IE44061B1 - Method of purifying alkylphenols - Google Patents
Method of purifying alkylphenolsInfo
- Publication number
- IE44061B1 IE44061B1 IE577/77A IE57777A IE44061B1 IE 44061 B1 IE44061 B1 IE 44061B1 IE 577/77 A IE577/77 A IE 577/77A IE 57777 A IE57777 A IE 57777A IE 44061 B1 IE44061 B1 IE 44061B1
- Authority
- IE
- Ireland
- Prior art keywords
- crystals
- alkylphenol
- tert
- washing
- space
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
1514702 Purification of alkylphenols STERLITAMAX OPYTNO PROMYSH NEFTEKHIMISCHE ZAVOD and NOVOKUIBYSHEV FILIAL GIPROKAUCHUKA 17 March 1977 [17 March 1976] 11313/77 Heading C2C A method of purifying an alkylphenol from impurities contained therein, comprises effecting continuous crystallization of alkylphenol fed at a rate of from 0À12 to 0À31 hr-1 and washing the resulting crystals in a layer formed by the said crystals and moving downwards at a rate of from 0À1 to 1À0 hr-1, washing being performed with a solvent inert towards alkylphenol and moving in counterflow to the crystals at a rate of from 0À09 to 0À35 hr-1, and wherein the said washing is carried out in a washing element in the form of a vertical tube in which the crystals of alkylphenols are maintained in the form of a movable bed, the dimension of the same vertical tube being such that the ratio of the height of the moving layer of the crystals to the diameter of the crystal bed is at least 3.
Description
This invention relates to a method of purifying alkylphenols.
- Methyl - 2,6 - di - tert, butylphenol is a light-coloured phenol stabilizer which does not colour the material being protected and is non-toxic. It is used as a stabilizer for synthetic rubbers, polyethylene, and chemical fibres, as well as an antioxidative additive to oils, fuels, and other petroleum products.
- Methyl - 2,6 - di - tert, butylphenol also finds application in the food industry for stabilizing solid animal oils, and in medicine.
Another known phenol stabilizer is bis - (5 - methyl 3 - tert, butyl -2 - hydroxy - phenol) - methane.
The present invention provides a method of purifying an alkylphenol from impurities contained therein, comprising effecting continuous crystallization of alkylphenol fed at a space-time velocity of from 0.12 to 0.31 hr-1 and washing the resulting crystals in a layer formed by the said crystals and moving downwards at a space-time velocity of from 0.1 to 1.0 hr \ washing bein performed with a solvent inert towards alkylphenol and moving in counterflow to the crystals at a space-time velocity of from 0,09 to 0.35 hr and wherein the said washing is carried out in a washing element in the form of a vertical tube in which the crystals of alkyl44061
- 3 phenol are maintained in the form of a movable bed, the dimensions of the said vertical tube being such that the ratio of the height of the moving layer of the crystals to the diameter of the crystal bed is at least 3.
The solvent may be suitably ethyl alcohol, methyl alcohol, isopropyl alcohol, acetone, gasoline, or any other suitable solvent which dissolves alkylphenol and impurities contained therein and which is inert towards alkylphenol.
The present invention makes it possible to run the process continuously and to obtain alkylphenols with a high degree of purity. The content of the product is from 99.99 to 100 wt.%; the yield is high due to minimum losses of the product. in addition, the solvent consumption is reduced considerably. Alkylphenols, in particular 4 - methyl - 2,6 - di - tert, butylphenol, purified by using the method according to the invention, meets all the necessary requirements: its melting point is 69.5 - 70°C, its colour is white, and the content of impurities therein is up to 0.01 wt. %.
The method according to Lhe invention is carried out in a simple manner. Crystallization is conducted in a continuous-action crystallizer provided with a washing element in the form of a vertical tube. The initial alkylphenol containing impurities is fed continuously as a solution in ethyl or methyl alcohol into the crystallizer. The solvent is chosen depending on the nature of the alkylphenol to be purified.
The space-time velocity of feed of alkylphenol solution delivered for crystallization is from 0.12 to 0.31 hr-1. Crystallization is conducted under continuous stirring at a temperature of from + 15 to + 20°C.
440C
- 4 The crystals formed in the crystallizer pass continuously into the washing element and form a layer over the whole volume thereof. The layer of the crystals moves continuously downwards at a space-time velocity of from 0.1 to 1.0 hr-1. The solvent moves in the washing element upwards at a space-time velocity of from 0.09 to 0.35-^. Thus, washing is performed in a layer of crystals which moves in a vertical direction.
The solvent dissolves impurities present on the surface of the crystals and, after having passed through the washing element in the upward direction, enters the crystallizer where excess solvent is removed and can be recycled. Washing and crystallization of alkylphenol are conducted in the same solvent. The washed crystals of the product pass continuously into a sampler and then for drying.
The space-time velocity of feeding alkylphenol solution to crystallization, is as stated above, from 0.12 to 0.31 hr-l. Although the crystallization process can be conducted at a lower space-time velocity of alkyl· phenol feed this is undesirable, since then the time of crystallization increases. If alkylphenol is fed at a space-time velocity higher than that stated above, crystallization becomes incomplete, which is also undesir25 able. Thus, the crystallization process is adversely affected if the space-time velocity of alkylphenol flow is higher or lower than the above-stated limits.
The space-time velocities at which the layer of crystals and solvent move in the washing element must be within the above-stated range. When the space-time velocity of the layer of crystals is below 0.1 hr- , it is difficult to maintain the moving layer. When the space-time velocity is above 1.0 hr \ the risk of the mother liquor entering the washing element from the
440G1
- 5 crystallizer becomes higher, which is undesirable, since the product being purified becomes contaminated.
If the solvent moves in the washing element at a space-time velocity below 0,09 hr , the washing of the crystals is insufficient and the product being purified is contaminated. If the solvent moves in the washing element at a space-time velocity above 0.35 hr-^, there occurs longitudinal stirring of the crystals, their turbulence, and entrainment by the solvent into the crystallizer; as a result the required layer of the crystals in the washing element is disturbed.
The present invention is of commercial value, since the solvent is consumed in smaller amounts than in previously known methods, while the yield and purity of the product are higher.
The invention will be further described with reference to the following illustrative Examples.
Example 1
Λ
A crystallizer having a capacity of 1000 ml, pro20 vided with a stirrer, a washing element and a sampler, was preliminarily filled with a mother liquor of 4 methyl - 2,6 - di - tert, butylphenol in ethyl alcohol saturated at + 15°C. Alkylpnenol of the following composition was fed into the crystallizer at a space25 time velocity of 0.12 hr under continuous stirring:
- methyl - 2,6 - di - tert, butyl-
phenol 90 wt. % monalkylphenol 3 wt. % 2,6 - di - tert, butylphenol 3 wt. % 2,4,6 - tri - tert, butyl- phenol 4 wt. 7o
Alkylphenol was fed as a 50½ solution in ethyl
440 61
- 6 alcohol. Crystallization was conducted at + 15°C.
The crystals of 4 - methyl - 2,6 - di - tert, butylphenol formed in the crystallizer moved as a layer downwards through a vertical washing element, 30 mm in diameter and 300 mm in height, at a space-time velocity of 0.38 hr~^. Ethyl alcohol moved in the washing element at a space-time velocity of 0.14 hras a counterflow. The solvent, passing upwards through the washing element, washed the remaining impurities from the surface of the crystals, dissolved them and passed into the crystallizer, from where excess solvent was removed. The washed crystals of 4 - methyl - 2,6 di - tert, butylphenol from the washing element were delivered continuously into the sampler, and from there for drying. After 50 hours of operation, 4,000 g of
- methyl - 2,6 - di - tert, butylphenol were obtained with a melting point of 69.5~7O°C (69.0 - 70.0°C as reported in the literature). The composition of the crystalline product was:
4 - methyl - 2,6 - di - tert.
butylphenol 99-99 wt. % monoalkylphenol 0.01 wt. %
The crystals obtained were white.
Example 2
Under the conditions described in Example 1, a
50% solution of alkylphenol in methyl alcohol of the following composition was fed into the crystallizer at a space-time velocity of 0,12 hr
- methyl - 2,6 - di - tert.
butylphenol 04 wt. % 2,6 - di - tert, butylphenol 3 wt. % 2,4,6 - tri - tert, butylphenol 3 wt. σ/ /σ Methyl alcohol moved at a space-time velocity of 0.14
hr 1 in counter-flow to the crystals of 4 - methyl 35 2,6- di- tert, butylphenol, which moved as a layer at
- 7 a space-time velocity of 0.4 hr 1 in the vertical washing element. The crystals of 4 - methyl - 2,6 di - tert, butylphenol were removed continuously through the sampler. After 50 hours of operation,
4,200 g of 4 - methyl - 2,6 - di - tert, butylphenol were obtained with a melting point of 69.5-7O.O°C.
The composition of the crystalline product was:
- methyl - 2,6 - di - tert.
butylphenol 99.99 wt. %
2,6 - di - tert, butylphenol 0.01 wt. %
The crystals obtained were white.
Example 3
Under the conditions described in Example 1, a 50% solution of alkylphenol in ethyl alcohol of the following composition was fed at a space-time velocity of 0.31 hr1 into the crystallizer:
- methyl - 2,6 - di - tert.
butylphenol 94 wt. %
2,6 - di - tert, butylphenol 3 wt. %
2,4,6 - tri - tert, butylphenol 3 wt. %
Ethyl alcohol moved at a space-time velocity of 0.35 hr-1 in counter-flow to the crystals of 4 - methyl 2,6 - di - tert, butylphenol, which moved as a layer at a space-time velocity of 1.0 hr 1 in the vertical washing element. The crystals of 4 - methyl - 2,6 - di - tert.
butylphenol were removed continuously through the sampler After 50 hours of operation, 10,500 g of 4 - methyl 2,6 - di - tert, butylphenol were obtained, with a melting point of 09.5-70.0°C. The composition of the crystalline product was:
- methyl - 2,6 - di - tert, butylphenol
2,6 — di - tert, butylphenol
The crystals obtained were white.
99.99 wt. %
0.01 wt. %
- 8 061
Example 4
Under the conditions described in Example 1, a 50% solution of alkylphenol in ethyl alcohol of the following composition was fed at a space-time velocity of 0.23 hr-1 into the crystallizer:
- methyl - 2,6 - di - tert, butylphenol 94 wt. %
2.6 - di - tert, butylphenol 3 wt. %
2.4.6 - tri - tert, butylphenol 3 wt. %
Ethyl alcohol moved at a space-time velocity of 0.13 hrl in counter-flow to the crystals of 4 methyl - 2,6 - di - tert, butylphenol, which moved, as a layer at a space-time velocity of 0.13 hr-1 in the vertical washing element. After 50 hours of operation, 7,900 g of 4 - methyl - 2,6 - di - tert, butylphenol were obtained with a melting point of 69.5-7O°C. The composition of the crystalline product was:
- methyl - 2,6 - di - tert, butylphenol
2,6 - di - tert, butylphenol The crystals obtained were white
99.99 wt. % 0.01 wt. 1
Example 5
Under the conditions described in Example 1, a 30% solution of alkylphenol in gasoline of the following composition was fed at a space-time velocity of 0.12 hr into the crystallizer:
bis -(5- methyl - 3 - tert, butyl 2 - hydroxyphenyl)methane 98 wt. %
- tert, butyl - 4 - methylphenol 1 wt. %
2,6 - di - tert, butyl - 4 - methylphenol l wt. %
Crystallization was conducted at + 20°C under stirr44061
- 9 ing. The crystals of bis -(5- methyl - 3 - tert, butyl - 2 - hydroxyphenyl)methane formed in the crystallizer’ moved as a layer at a space-time velocity of 0.24 hr~^ in the vertical washing element, where gasoline moved in counterflow at a space-time velocity of 0.09 hr- . The washed crystals of bis -(5- methyl - 3 - tert, butyl - 2 - hydroxyphenol )methane were delivered continuously to the sampler and from there for drying. After 20 hours of operation, 1,000 g of bis -(5- methyl - 3 - tert, butyl - 2 - hydroxyphenyl ) - methane were obtained with a melting point of 129.3-130.0°C. No impurities were found in the product by chromatographic analysis.
Example 6
Under the conditions described in Example 1, a 50/ solution of alkylphenol in ethyl alcohol of the
following composition was fed at a of 0.12 hr 1 into the crystallizer: space-time velocity 2,6 - di - tert, butylphenol 9?.7 wt. ? 2,4 - di - tert, butylphenol 0.55 wt. % 2,4,6 - tri - tert, butyl- phenol 0.44 Wt. % ortho - tert, butylphenol 0.31 Wt. %
Ethyl alcohol moved at a space-time velocity of 0.14 hr“l in counterflow to the crystals of 2,6 -ditert. butylphenol, which moved as a layer at a spacetime velocity of 0.4 hr in the vertical washing element. The crystals of 2,6 - di - tert, butylphenol were removed continuously through the sampler. After 50 hours of operation, 4,100 g of 2,6 - di - tert, butylphenol
440 61 were obtained with a melting point of 35-5-36°C (the melting point as reported in the literature is 35.0-36.0°C). No impurities were found in the product by chromatographic analysis.
Example 7
Under the conditions described in Example 1, a 50% solution of alkylphenol in ethyl alcohol of the following composition was fed at a space-time velocity of 0.12 hr- into the crystallizer:
2.4.6 - tributylphenol
2.6 - di - tert, butylphenol 2,4 “ di - tert, butylphenol
97.0 wt. % 2.0 wt. % 1.0 wt. %
Ethyl alcohol moved at a space-time velocity of 0.14 hr in counterflow to the crystals of 2,4,6 15 tri - tert, butylphenyl, v/hich moved as a layer at a space-time velocity of 0.38 hr-1 in the vertical washing element. The crystals of 2,4,6 - tri - tert, butylphenol were removed continuously through the sampler. After 50 hours of operation, 4j3OO g. of 2,4,6 - tri - tert.
butylphenol were obtained with a melting point of 130131.0°C (the melting point as reported in the literature is 13O-131°C). No impurities were found in the product by chromatographic analysis.
Claims (4)
1. A method of purifying an alkylphenol from impurities contained therein, comprising effecting continuous crystallization of alkylphenol fed at a space-time 5 velocity of from 0,12 to 0.31 hr and washing the resulting crystals In a layer formed by the said crystals and moving downwards at a space-time velocity of from 0.1 to 1.0 hr - ''', washing being performed with a solvent inert towards alkylphenol and moving in count10 erflow to the crystals at a space-time velocity of from 0.09 to 0.35 hr -1 , and wherein the said washing is carried out in a washing element in the form of a vertical tube in which the crystals of alkylephenol are maintained in the form of a movable bed, the dimensions 15 of the said vertical tube being such that the ratio of the height of the moving layer of the crystals to the diameter of the crystal bed is at least 3.
2. A method as claimed in claim 1, wherein the solvent is ethyl alcohol, methyl alcohol, isopropyl alcohol, 20 acetone or gasoline.
3. A method of purifying an alkylphenol, substantially as herein described in any of the foregoing Examples.
4. An alkylphenol purified by the method as claimed in any of claims 1 to 3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU762334592A SU622257A1 (en) | 1976-03-17 | 1976-03-17 | Alkylphelol purifying method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE44061L IE44061L (en) | 1977-09-17 |
| IE44061B1 true IE44061B1 (en) | 1981-07-29 |
Family
ID=20652312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE577/77A IE44061B1 (en) | 1976-03-17 | 1977-03-16 | Method of purifying alkylphenols |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS52131536A (en) |
| AT (1) | AT350524B (en) |
| BE (1) | BE852507A (en) |
| BR (1) | BR7701639A (en) |
| DE (1) | DE2711712A1 (en) |
| DK (1) | DK115177A (en) |
| ES (1) | ES456964A1 (en) |
| FI (1) | FI770849A (en) |
| FR (1) | FR2344516A1 (en) |
| GB (1) | GB1514702A (en) |
| IE (1) | IE44061B1 (en) |
| NL (1) | NL7702863A (en) |
| NO (1) | NO770936L (en) |
| PT (1) | PT66309B (en) |
| SE (1) | SE7702987L (en) |
| SU (1) | SU622257A1 (en) |
-
1976
- 1976-03-17 SU SU762334592A patent/SU622257A1/en active
-
1977
- 1977-03-14 AT AT172477A patent/AT350524B/en not_active IP Right Cessation
- 1977-03-16 PT PT66309A patent/PT66309B/en unknown
- 1977-03-16 SE SE7702987A patent/SE7702987L/en unknown
- 1977-03-16 DK DK115177A patent/DK115177A/en unknown
- 1977-03-16 JP JP2811477A patent/JPS52131536A/en active Pending
- 1977-03-16 NO NO770936A patent/NO770936L/en unknown
- 1977-03-16 NL NL7702863A patent/NL7702863A/en not_active Application Discontinuation
- 1977-03-16 IE IE577/77A patent/IE44061B1/en unknown
- 1977-03-16 BE BE175815A patent/BE852507A/en unknown
- 1977-03-16 FR FR7707853A patent/FR2344516A1/en active Granted
- 1977-03-17 ES ES456964A patent/ES456964A1/en not_active Expired
- 1977-03-17 FI FI770849A patent/FI770849A/fi not_active Application Discontinuation
- 1977-03-17 BR BR7701639A patent/BR7701639A/en unknown
- 1977-03-17 GB GB11313/77A patent/GB1514702A/en not_active Expired
- 1977-03-17 DE DE19772711712 patent/DE2711712A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52131536A (en) | 1977-11-04 |
| FI770849A (en) | 1977-09-18 |
| FR2344516A1 (en) | 1977-10-14 |
| BE852507A (en) | 1977-09-16 |
| DE2711712A1 (en) | 1977-09-29 |
| DK115177A (en) | 1977-09-18 |
| ES456964A1 (en) | 1978-02-16 |
| BR7701639A (en) | 1977-11-08 |
| NO770936L (en) | 1977-09-20 |
| IE44061L (en) | 1977-09-17 |
| GB1514702A (en) | 1978-06-21 |
| SU622257A1 (en) | 1979-03-15 |
| SE7702987L (en) | 1977-09-18 |
| ATA172477A (en) | 1978-11-15 |
| PT66309B (en) | 1978-08-11 |
| AT350524B (en) | 1979-06-11 |
| FR2344516B1 (en) | 1978-12-29 |
| NL7702863A (en) | 1977-09-20 |
| PT66309A (en) | 1977-04-01 |
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