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6-4 7%. 6226. Agent Nov. 14, 1950 W. D., SMUTZ 2,529,887 PROCESS FOR THE PREPARATION OF ANSOLE Filed May 19, 1949 i O creaseaxxx CONDENSER SODUM HYDROXDE PHENOL HEAT EXCHANGER INVENTOR. WALTER D. SMUTZ 6-4 7%. 6226. AGENT Patented Nov. 14, 1950 2,529,887 UNITED STATES PATENT OFFICE 2,529,887 PROCESS FOR THE PRE PARATION OF ANSOLE Walter D. Smutz, Warrensville Heights, Ohio, as signor to E. E. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware Application May 19, 1949, Serial No. 94,226 Clains, (C. 260-612) 2 This invention relates to the manufacture of portion of the still which contains a large body anisole. More particularly it relates to continu Of not a queous Sodium phenate. ous processes in which a methylating agent for The base of the still is preferably conically phenol is added continuously to a stream of refor Shaped to facilitate the collection and withdrawal tified aqueous sodium phenate maintained in froin the Still of Crystalline Sodium Sulfate Which turbulent flow. The stream is heated to form is a by-product of the ainiSole process. The Sodi anisole therein. The anisole is separated and un un. Sulfate is withdra Win thru line 9 according to reacted aqueous sodium phenate is refortified by the enbodiment of the invention illustrated in adding phenol and an alkaline Sodium compound. the dra Wing. A stream of the refortified aqueous sodium phe 10 Hot a queous Sodiun phenate is withdrawn nate is then recycled for admixture with the from Still thru line 5. This hot aqueous Sodium Aethylating agent. phenate is refortified by the addition of Sodium This application is a continuation-in-part of hydroxide thru line and phenol thru line . my copending applications Serial No. 724,718, line Sodium hydroxide and phenol are added in filed January 27, 1947, now U. S. Patent 2,490,842 5 Substantially Stoichiometric proportions and in issued December 13, 1949, and Serial No. 15,760 aimou Eat Sufficient to naaintain the sodium phenate filed March 19, 1948, now abandoned. strength in the refortified Solution at a prede It is an object of this invention to provide proc termined value. After an intimate mixing of esses which are practical and economical for the newly added Sodium hydroxide and phenol, the commercial production of anisole in high 2) as in pipe line mixer 6, to give the refortified hot yield using as reactants phenol, a methylating aqueous Sodium phenate, dimethyl sulfate is agent for phenol, and an alkaline Sodium COn added to a turbulent stream of the refortified pound selected from the class consisting of Sodium liquid ahead of the inlet of a pump 7. hydroxide and a sodium carbonate. Other ob The pump 7 following the inlet point of the jects and advantages of the invention Will become 25 dimethyl Sulfate is preferably a centrifugal pump apparent from the following description and ac So aS to effect a rapid allinoSt instantaneous mix coinpanying drawing. ing of the dimethyl Sulfate with the aqueous sodi Processes of the invention are illustrated in the in phenate So that local excesses of the dimethyl drawing on which there is shown in Senidia Sulfate are avoided. grammatical form an apparatus adapted for use 30 A homogeneous liquid maSS flows from pump 7 in the practice of a preferred embodiment of the into heat eXchanger 3. In the heat exchanger, present invention. In the processes illustrated Sufficient heat is introduced into the reacting mass by the drawing, dinnethyl Sulfate is used as the to effect substantial completion of the anisole methylating agent and the alkaline SOdium Com forming reaction and to Steain distill anisole pound employed is sodium hydroxide. 3 5 present in the maSS. The heated reacting mass Having reference to the drawing, there Will be then leaves the heat eXchanger thru pipe 2 and seen as a central unit a still . The still has an is expanded into Still at point 4 as previously inet pipe 2 leading from the heat eXchanger 3 described. into the upper part of the still at point 4 and an The items in the drawing which have not yet outlet pipe 5 leading thru a pipe line mixer 6 and () been referred to relate to the recovery of the a punp to the heat eXchanger 3, thus pernit product anisole and the by-product sodium sul ting a cyclic flow of materials. The still also has fate and they will be considered in more detail other outlet and inlet lines as will be more fully later. described later. Turning now to a consideration in greater de According to the processes of the invention ill 45 tail of the operating conditions of applicant's lustrated in the drawing, an inlet pipe 2 conveys preferred proceSS illustrated by the drawing, it a heated aqueous reacting maSS containing ani is to be noted at the OutSet that still contains sole, sodium phenate, and Sodium Sulfate from a volume of a dueois Sodium phenate which is the heat, exchanger 3 to the upper part of the large compared with the volume of materials stil. The upper part of the still is preferably 50 added to the proceSS pei minute. For example, cylindrical and the heated reacting maSS is ex according to a preferred embodiment, the process panded into this upper part tangentially at point is operated so that there is maintained in the still 5, thus imparting a rotatory motion to the heated from 500 to 1500 gallions of aqueous. Sodium aSS. phenate for each gallon of materials added to the Upon expanding the heated mass into the still 55 process per minute. Additionally the process is at point 4, a mixture of anisole and water is operated so that the amount of aqueous sodium vaporized or “flashed off' from the maSS and phenate withdrawn for recycle is only a fraction leaves the still thru line 8. The unvaporized re of the volume contained in the still. For example, mainder of the mass which consists predoni the volume of aqueous sodiun phenate in the Still nantly of aqueous sodium phenate and a Small 60 is preferably from 2 to 6 gallons for each gallon of amount of sodium sulfate drops into the lower the solution withdrawn per minute for recycle, 2,529,887 3 4. The retention of a large body of aqueous what with the strength of the sodium phenate so sodium phenate in the still serves a multiple func lution. Preferably the rate of addition is from tion. The liquid body in the still acts as a reser 0.5 thru 1.0 part by weight of dimethyl sulfate voir for the reactant, sodium phenate, as a source per 1000 parts by weight of the refortified aqueous of constant supply of a uniform liquid to serve as s Sodium phenate solution. a diluent in the reaction process and in general According to the invention, the rate of addi as a “flywheel' for the process; that is, the body tion of dimethyl sulfate is also coordinated with of liquid in the still has a function which is anal the additions of sodium hydroxide and phenol ogous to a flywheel in a machine in that the so that these three reactants are introduced into body of liquid acts to moderate and minimize, be ) the system in Substantially the Stoichiometric cause of its mass, fiuctuations and variations in proportions required for the formation of anisole. the addition of reactants, temperatures and usual In other words, Substantially one-half mol of process variables, thus stabilizing the process. dimethyl Sulfate is added for each mol of phenol As mentioned previously, sodium hydroxide and added to the system. phenol are introduced thru pipes 0 and , re The homogeneous liquid leaving pump paSSes spectively, into hot aqueous sodium phenate with into heat exchanger 3. In the heat exchanger drawn from still thru line 5. The Sodium hy the reacting mass is heated to a temperature droxide and the phenol are added in Substantially - above 106° C. and preferably to a temperature of st oichiometric proportions for the formation of 108° C. thru 1.15° C. The reacting mass in the sodium phenate to form what has been termed 20 heat exchanger is maintained under pressure, the refortified aqueous sodium phenate. It is preferably a pressure of 15 thru 45 pounds per Sq. preferred that the aqueous Sodium phenate So inch gauge. Sufficient heat is introduced into lution in the reaction cycle be maintained sub the reacting mass to steam distill the anisole pres stantially neutral, that is, that where there be no ent in the maSS. appreciable excess of either sodium hydroxide or 2 5 As pointed out previously, the heated reacting phenol in the liquid maSS. To maintain this mass from the heat exchanger is passed into the neutral condition, it may be necessary Occasion vapor space of still . Preferably the heated ally to add more than the stoichiometric amount mass is expanded tangentially into the Vapor of sodium hydroxide but ordinarily once the proc space of the still at point 4, thus imparting a ess has been operated for awhile and Stabilized at 30 rotatory motion to the heated mass as it is in uniform conditions, it is not necessary to vary the troduced into the distillation Zone. sodium hydroxide and phenol from approximately Upon expansion into the vapor Space of the stoichiometric proportions. distillation Zone, a mixture of anisole and Water The refortified aqueous solution of sodium flashes off from the heated mass. The ratio of phenate should contain at least 28 per cent by ) weight of sodium phenate and more preferably it Water to anisole in the vapors which flash off contains from 35 thru 45 per cent sodium phenate.
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