CN1078195C - Krueger Andrzej, Tkacz Boguslaw, Pers Tatian et al. (PL) - Google Patents
Krueger Andrzej, Tkacz Boguslaw, Pers Tatian et al. (PL) Download PDFInfo
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- CN1078195C CN1078195C CN 97110553 CN97110553A CN1078195C CN 1078195 C CN1078195 C CN 1078195C CN 97110553 CN97110553 CN 97110553 CN 97110553 A CN97110553 A CN 97110553A CN 1078195 C CN1078195 C CN 1078195C
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Abstract
A method for continuously preparing 12 alkyl phenol by propylene tetramer alkyl phenol under the existence of cation exchange resin activator in a form of sulfonic acid styrene-divinylbenzene copolymer, makes a reaction mixture contact with big hole type activator, obtains two fractions by distilling the alkyl product, and obtains the 12 alkyl phenol by reclaiming from the high boil point fraction by conventional method. The low boil point fraction is divided into two liquid flows, the first liquid flow is recycled and filled into a phenol alkyl device, and another liquid is added with water and divided into a hydrocarbon layer and a phenol layer, the phenol layer enters the composing technics for the 12 alkyl phenol after being distilled, dehydrated and recycled.
Description
The present invention relates to a kind of in the ion-exchange resin catalyzed method for preparing dodecyl phenol down with the continuous alkylated phenol of the propylene tetramer.
Dodecyl phenol is mainly used in detergent additive (it exists with the calcium and the magnesium phenates of alkalescence therein) and the non-ionic detergent (ethoxylation or propenoxylated dodecyl phenol) and the anionic detergent (sulfation or Sulfonated dodecyl phenol) of preparation lubricating oil.Phenol is catalyzer with the alkylated reaction of alkene with acid, and the concentration of acid can be 1-50% (weight) in reaction mixture.Especially, the strong-acid ion exchange resin of sulfonated styrene diethylene benzene copoly mer form is preferred catalyst for alkylation reaction.
According to the method for patent No.WO88/03133, the alkene that phenol and petroleum distillation residue thermo-cracking obtain reacts and can prepare monoalkyl phenol.In the presence of, 110 ℃ of temperature 100% excessive with respect to alkene and the catalyst A mberlyst-15, use C at phenol
12Olefin alkylation phenol, the productive rate of dodecyl phenol are 88%.
In Japanese Patent JP6228438, phenol and C
12-C
30The alkylated reaction of alkene is a catalyzer with the ion exchange resin based on the strongly-acid sulphonated polystyrene, and this reaction has high thermostability and good selectivity.Because the concentration of dialkyl group phenol lower (about 3wt%) in alkylate does not need underpressure distillation that it is separated.
According to the method for Poland Patent No.167907, in the presence of the ion-exchanger catalyzer of forming by macropore and gel type cation exchanger, use C
12The successive reaction of olefin alkylation phenol has high selectivity, removes inert material and water by crystallization from reaction medium.This method can obtain high and stable productive rate.But in order by solvent extraction phenol and hydrocarbons to be separated the liquid after crystallization, need be on equipment the added solvent regenerating unit.
The object of the present invention is to provide a kind of the needs to remove inert material and water and solvent extraction step, have the stable and high productive rate and the continuous preparation method of dodecyl phenol optionally by crystallization.
Main points of the present invention are, in method with propylene tetramer alkylated phenol in 80-150 ℃ of temperature range, contain the macroporous cation exchange resin catalyst that is no less than 10% (weight) Vinylstyrene in the presence of, make the reaction mixture that contains phenol, the propylene tetramer, dodecyl phenol, join other alkylate, stable hydrocarbon and water in the circulating system and various raw materials with 5h at the most
-1Space velocity by catalyst bed, alkylate is divided into two fractions thereon, a fraction boiling point is lower than 250 ℃, another fraction boiling point is higher than 250 ℃.From the high boiling point fraction, reclaim dodecyl phenol, and boiling point is lower than 250 ℃ lightweight fraction and is divided into two strands of liquid streams with ordinary method.One liquid stream recirculation enters in the alkylation of phenol device; And in another strand liquid stream, adding the water that is no more than 10wt%, it is divided into hydrocarbon layer and phenol layer down at 20-50 ℃.Recirculation portion separatory stream is 20: 1 to 5: 1 with the weight ratio of another processed liquid stream.The recirculation behind distillation dehydration of phenol layer enters in the reaction system, and mainly contains unreacted C
12The hydrocarbon layer of paraffinic hydrocarbon is then removed from system.
Embodiment 1
Make contain 31.5% (weight) phenol, 10.4% (weight) contains C
12The reaction mixture of the propylene tetramer, 43.8% (weight) dodecyl phenol of paraffinic hydrocarbon, 14.2% (weight) other alkylphenol and 0.1% (weight) water in 95-100 ℃ of temperature range with 1h
-1Space velocity is by the macroporous type Amberlyst-36 cation exchange resin catalyst bed of phenol-dehydration.From mixture, obtain the lightweight fraction that boiling point is lower than 250 ℃, wherein contain 71.7% (weight) phenol, 4.5% (weight) C
12Alkene, 18.1% (weight) C
12Paraffinic hydrocarbon, 1.2% (weight) dodecyl phenol, 4.4% (weight) other alkylphenol and 0.3% (weight) water.95% (weight) of resulting this fraction is recycled in the alkyl plant, makes its concentration reach 1.75% (weight) and in 5% (weight) of remainder, add distilled water.Produce layering after placing 15 minutes under 20 ℃, one is the phenol layer, and one for containing 10.9% (weight) phenol, 16.6% (weight) C
12The hydrocarbon layer of alkene, 5.5% (weight) alkylphenol and 0.6% (weight) water.The recirculation behind distillation dehydration of phenol layer enters in the synthesis technique of dodecyl phenol.
Embodiment 2
Adding distilled water in 20% (weight) of the lightweight fraction in the embodiment 1 makes its concentration reach 5.3% (weight).Produce layering after placing 20 minutes under 50 ℃, one is the phenol layer, and one for containing 6.4% (weight) phenol, 17.5% (weight) C
12Alkene, 69.9% (weight) C
12The hydrocarbon layer of paraffinic hydrocarbon, 5.9% (weight) alkylphenol and 0.3% (weight) water.As embodiment 1, the recirculation behind distillation dehydration of phenol layer enters in the synthesis technique of dodecyl phenol.
Claims (1)
- One kind in 80-150 ℃ of temperature range, in the presence of the cation exchange resin catalyst of sulfonated styrene diethylene benzene copoly mer form, the method for preparing dodecyl phenol with propylene tetramer alkylated phenol continuously, wherein, make the reaction mixture that contains phenol, the propylene tetramer, alkylate, stable hydrocarbon and water with 5h at the most -1Space velocity with contain the macroporous type catalyzer that is no less than 10% (weight) Vinylstyrene and contact, alkylate obtains two kinds of fractions through distillation thereon: a kind of fraction boiling point is lower than 250 ℃, another kind of fraction boiling point is higher than 250 ℃, reclaim from the high boiling point fraction with ordinary method subsequently and obtain dodecyl phenol, and the lightweight fraction that boiling point is lower than 250 ℃ is that 20: 1 to 5: 1 (weight) is divided into two liquid streams with ratio, the recirculation of previous liquid stream is entered in the alkylation of phenol device, and add the water that is no more than 10% (weight) amount and under 20-50 ℃ of temperature, be divided into hydrocarbon layer and phenol layer in another liquid stream, latter's recirculation behind distillation dehydration enters in the synthesis technique of dodecyl phenol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL31622096A PL182406B1 (en) | 1996-09-19 | 1996-09-19 | Method of obtaining dodecyl phenol |
| PL316220 | 1996-09-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1176958A CN1176958A (en) | 1998-03-25 |
| CN1078195C true CN1078195C (en) | 2002-01-23 |
Family
ID=20068330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97110553 Expired - Fee Related CN1078195C (en) | 1996-09-19 | 1997-04-17 | Krueger Andrzej, Tkacz Boguslaw, Pers Tatian et al. (PL) |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1078195C (en) |
| PL (1) | PL182406B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657723B (en) * | 2013-12-24 | 2015-05-27 | 王金明 | Preparation method of catalyst for preparing dodecyl phenol |
| CN109053384A (en) * | 2018-08-07 | 2018-12-21 | 广东锦昱材料科技有限公司 | A kind of branch cetyl phenol produced using four polybutene as raw material |
| CN108929198A (en) * | 2018-08-07 | 2018-12-04 | 广东锦昱材料科技有限公司 | A kind of side chain dodecyl benzen phenol produced using three polybutene as raw material |
| CN109776600A (en) * | 2019-01-20 | 2019-05-21 | 南雄志一精细化工有限公司 | A kind of environment protection liquid phosphite antioxidant |
-
1996
- 1996-09-19 PL PL31622096A patent/PL182406B1/en not_active IP Right Cessation
-
1997
- 1997-04-17 CN CN 97110553 patent/CN1078195C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176958A (en) | 1998-03-25 |
| PL316220A1 (en) | 1998-03-30 |
| PL182406B1 (en) | 2001-12-31 |
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