Process for preparation of n-propyl benzene
09688589 ยท 2017-06-27
Assignee
Inventors
Cpc classification
C07C2/72
CHEMISTRY; METALLURGY
C07C2/72
CHEMISTRY; METALLURGY
Y02P20/52
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C07C2/72
CHEMISTRY; METALLURGY
Abstract
Disclosed is a process for preparation of n-propyl benzene. The process gives high selectivity and yield of n-propyl benzene by single step catalytic alkylation that involves contacting a mixture of aromatic hydrocarbon having an active hydrogen on a saturated -carbon, such as toluene, and an alkene, such as ethylene, in presence of a metal catalyst, a solid support, and an initiator. Following the alkylation, aqueous and organic phases are separated from a reaction mixture. The aqueous phase is separated for recovery of the catalyst, the solid support, and un-reacted aromatic hydrocarbon (e.g., toluene); and the organic phase is separated for obtaining n-propyl benzene and byproduct. Thus, the catalyst phase can be recovered and recycled in the next alkylation reaction. Also, the process facilitates recovery and recycling of the byproduct for the better selectivity.
Claims
1. A process for the preparation of n-propyl benzene, the process comprising the steps of: (a) adding a first amount of dry toluene and a dry solid support comprising an alkali metal carboxylate to a first reactor to form a mixture; (b) adding an alkali metal catalyst and oleic acid to the mixture prepared in step (a) to form a reaction mass, and closing and agitating the first reactor for a time period of about 30 minutes to about 1 hour; (c) flushing the first reactor with nitrogen gas, and heating the reaction mass to a temperature in a range of about 185 C. to about 190 C. for about 15 minutes to activate the catalyst; (d) adding a second amount of dry toluene and a first amount of initiator selected from di-tert-butyl peroxide, azo-iso-bis butyronitrile, or iso-amyl nitrite to a second reactor, flushing the second reactor with nitrogen gas, and stirring for about 15 minutes to about 30 minutes, then transferring the second amount of dry toluene and first amount of initiator from the second reactor to the first reactor; (e) heating the first reactor to a temperature in a range of about 180 C. to about 220 C., then adding ethylene to the first reactor to form a reaction medium comprising n-propyl benzene; (f) periodically adding a second amount of initiator selected from di-tert-butyl peroxide, azo-iso-bis butyronitrile, or iso-amyl nitrite to the first reactor, and maintaining the reaction medium at a temperature range of about 180 C. to about 220 C. for about 1 hour to about 5 hours while agitating the reaction medium at about 35 kg/cm.sup.2 to about 40 kg/cm.sup.2 and monitoring ethylene consumption, wherein a sum total amount of said initiators added in step (d) and step (f) is about 50 ppm to about 100 ppm; (g) cooling the reaction medium to room temperature, then adding an amount of methanol and then adding an amount of water to the reaction medium; (h) separating the reaction medium into an aqueous phase comprising the catalyst, solid support and un-reacted toluene, and an organic phase comprising n-propyl benzene and byproduct; and (i) analyzing the organic phase and separating the n-propyl-benzene from the byproduct.
2. The process of claim 1, wherein the n-propyl benzene is separated from the byproduct by fractional distillation, and analyzed by gas chromatography.
3. The process of claim 1, wherein the alkali metal carboxylate is potassium carbonate.
4. The process of claim 1, wherein the alkali metal catalyst is selected from the group consisting of sodium, lithium, and a combination thereof.
5. The process of claim 1, further comprising recovering the un-reacted toluene from the aqueous phase and using at least a portion of the recovered un-reacted toluene in step (a).
6. The process of claim 1, wherein said byproduct comprises a 3-phenyl-pentane.
7. The process of claim 6, wherein at least a portion of the byproduct is recycled to the first reactor.
Description
BRIEF DESCRIPTION OF THE DRAWING
(1)
DETAILED DESCRIPTION
(2) It should be understood that this invention is not limited to the particular methodology, protocols, and reagents, etc., described herein and as such may vary. The terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention, which is defined solely by the claims.
(3) As used herein and in the claims, the singular forms include the plural reference and vice versa unless the context clearly indicates otherwise. The term or is inclusive unless modified, for example, by either. Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein should be understood as modified in all instances by the term about.
(4) All patents and other publications identified are expressly incorporated herein by reference for the purpose of describing and disclosing, for example, the methodologies described in such publications that might be used in connection with the present invention. These publications are provided solely for their disclosure prior to the filing date of the present application. Nothing in this regard should be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention or for any other reason. All statements as to the date or representation as to the contents of these documents is based on the information available to the applicants and does not constitute any admission as to the correctness of the dates or contents of these documents.
(5) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as those commonly understood to one of ordinary skill in the art to which this invention pertains. Although any known methods, devices, and materials may be used in the practice or testing of the invention, the methods, devices, and materials in this regard are described herein.
(6) The various aspects of the invention are accomplished, and the problems and shortcomings associated with the prior art techniques and approaches thereof are overcome, by the embodiments as described below.
(7) The present embodiments provide a process for preparation of n-propyl benzene. In one embodiment, the process gives high selectivity and yield of n-propyl benzene by single-step catalytic alkylation that involves contacting a mixture of toluene and ethylene, over an alkali metal such as lithium or sodium and alkali metal carboxylate like potassium carbonate, in presence of initiators/promoters such as di-ter-butyl peroxide (DTBP), azo-iso-bis butyronitrile (AIBN), and iso-amyl nitrite.
(8) Referring to
(9) At step (30) of an embodiment, the process (200) involves adding alkali metal catalyst and oleic acid as a dispersing agent to the mixture to form a reaction mass. The alkali metal catalyst can be selected from sodium, lithium, or a combination thereof. In an embodiment, molten sodium metal or lithium metal can be used and coated on the solid support. After addition of the alkali metal catalyst and oleic acid, the first reactor can be closed and agitated for a time period of about 30 minutes to about 1 hour.
(10) At step (40), the process (200) of an embodiment may involve flushing nitrogen gas to the first reactor, which creates inertness therein. At step (50), the process (200) may involve heating the reaction mass at a temperature in a range of about 185 C. to about 190 C. for about 15 minutes.
(11) At step (60), the process (200) may involve adding an aromatic hydrocarbon and an initiator to a second reactor. In a particular embodiment, the aromatic hydrocarbon is toluene. The initiator may be selected from di-ter-butyl peroxide, azo-iso-bis butyronitrile, iso-amyl nitrite, or a combination thereof. The nitrogen gas can then be flushed inside the second reactor, and the contents of the second reactor kept under stirring for a time period of about 15 minutes to about 30 minutes. Then, a bottom liquid discharge valve of the second reactor can be connected to the first reactor.
(12) At step (70) shown in
(13) At step (80), the process (200) may involve periodically adding a small amount of the initiator to the first reactor. The reaction may be continued until a desired consumption of ethylene is observed. The reaction mixture can be maintained at a temperature in a range of about 180 C. to about 220 C. for longer than 1 hour to 5 hours while agitating the reaction mixture at about 35 kg/cm2 to about 40 kg/cm2. Once the desired consumption of ethylene is observed, the reaction mixture may be cooled to room temperature.
(14) At step (90), the process (200) may involve adding desired amount of methanol and water to the reaction mixture. The reaction mixture may then be taken out of the first reactor.
(15) At step (100), the process (200) may involve separating an aqueous phase and an organic phase from the reaction mixture. The aqueous phase can be separated for recovery of the catalyst, catalyst support, and un-reacted toluene; and the organic phase can be separated for obtaining n-propyl benzene and byproduct. At step (110), the process (200) may involve analyzing the organic phase. In a particular embodiment, the organic phase is analyzed by gas chromatography (hereinafter the GC). The purity of n-propyl benzene has been found to be 99.82% by the GC analysis. The process (200) ends at step (120).
(16) The process embodied in
(17) In an embodiment of the process (200), among the products that can be synthesized more efficiently using alkyl benzenes, such as iso-butyl benzene, prepared in accordance with this embodiment, include members of the family of compounds that comprise the 2-aryl propionic acid derivatives. Specially, ibuprofen, a commercially successful, over-the-counter analgesic, can be synthesized using isobutyl benzene prepared as a raw material. Similarly, in another embodiment, among the products that can be synthesized more efficiently using alkyl benzenes, include 3-isobutyl-toluene and sec-butyl benzene, starting from m-xylene-propylene and ethylbenzene-ethylene, respectively.
(18) The embodiments are further illustrated hereinafter by means of examples.
EXAMPLES
Example 1
Preparation of n-Propyl Benzene Using Potassium Carbonate as the Solid Support for Sodium Catalyst without Initiator (Control Experiment)
(19) The first reactor is a 2 liter capacity high-pressure stirred reactor. To the first reactor, dry toluene, dry potassium carbonate, sodium metal catalyst and oleic acid as the dispersing agent were added. The first reactor was then closed, and the agitation of the first reactor was started. The first reactor was flushed with nitrogen gas. Then the reaction mass was heated for 15 minutes at a temperature in a range of about 185 C. to about 190 C. to activate the catalyst.
(20) Meanwhile, a small amount of dry toluene was taken in the second reactor. The second reactor is a 500-ml capacity stirred high pressure reactor. Nitrogen was flushed to the contents of the second reactor and kept under stirring. The bottom liquid discharge valve of the second reactor was connected to the first reactor and the vents of both of the reactors were connected.
(21) Once the desired reaction temperature of the first reactor was attained, a desired amount of ethylene was added to the first reactor with the help of ethylene cylinder. The addition of ethylene caused the pressure of the first reactor to rise initially and subside slowly as the ethylene consumption took place. The reaction was continued until desired consumption of ethylene was observed, and then the reaction mass was cooled to room temperature. To the reaction mass, a desired amount of methanol followed by water was added. The reaction mixture was taken out of the first reactor, and a lower aqueous phase and an upper organic phase were separated. The organic phase was analyzed using GC. The GC model used was Shimadzu-17 A, the Column used was DB Petro 100 m length (ID 0.25 mm, film thickness 0.5 micron), FID detector, Injector temperature 250 C., Detector temperature 260 C., Initial temperature 80 C., hold time 2 minutes, heating rate 4 C./min, final temperature 250 C. for 30 minutes, nitrogen flow rate 1.4 ml/min, split ratio 1:80. The results of the various examples are as shown in the following Table-1.
(22) TABLE-US-00001 TABLE 1 Examples - 1.1 and 1.2 using potassium carbonate as catalyst support Example Number Example-1.1 Example-1.2 Charge to 2-L Reactor Dry toluene, gm 922 920 Ethylene Gas Lot-1, gm 98 70 Lot-2, gm 43 70 Potassium carbonate, gm 78 78 Sodium metal, gm 9.2 9.2 Oleic acid, gm 2.5 2.5 Methanol, gm 32 32 Water, gm 600 600 Charge to 500-ml Reactor Dry toluene 0 184 Process conditions Maximum reaction temp., C. 180.9 210.1 Maximum reaction press., kg/cm.sup.2 30.7 44.8 Final reaction press., kg/cm.sup.2 7.6 9.5 Reaction time in hr 4.5 5 Output of reaction mass Wt. of organic layer, gm 904 1181 Wt of aqueous layer, gm 698 694 Analysis, wt % Hexenes, wt % 0.085 0 Toluene, wt % 80.889 61.453 n-Propyl Benzene (NPB), wt % 15.891 23.821 3-PP (**) and Heavies, wt % 2.997 14.726 Reaction performance Toluene to Ethylene mol ratio 1.99 2.40 Quantity of NPB, gm 143.65 281.33 Selectivity based on toluene, % 57.76 57.02 Toluene per pass conversion, % 20.68 34.26 NPB to 3-PP & Heavies ratio 5.3 1.62
Example 2
Preparation of n-Propyl Benzene Using Potassium Carbonate as the Solid Support for Sodium Catalyst and the Initiator
(23) The first reactor was a 2 liter capacity high pressure stirred reactor. To the first reactor, dry toluene, dry potassium carbonate, sodium metal catalyst, and oleic acid (as the dispersing agent), was added. The first reactor was then closed and the agitation of the first reactor was started. The first reactor was flushed with nitrogen gas. Then the reaction mass was heated for 15 minutes at temperature in a range of about 185 C. to about 190 C. to activate the catalyst.
(24) Meanwhile, about 184 gm of dry toluene was taken in the second reactor and 50 ppm to 100 ppm of di-ter-butyl peroxide (DTBP) (as the initiator) was added thereto. The second reactor was a 500-ml capacity stirred high-pressure reactor. The nitrogen was flushed to the contents of the second reactor and kept under stirring. The bottom liquid discharge valve of the second reactor was connected to the first reactor, and the vents of both the reactors were connected.
(25) Once the desired reaction temperature of the first reactor was attained, a desired amount of ethylene was added to the first reactor with the help of ethylene cylinder. The addition of ethylene caused the pressure of the first reactor to rise initially and subside slowly as the ethylene consumption took place. The reaction was continued until a desired consumption of ethylene was observed, and then the reaction mass was cooled to room temperature. To the reaction mass, a desired amount of methanol followed by water was added. The reaction mixture was taken out of the first reactor, and a lower aqueous phase and an upper organic phase were separated. The organic phase was analyzed using the GC as mentioned in Example 1. The details and the results of the examples 2.1 to 2.8 are shown in the following Table-2.
(26) TABLE-US-00002 TABLE 2 Examples - 2.1 to 2.8: potassium carbonate as catalyst support with DTBP as initiator Example Number: Example-2.1 Example-2.2 Example-2.3 Example-2.4 Charge to 2-L Reactor Dry toluene, gm 922 922 922 922 Ethylene Gas Lot-1, gm 70 140 140 90 Lot-2, gm 70 10 Potassium carbonate, gm 78 78 78 78 Sodium metal, gm 8.7 9.2 9.2 9.2 Oleic acid, gm 2.5 2.5 2.5 2.5 Methanol, gm 32 32 32 32 Water, gm 600 600 600 600 Charge to 500-ml Reactor Dry toluene 184 184 184 184 Initiator, DTBP(*), mg 60 120 60 60 Process conditions Maximum reaction temp., C. 182.2 185.5 190.8 190.6 Maximum reaction press., kg/cm.sup.2 36.6 32.2 37.8 33 Final reaction press., kg/cm.sup.2 11.3 7.6 9.3 12.1 Reaction time in hr 2.45 3 3 3.25 Output of reaction mass Wt. of organic layer, gm 1106 1115 1149 1117 Wt of aqueous layer, gm 707 702 718 703 Analysis, wt % Hexenes, wt % 0.12 0.077 0.025 0.1037 Toluene, wt % 73.86 78.346 55.97 72.6199 n-Propyl Benzene (NPB), wt % 21.2 17.327 32.91 20.6993 3-PP (**) and Heavies, wt % 4.41 4.014 10.966 6.42 Reaction performance Toluene to Ethylene mol ratio 2.40 2.40 2.40 3.36 Quantity of NPB, gm 234.47 193.20 378.14 231.21 Selectivity based on toluene, % 62.61 64.28 62.9 60.53 Toluene per pass conversion, % 26.01 20.87 41.75 26.52 NPB to 3-PP & Heavies ratio 4.81 4.32 3.01 3.22 Example Number: Example-2.5 Example-2.6 Example-2.7 Example-2.8 Charge to 2-L Reactor Dry toluene, gm 920 920 920 920 Ethylene Gas Lot-1, gm 45 140 50 45 Lot-2, gm 48 75 48 Potassium carbonate, gm 78 78 78 78 Sodium metal, gm 8.7 9.2 9.2 9.2 Oleic acid, gm 2.5 2.5 2.5 2.5 Methanol, gm 32 32 32 32 Water, gm 600 600 600 600 Charge to 500-ml Reactor Dry toluene 184 184 184 184 Initiator, DTBP (*), mg 120 65 62 60 Process conditions Maximum reaction temp., C. 190.1 195.34 195.4 192.4 Maximum reaction press., kg/cm.sup.2 18.6 31.8 34.2 38.7 Final reaction press., kg/cm.sup.2 8.7 9.2 11.8 10.3 Reaction time in hr 3 3.5 3.25 3.5 Output of reaction mass Wt. of organic layer, gm 1109 1134 1143.2 1107 Wt of aqueous layer, gm 699 698 702 545 Analysis, wt % Hexenes 0.086 0.076 0.0863 0.3792 Toluene 80.7862 63.93 62.5214 62.975 n-Propyl Benzene (NPB) 15.5083 24.6894 25.364 24.87 3-PP (**) and Heavies 3.4307 11.1819 11.898 11.62 Reaction performance Toluene to Ethylene mol ratio 3.61 2.40 2.69 3.61 Quantity of NPB, gm 171.99 279.98 289.96 275.31 Selectivity based on toluene 63.37 56.63 57.11 51.88 Toluene per pass conversion 18.85 34.33 35.26 36.85 NPB to 3-PP & Heavies ratio 4.52 2.21 2.13 2.14 (*) DTBP-Di-tert-butyl peroxide; (**) 3-Phenyl pentane.
Example 3
Preparation of n-Propyl Benzene Using Potassium Carbonate as the Solid Support for Sodium Catalyst with the Initiator
(27) In this example, preparation of n-propyl benzene was carried out using potassium carbonate as the solid support, sodium as the metal catalyst and azo-iso-bis butyronitrile (AIBN) as the initiator. The steps of the process (200) are similar as mentioned in example 2 and the same are not again described herein for the sake of the brevity of the invention. The details and the results of the examples 3.1-3.3 are shown in the following Table-3.
(28) TABLE-US-00003 TABLE 3 Examples 3.1 to 3.3: potassium carbonate as catalyst support, AIBN as initiator Example Number Example- Example- Example- 3.1 3.2 3.3 Charge to 2-L Reactor Dry toluene, gm 920 920 920 Ethylene Gas Lot-1, gm 135 120 165 Lot-2, gm Potassium carbonate, gm 78 78 78 Sodium metal, gm 9.2 9.2 9.2 Oleic acid, gm 2.7 2.7 2.7 Methanol, gm 32 30 30 Water, gm 604 600 600 Charge to 500-ml Reactor Dry toluene 184 184 184 Initiator, AIBN (*), mg 64 60 60 Process conditions Maximum reaction temp., C. 221.8 190.8 195.2 Maximum reaction press., kg/cm.sup.2 53.4 37.4 46.3 Final reaction press., kg/cm.sup.2 16.4 19.9 13.2 Reaction time in hr 3.5 4.25 4.25 Output of reaction mass Wt. of organic layer, gm 1198 1118 1190 Wt of aqueous layer, gm 707 698 701 Analysis, wt % Hexenes, wt % 0.1849 0.2191 0.0808 Toluene, wt % 54.5393 69.9528 55.2322 n-Propyl Benzene (NPB), wt % 27.9853 21.6334 28.274 3-PP (**) and Heavies, wt % 16.981 8.0656 16.2886 Reaction performance Toluene to Ethylene mol ratio 2.49 2.80 2.04 Quantity of NPB, gm 335.26 241.86 336.46 Selectivity based on toluene, % 57.04 57.60 57.74 Toluene per pass conversion, % 40.82 29.16 40.47 NPB to 3-PP & Heavies ratio 1.65 2.68 1.74 (*) AIBN-Azo-Iso-bis Butyro Nitrile; (**) 3-Phenyl pentane.
Example 4
Preparation of n-Propyl Benzene Using Potassium Carbonate as the Solid Support for Sodium Catalyst with the Initiator
(29) In this example, preparation of n-propyl benzene was carried out using potassium carbonate as the solid support, sodium as the metal catalyst, and iso-amyl nitrite as the initiator. The steps of the process (200) are similar as mentioned in Example 2, and the same are not again described herein for the sake of the brevity. The details and the results of the examples 4.1-4.3 are shown in the following Table-4.
(30) TABLE-US-00004 TABLE 4 Examples-4.1 to 4.3: potassium carbonate as catalyst support, iso-amyl nitrite as initiator Example Number Example- Example- 4.1 Example-4.2 4.3 Charge to 2-L Reactor Dry toluene, gm 920 920 920 Ethylene Gas Lot-1, gm 95 127 127 Lot-2, gm Potassium carbonate, gm 78 78 78 Sodium metal, gm 9.3 9.18 9.18 Oleic acid, gm 2.5 2.5 2.5 Methanol, gm 32 32 32 Water, gm 604 600 600 Charge to 500-ml Reactor Dry toluene 184 184 184 Initiator, iso-Amyl Nitrite, mg 120 64 64 Process conditions Maximum reaction temp., C. 195.5 195.1 195.1 Maximum reaction press. kg/cm.sup.2 39 43 43 Final reaction press. kg/cm.sup.2 12 19 19 Reaction time in hr 4.5 4.25 4.5 Output of reaction mass Wt. of organic layer, gm 1009 1106 1106 Wt. of aqueous layer, gm 721 708 698 Analysis, wt % Hexenes, wt % 0.0735 0.1106 0.1106 Toluene, wt % 74.038 70.324 70.324 n-Propyl Benzene (NPB), wt % 18.292 19.127 19.127 3-PP (**) and Heavies, wt % 7.542 10.3868 10.3868 Reaction performance Toluene to Ethylene mol ratio 3.54 2.65 2.65 Quantity of NPB, gm 184.57 211.54 211.54 Selectivity based on toluene, % 39.64 49.72 49.72 Toluene per pass conversion, % 32.33 29.55 29.55 NPB to 3-PP & Heavies ratio 2.43 1.84 1.84 (**) 3-Phenyl pentane.
Example 5
Preparation of n-Propyl Benzene Using Potassium Carbonate as the Solid Support for Lithium Metal Catalyst with Initiator
(31) In this example, preparation of n-propyl benzene was carried out using potassium carbonate as the solid support, lithium as the metal catalyst and di-ter-butyl peroxide (DTBP) as the initiator. The steps of the process (200) are similar as mentioned in Example 2, except the temperature range of 190 C. to 200 C., and the same are not again described herein for the sake of the brevity. The details and the results of the examples 5.1 and the control experiment (without initiator) are shown in the following Table-5.
(32) TABLE-US-00005 TABLE 5 Example-5.1, Control: potassium carbonate catalyst support, lithium metal catalyst, DTBP initiator Example Number Example-5.1 Control Example Charge to 2-L Reactor Dry toluene, gm 920 920 Ethylene Gas Lot-1, gm 70 70 Lot-2, gm 70 70 Potassium carbonate, gm 78 78 Sodium metal, gm 0 9.2 Lithium metal, gm 3 0 Oleic acid, gm 2.5 2.5 Methanol, gm 32 32 Water, gm 600 600 Charge to 500-ml Reactor Dry toluene 184 184 Initiator, DTBP, mg (*) 225 0 Process conditions Maximum reaction temp., C. 215.2 210.1 Maximum reaction press., kg/cm.sup.2 39 44.8 Final reaction press., kg/cm.sup.2 21 9.5 Reaction time in hr 8.5 5 Output of reaction mass Wt. of organic layer, gm 1178 1181 Wt of aqueous layer, gm 708 694 Analysis, wt % Hexenes, wt % 0 0 Toluene, wt % 63.863 61.453 n-Propyl Benzene (NPB), wt % 26.061 23.821 3-PP (**) and Heavies, wt % 9.802 14.726 Reaction performance Toluene to Ethylene mol ratio 2.40 2.40 Quantity of NPB, gm 307 281.33 Selectivity based on toluene, % 66.92 57.02 Toluene per pass conversion, % 31.86 34.26 NPB to 3-PP & Heavies ratio 2.66 1.62 (*) DTBP-Di-tert-butyl peroxide; (**) 3-PP-3-Phenyl pentane.
Example 6
Preparation of n-Propyl Benzene Using Potassium Carbonate as the Solid Support for Sodium Metal Catalyst and Recycling of the Alkali Metal Catalyst Along with Partial Recycling of 3-Phenyl Pentane
(33) In this example, preparation of n-propyl benzene was carried out using potassium carbonate as the solid support, sodium as the metal catalyst and di-ter-butyl peroxide (DTBP) as the initiator. The steps of the process (200) are similar as mentioned in Example 2 and the same are not again described herein for the sake of the brevity. The reaction mixture was siphoned out of the first reactor under pressure so that only the liquid phase was transferred. The liquid phase was used for collection of residual catalyst, potassium carbonate and un-reacted toluene, and the remaining organic phase was used for collection of 3-phenyl pentane. The residual catalyst and potassium carbonate so collected were then continuously recycled for at least 10-15 times in the next preparation cycles of n-propyl benzene.
(34) The details and the results of examples 6.1 to 6.5 for recycling the alkali metal catalyst are shown in Table-6. The details and the results of recycling the catalyst and part recycle of 3-phenyl pentane are reflected in the examples 7.1 and 7.2 for, shown in Table-7.
(35) TABLE-US-00006 TABLE 6 Examples-6.1-6.5: potassium carbonate catalyst support, sodium metal catalyst: recycle of alkali metal catalyst Example Number Example- Example- Example- Example- Example- 6.1 6.2 6.3 6.4 6.5 Remarks Fresh Catalyst Catalyst Catalyst Catalyst Cycle Recycle-1 Recycle-2 Recycle-3 Recycle-4 Charge to 2-L Reactor Dry toluene, gm 806 802 962 1010 1206 Initiator, DTBP, mg (*) 80 80 90 100 120 Ethylene Gas Lot-1, gm 180 165 154 158 138 Lot-2, gm 0 0 0 0 0 Potassium carbonate, gm 146 0 0 0 0 Sodium metal, gm 14.76 10.312 10.428 10.218 8.342 Oleic acid, gm 3.8 3 3 3.5 2.5 Methanol, gm 0 0 0 0 501 Water, gm 422 425 450 501 508 Process conditions Maximum reaction 228.5 211.2 212.3 216.1 208.2 temp., C. Maximum reaction 43 41 40 40 34 press. kg/cm.sup.2 Final reaction 8 7 6 7 7 press. kg/cm.sup.2 Reaction time in hr 2 1.15 1.45 1 1 Output of reaction mass Wt. of organic layer, gm 778 942 1037 1195 1396 Wt of aqueous layer, gm 422 434 459 505 1038 Analysis, wt % Toluene, wt % 42.580 39.721 48.625 50.613 62.294 n-Propyl Benzene 35.444 37.305 35.852 36.508 20.580 (NPB), wt % 3-PP (**) 19.909 20.846 13.820 11.150 6.001 Heavies, wt % 2.067 2.128 1.703 1.730 11.125 Reaction performance Toluene to Ethylene mol 1.39 1.36 1.48 1.90 1.95 ratio Quantity of NPB, gm 275.75 351.41 371.79 436.27 287.30 Selectivity based on 44.53 62.97 62.27 82.55 65.48 toluene, % Toluene per pass 58.90 53.35 47.58 40.12 27.89 conversion, % NPB to 3-PP ratio 1.78 1.79 2.59 3.27 3.43 NPB to Heavies ratio 17.15 17.53 21.05 21.11 1.85 (*) DTBP-Di-tert-butyl peroxide; (**) 3-Phenyl pentane.
(36) TABLE-US-00007 TABLE 7 Examples-7.1 and 7.2: potassium carbonate catalyst support, sodium metal catalyst, recycle of the catalyst and part recycle of 3-phenyl pentane Example Number Example-7.1 Example-7.2 Remarks Fresh Cycle Catalyst Recycle-1 Charge to 2-L Reactor Dry toluene, gm 774.97 781.74 Initiator, DTBP, mg (*) 80 80 3-PP (**) 26.03 26.26 Ethylene Gas Lot-1, gm 145 135 Lot-2, gm Potassium carbonate, gm 145 0 Sodium metal, gm 14.766 10.256 Oleic acid, gm 3.6 3 Methanol, gm 0 0 Water, gm 395 670 Process conditions Maximum reaction temp., C. 200.1 200.4 Maximum reaction press., kg/cm.sup.2 40 39 Final reaction press., kg/cm.sup.2 8 8 Reaction time in hr 1.5 1.5 Output of reaction mass Wt. of organic layer, gm 784 1020 Wt of aqueous layer, gm 398 832 Analysis, wt % Toluene, wt % 49.127 49.509 n-Propyl Benzene (NPB), wt % 33.867 33.214 3-PP (**) 14.159 14.948 Heavies, wt % 2.847 2.330 Reaction performance Toluene to Ethylene mol ratio 1.63 1.76 Quantity of NPB, gm 265.52 338.78 Selectivity based on toluene, % 51.17 91.19 Toluene per pass conversion, % 50.81 36.06 NPB to 3-PP ratio 3.27 2.76 NPB to Heavies ratio 11.90 14.25 (*) DTBP-Di-tert-butyl peroxide (**) 3-Phenyl pentane
Example 7
Purification of n-Propyl Benzene
(37) An atmospheric pressure fractional distillation assembly was used for the purification of n-propyl benzene. The fractional distillation assembly consists of 10 L capacity stirred jacketed distillation still having 50 mm diameter and 1500 mm height packed distillation column, reflux condenser, distillate receiver, top and bottom temperature indicators and the like. Ten (10) kg crude n-propyl benzene obtained from any of the examples 1 to 6 was added to the fractional distillation assembly. The crude material, under stirring, was heated with the help of a hot oil circulator. Toluene was recovered until the top temperature reached 110 C. to 125 C. and the bottom temperature reached 150 C. to 155 C., with the reflux ratio 2. The recovered toluene was recycled in a next n-propyl benzene synthesis run. Pure n-propyl benzene was collected at the top temperature of 165 C. to 170 C. and the bottom temperature of 180 C. to 190 C. During n-propyl benzene collection, a reflux ratio of 3 to 4 was maintained. In all distillation cuts, distillation residues were analyzed using the GC as mentioned under Examples 1 and 2. The purity of n-propyl benzene cut was found to be 99.82% by GC analysis.
(38) The embodiments described herein have the following advantages: (a) The process (200) facilitates reuse of higher alkylated product such as 3-phenyl pentane, alkali metal catalyst and the solid support that improves the selectivity and reduces the effluent load and thus the waste disposal and hence is economically and commercially attractive; (b) The initiators being aprotic in nature are required in very small amount, and improve the selectivity of starting alkyl benzene towards the desired product; (c) The process (200) is less hazardous because dry reagents are used and water is not used in a reaction zone; (d) The potassium carbonate powder improves distribution of catalyst by offering a large amount of surface area for spreading the metal catalyst thereon, thereby allowing a large mass transfer area for the reaction; (e) The potassium carbonate powder improves the contact area between the alkali metal catalyst and the alkyl benzene, and thereby improves the mixing and ensures the availability of the alkali metal catalyst throughout the first reactor; and (f) Compared with potassium, sodium and lithium are easily available, less hazardous to handle, and used in lesser amounts due to lower/lesser atomic weights.
(39) The foregoing embodiments are accomplished and the problems and shortcomings associated with prior art techniques and approaches are overcome as described in the present embodiments. Detailed descriptions of the embodiments are provided herein; however, it should be understood that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system, structure, or matter. The embodiments described above and the methods disclosed herein may suggest further modification and alterations to those skilled in the art. Such further modifications and alterations may be made without departing from the spirit and scope of the invention.