CN1009196B - Process for producing orthoalkylphenols - Google Patents
Process for producing orthoalkylphenolsInfo
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- CN1009196B CN1009196B CN 85105077 CN85105077A CN1009196B CN 1009196 B CN1009196 B CN 1009196B CN 85105077 CN85105077 CN 85105077 CN 85105077 A CN85105077 A CN 85105077A CN 1009196 B CN1009196 B CN 1009196B
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- phenol
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Abstract
The present invention relates to a method for producing orthoalkylphenol, which comprises the step that a liquid phase reaction is carried out by using phenol and alkene when an alumina catalyst exists. The present invention is characterized in that the water content in the liquid phase of a reaction system is kept not higher than 250 ppm.
Description
The present invention relates to utilize phenol and a kind of alkene to react the method for producing orthoalkylphenols.
As a kind of antioxidant, or as synthetic agricultural chemical, dyestuff or suchlike intermediate, o single-alkyl phenol is very useful.In the presence of various catalyzer, phenolic compound and a kind of alkene are reacted, be well-known with the method for producing a kind of o single-alkyl phenol, for example United States Patent (USP) 3290389 has disclosed one with the method for gama-alumina as catalyzer.Gama-alumina does not have corrodibility and is easy to handle, so it is a kind of ideal catalyzer.Reduce than very fast but its shortcoming is its catalytic activity, thereby the reaction conversion ratio of phenol is just very low, people once proposed some recommendation on improvements and overcame these shortcomings.Japanese patent publication 9663/1977(United States Patent (USP) 3670030 for example) (Japanese Examined Patent Publication No.9663/1977(U.S.Patent 3670030)) suggestion adds entry in reactive system, to prevent the rapid reduction of gama-alumina catalytic activity, this document discloses, such as in the phenolic compound of phenol or hydroxyanisol and the reaction process such as the alkene of iso-butylene or 2-methyl butene-2, in the water of phenolic compound weight adding 500～5000ppm, can avoid the rapid reduction of catalytic activity.
Yet as present inventor's result of study, we find in the liquid phase reaction of gama-alumina as the phenol of catalyzer and alkene.When the water-content in the reactive system drops to when quite low, the catalytic activity of gama-alumina increases on the contrary.That is to say that phenol has water absorbability and be easy to draw moisture content from air.This is from the following fact clearly: the permission purifying phenol-405 of industrial standards such as the D-2489-68 of United States Patent (USP) testing of materials association (ASTM) contains the water that accounts for weight 0.2% at most, purifying phenol-the 405th, a kind of industrial commodity phenol, the order of magnitude of its water content is generally 300～2000ppm at hundreds and thousands of ppm.In addition, aluminium oxide catalyst also contains planar water.So water-content reaches into hundred ppm at least in the liquid phase of reactive system, as 500～5000ppm.The present inventor has been found that aluminium oxide catalyst can not reach enough activity in the reactive system of water content like this.But when the water-content of liquid phase was reduced to a predetermined level, the catalytic activity of aluminium oxide catalyst can increase significantly, and the selectivity of o single-alkyl phenol is improved too, and can reduces the generation of byproduct dialkyl group phenol.Moreover the preparation method that we also find aluminium oxide catalyst also has a significant impact the transformation efficiency and the selectivity of above-mentioned reaction.
The objective of the invention is provides a method of producing o single-alkyl phenol with good productive rate efficiently by active oxidation Al catalysts in the liquid phase reaction of alkene and phenol.
This purpose of the present invention can reach by a kind of method of producing o single-alkyl phenol, this method is included under the aluminium oxide catalyst existence alkene and phenol is reacted in liquid phase, the content that it is characterized in that water in the reactive system liquid phase remains on a weight that is not higher than 250ppm(in liquid phase) level on.
With reference to preferable embodiment, we will describe the present invention in detail.
In the present invention, react with alkene and phenol, we use C always
2-C
20Alkene is as raw material olefin.As an example, we can enumerate ethene, propylene, 1-butylene (alpha-butylene), β-butylene, iso-butylene, α-amylene, γ-amylene or β-isopentene especially.In the middle of them, (promptly has R with the secondary alkene that such as propylene or 1-butylene, can generate the secondary carbonium ion
1-HC=CH-CR
2R
3R
4The alkene of structural formula, R in the formula
1To R
4Each be hydrogen atom or alkyl) for well.For every mol phenol, use 0.1 to 10 molar this class alkene usually.
We adopt aluminium oxide catalyst as the effective catalyst in the method for the present invention.Aluminum oxide with catalytic activity is exactly the said gama-alumina in front.Its various preparation methods have been well-known.As an example, we can enumerate (1) here with a kind of sodium aluminate aqueous solution that makes with Bel's (Bayer) method of carbonic acid gas hydrolysis, the throw out that oven dry is generated, the thus obtained aluminium hydroxide of roasting and make aluminum oxide; (2) a kind of aluminium alkoxide of hydrolysis.The consequent aluminium hydroxide of roasting and make aluminum oxide; (3) such as the aqueous solution of the mineral acid aluminium salt of Tai-Ace S 150, aluminum nitrate or aluminum oxide and alkaline reagents neutralization such as ammoniacal liquor and aqueous sodium hydroxide solution, the aluminium hydroxide that roasting generates thus and make aluminum oxide; (4) the above-mentioned mineral acid aluminium salt of thermal degradation and make aluminum oxide in air.
In the method for the invention, the above-mentioned various aluminum oxide that make with ordinary method can be used as catalyzer, and the sodium potassium content in the aluminium oxide catalyst is advisable to be no more than 500ppm.Preferably be no more than 100ppm.Aspect the conversion and selectivity of reaction, use such aluminium oxide catalyst can obtain good result.For obtaining the catalyzer of this low sodium potassium content, be advisable to adopt aforesaid method 2.
A preferable embodiment of employed aluminium oxide catalyst in the preparation method of the present invention is described now.
Is the aluminium alkoxide such as aluminum ethylate, aluminum isopropylate, aluminium secondary butylate or trimethyl carbinol aluminium-its molecular formula Al(OR)
3R is a C in the formula
2-C
30Alkyl group be scattered in 3～500 times one by one in 0～100 ℃ water of its mole number, 400～1000 ℃-with 500～700 ℃ be-the consequent aluminum hydroxide precipitate of roasting temperature 0.01～20 hour.
When carrying out in being reflected at a suspension-type system, the amount of catalyzer used in the present invention is 0.001 to 0.3 times of phenol weight normally.Used catalyzer is normally Powdered or granular.
The reaction of alkene and phenol is normally carried out under 150～400 ℃ condition, is advisable with 180～300 ℃.If temperature is low excessively, then speed of response is with slack-off, if temperature is too high, the generation of undesirable byproduct will increase.Being reflected at is enough to make raw material phenol to keep carrying out under the pressure of liquid state under temperature of reaction.Common pressure is 1～50Kg/cm
2Under the situation of the suspension-type reactive system that uses catalyzer, the reaction times is generally 0.1～50 hour.
Reaction of the present invention can be carried out in discontinuous system, semicontinuous system or continuous system.As for reaction method, adducible a kind of method is to make the mixture of phenol and alkene by the fixed bed of catalyzer is housed under reaction conditions; Another kind method is that catalyzer is suspended in the phenol, adds alkene to react within the predetermined time under reaction conditions.The reaction that the present invention carried out usually need not any special solvent, yet according to circumstances needs, and can select any organic solvent for use.
After reaction is finished, usually with-for example-filtering method separates catalyzer from reaction mixture, with ordinary method distillation reaction mixture, can reclaim needed o single-alkyl phenol with this method again.
In the present invention, the most important thing is when phenol and olefine reaction, make the content of water in the reactive system liquid phase maintain a weight that is not higher than 250ppm(in liquid phase) level, be advisable not to be higher than 200ppm, preferably be not higher than 150ppm.In fact, raw material phenol is moisture absorption, and commercially available phenol contains the moisture content of 300～2000ppm usually, and aluminum oxide is passed because its water-absorbent also contains moisture after preparation in time.Therefore, if this phenol and aluminium oxide catalyst directly are put to use.In the liquid phase of reactive system, will have at least the water-content of hundreds of ppm.So, be necessary in the present invention tentatively moisture to be removed from phenol and catalyzer so that the water-content in the reaction soln liquid phase is not higher than 250ppm.
The removing water treatment and can be undertaken by following method of raw material phenol as distillation method, promptly blows to nitrogen or the such rare gas element of argon in the warmed-up phenol and goes; Or use such as the such water-retaining agent of molecular sieve, zeolite, aluminum oxide and ion exchange resin and handle.For aluminium oxide catalyst, normally before being put to use, it removes water treatment by heating, method suitable especially in actually operating is that with raw material phenol and aluminium oxide catalyst Hybrid Heating, a kind of rare gas element of the usefulness that will dewater then is blown in the heated mixture; Add thermal distillation phenol and mixture of catalysts; Or when adding thermal distillation, be aided with rare gas element.In these methods, dewatering of phenol and aluminum oxide carried out simultaneously, and after removing moisture, and alkene is introduced in the phenol and mixture of catalysts after dewatering, and the reaction of phenol and alkene can be carried out immediately.
A kind of preferable embodiment of the present invention will be expressed as follows especially:
Phenol and aluminium oxide catalyst packed into one be equipped with in the reactor of distillation tower, heat this mixture with ordinary method and distill.Distillation is depressed at normal atmospheric and is carried out, and with this understanding, distillation temperature is about 140～185 ℃.Distillation procedure equally also can carry out under decompression or supercharging.About distillation tower, can directly use or through suitably adjusting the back use such as the common tower of sieve-tray tower or packing tower.Distillation is under refluxad carried out usually.In order to remove the amount of anhydrating and reducing distilled phenol effectively, reflux ratio is the bigger the better, and suitable reflux ratio also is to determine according to the consideration to necessary energy, distillate cost recovery or the like aspect.In some cases, carry out under the condition that distillation can be in whole reflux course continuously or be in batches discharged the higher phenol of the water content that accumulates in cat head.The phenol that is discharged from can reclaim in the back that dewaters, and again as raw material.
When carrying out aforesaid operations, when the water-content in the phenol was reduced to desirable degree, distillation was promptly accused and is finished, and behind the alkene adding reactor, promptly began alkylated reaction.
After reaction is finished,, only liquid phase is discharged from reactor then and it is distilled, promptly obtain needed o single-alkyl phenol by filtering or sedimentation is separated liquid phase and catalyzer.The catalyzer of separating can be reused till catalytic activity will lose, so again with fresh phenol injecting reactor and to remove water treatment with above-mentioned same mode, then, add alkene, repeats above-mentioned operation.In another case, after reaction is finished, the muddy reaction mixture is ejected in reactor, liquid phase and catalyzer are separated, distill liquid phase then, can obtain needed o single-alkyl phenol through filtering.In this case, be in the fresh phenol injecting reactor, and it is removed water treatment, add the above-mentioned catalyzer that is separated then, after adding alkene, begin alkylated reaction again.
According to method of the present invention, by the liquid phase water content of reactive system is adjusted to a level that is not higher than 250ppm, the catalytic activity of aluminium oxide catalyst can be significantly improved, phenol conversion and can improve significantly for the selectivity of o single-alkyl phenol, and can obtain the needed o single-alkyl phenol of good yield.
In addition, by using the aluminium oxide catalyst of low sodium potassium content, can further improve activity of such catalysts.
Now, we are described in further detail the present invention with reference to example.Yet should be appreciated that the present invention never is subjected to any restriction of these object lessons.
Example 1～4 and comparative example 1～3
500 gram (5.31 gram molecular weight) phenol (water-content 300ppm) of commercially available reagent grade and the aluminium oxide catalyst (water-content of share as shown in table 1; Account for heavy by 2.5%) put into 1 liter of autoclave that distillation column is equipped with at a top, this mixture heating up to be distilled to about 185 ℃, distillation proceeds to that water-content reaches till the level shown in the table 1 in the reactive system liquid phase.
In comparative example 3, do not distill except that water treatment.
Add propylene then, total pressure is maintained 4Kg/cm
2On the level of gauge pressure, make and be reflected at 220 ℃ and carry out, till the conversion of phenol reaches predetermined degree, the needed reaction times is also constantly decided thus, and we have measured needed product with gc analysis, i.e. o-isopropyl phenol (OIPP), and byproduct, promptly 2,6 or 2, the selectivity of 4-diisopropyl phenol (DIPP).What obtain thus the results are shown in Table 1.
About aluminium oxide catalyst, we are put to commercially available hydrated alumina use in 600 ℃ of roastings in air after 4 hours.This hydrate is with aluminium alkoxide Al(OR)
3(R=C
2-C
30Alkyl) the dry then and preparation of hydrolysis (this hydrate trade name: Pural-SB is made by Condea Chemie company, and impurities has 0.008% SiO
2, 0.005% Fe
aO
3, 0.004% Na
3O and 0.4% carbon).
Fairly obvious, according to last table result, compare with comparative example, under the situation of example of the present invention, it is about 70% that the transformation efficiency of phenol just reached in the short reaction times, and lower to the selectivity of byproduct DIPP, and higher to the selectivity of needed product OIPP.
Example 5 and comparative example 4
Except replacing propylene as the alkene with 1-butylene, this example is to react with mode same described in the example 1.The results are shown in table 2.In table 2, OSBP represents needed product, i.e. o-sec-butyl phenol, and DSBP vice product, promptly 2,6-or 2,4-di sec-butylphenol.
Example 6～8 and comparative example 5～7
Except that the catalyzer that uses with method preparation shown in following, phenol and propylene are to react with method same described in the example 1.The results are shown in Table 3
Catalyst A:
The sodium aluminate aqueous solution that makes with Bel (Bayer) method with the carbonic acid gas hydrolysis, the throw out that oven dry generates thus and obtain aluminium hydroxide obtains aluminum oxide through roasting.Na and K content: 220ppm.
Catalyst B:
Dissolving 200 gram Tai-Ace S 150 (Al in a premium on currency
2(SO
4)
314～18H
2O).The ammonia soln of 10% weight percent is splashed in this solution, reach till 7 up to the pH value.The aluminium hydroxide flushing back of gained is dried down at 120 ℃, in air,, obtain aluminum oxide in 600 ℃ of roastings 4 hours.Na and K content: 150ppm.
The water (about 2 liters) that adds 10 times in 200 gram commercially available reagent level isopropanol aluminium is heated to 80 ℃ and is hydrolyzed.Distillation to be removing Virahol, remaining material under 120 ℃ of temperature, dry and further in air in 660 ℃ of roastings 4 hours, obtain aluminum oxide.Na and K content: 20ppm.
Fairly obvious, according to the result of table 3, which kind of no matter adopts prepare the method for aluminium oxide catalyst, it all is effective reducing water-content in reactive system.It is equally clear that when water-content was low, the content of Na and K was few more in the aluminium oxide catalyst, catalytic activity is just strong more.
Example 9
Make industrial commodity phenol (water content: 300ppm) pass through molecular sieve 4A post (trade(brand)name is made by Gaskuro Kogyo company) so that its water-content is reduced to 55ppm.Be recovered in and be used for catalyst for reaction in the example 1 and it is directly reused as catalyzer.By using such phenol and aluminium oxide catalyst.Reaction the results are shown in Table 4 to carry out with the same mode of example 1.
Table 2
Water contains the reaction preference (%) of catalyzer phenol
Amount concentration (the gram transformation efficiency time
Ppm molecule %) (%) (minute) OSBP DSBP
Example 5 110 5.0 70.4 65 98.2 1.8
Compare 520 5.0 69.3 600 95.6 4.4
Example 4
* 12.0 mol %=2.17%(by weight)
* 25.0 mol %=5.42%(by weight)
Table 4
The reaction preference (%) of water-content catalyzer phenol
Concentration (the gram transformation efficiency time
Ppm molecule %) (%) (branch) OIPP DIPP
Example 50 2.0 71.6 20 96.9 3.0
9
Claims (7)
1, produce a kind of method of o single-alkyl phenol, this method comprises, in the presence of aluminium oxide catalyst, phenol and propylene or butylene is reacted under liquid phase, it is characterized in that, in the liquid phase of reactive system, keeps water-content not to be higher than 250ppm.
2, according to the process of claim 1 wherein that water-content is not higher than 200ppm.
3, according to the process of claim 1 wherein that water-content is not higher than 150ppm.
4, according to the process of claim 1 wherein that the sodium potassium content in aluminium oxide catalyst is not higher than 500ppm.
5, according to the method for claim 4, catalyzer wherein is to make by the aluminium hydroxide that obtains behind the roasting hydrolyzable alkoxy aluminium alcoholates.
6, according to the method for claim 1, this method is included under the existence of aluminium oxide catalyst, react with phenol and propylene or butylene: it is characterized in that before reaction, the mixture of heating and distillation phenol or phenol and aluminium oxide catalyst removes water treatment, till the water-content of liquid phase is not higher than 250ppm, and reaction is to be undertaken by adding alkene in this phenol that has reduced moisture and mixture of catalysts.
7, according to the method for claim 7, wherein distillation is to carry out under the condition that feeds rare gas element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105077 CN1009196B (en) | 1984-07-05 | 1985-07-03 | Process for producing orthoalkylphenols |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59139385A JPS6118739A (en) | 1984-07-05 | 1984-07-05 | Preparation of orthoalkylphenol |
| CN 85105077 CN1009196B (en) | 1984-07-05 | 1985-07-03 | Process for producing orthoalkylphenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105077A CN85105077A (en) | 1986-12-31 |
| CN1009196B true CN1009196B (en) | 1990-08-15 |
Family
ID=25741838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105077 Expired CN1009196B (en) | 1984-07-05 | 1985-07-03 | Process for producing orthoalkylphenols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1009196B (en) |
-
1985
- 1985-07-03 CN CN 85105077 patent/CN1009196B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85105077A (en) | 1986-12-31 |
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