process |
| CN102320930A (en) * | 2011-05-30 | 2012-01-18 | 常州大学 | Method for preparing alkylphenol products and method for effectively governing wastewater |
| CN102320930B (en) * | 2011-05-30 | 2014-06-18 | 常州大学 | Method for preparing alkylphenol products and method for effectively governing wastewater |
| CN108689806A (en) * | 2018-05-06 | 2018-10-23 | 陕西巴斯腾科技有限公司 | A kind of method of cresols product rectifying still raffinate recycling cresols |
| CN110746276A (en) * | 2019-12-05 | 2020-02-04 | 万华化学集团股份有限公司 | Method for producing o-tert-butylphenol and p-tert-butylphenol by rectification and crystallization |
| CN110746276B (en) * | 2019-12-05 | 2022-08-02 | 万华化学集团股份有限公司 | Method for producing o-tert-butylphenol and p-tert-butylphenol by rectification and crystallization |
| CN112574008A (en) * | 2020-12-25 | 2021-03-30 | 南京晶典抗氧化技术研究院有限公司 | Method for synthesizing 2, 6 di-tert-butylphenol by using environment-friendly heterogeneous catalyst |
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