Патент USA US2129896код для вставки
Sept. 13, 1938. 2,129,896 D. s. WHITEMAN APPARATUS AND METHOD FOR SULÉHONATING FATTY COMPOUNDS 2 Sheets-Sheet 1 Filed Jan. 50, 1935 mm1vA r Wk «wmm R.wv l f „J W va y, f f . I Sept. 13, 1938. 2,129,896 D. s. WHITEMAN APPARATUS AND METHOD FOR SULPHONATING FATTY COMPOUNDS Filed Jari. so, 1935 'x1 ìm www: Y, í /y/ Mí 4 2 sheets-sheet 2 g Mez/Í ,Ésa /z//m ‘ . _ y /Èd M s.“ www@ 2,129,896 Patented Sept. 13, 1938 UNITED STATES PATENT OFFICE 2,129,896 APPARATUS AND METHOD FOR SULPHO NATING FATTY COMPOUNDS Daniel S. Whiteman, Philadelphia, Pa., assignor to Reilly-Whiteman-Walton Company, Conshohockcn, Pa., a corporation of Pennsylvania Application January 30, 1935, Serial No. 4,055 ' 20 Claims. (Cl. 87-12) Further purposes appear inthe specification My invention relates to methods and apparatus for sulphonating fatty compounds, such for ex ample- as glyceryl esters of fatty acids or fatty acids. ` A purpose of my invention is to treat any quan agent as a continuous process accompanied by mechanical mixing, without burning or discolor E ing the fatty compound and without extensive hydrolysis in the case of a fatty oil. A further purpose is to produce sulphonated fatty oils of comparatively low free 'fatty acid content. A further purpose is to subject the -sulphonat ing temperature of fatty oils to more accurate control and at the same time to make the temper ature of fatty oil sulphonation less critical. 'A further purpose is to permit the operation 'upon fatty compounds at higher sulphonating temperatures without harmfully alfecting the re . A further purpose is to maintain continuous control at all times of the proportions of fatty compound and sulphonating agent fed to a sul phonation mixing vessel. _ A further purpose is to continuously mechan ically mix a fatty compound and sulphuric acid or another sulphonating agent quickly and inti 0 The present application relates both to the methods involved and to the apparatus used. ' tity of fatty compound, large or small, with sul phuric acid or another suitable> sulphonating sulting product. and in the claims. mately, to cool the reacting ingredients rapidly by -removing them from the‘zone of initial mixing and holding them at reduced temperature for a suñicient time to complete the reaction, to mix In the drawings I have shown one main em~ bodiment of the invention, with a modification, choosing the main embodiment and modification from the standpoints of convenience in illustra tion of the principles involved, satisfactory oper ation and simplicity. , 10A All of the drawings are schematic, and are in tended to avoid _details which any person skilled in the art can readily supply. Figure 1 is a diagrammatic view of a typical apparatus constructed in accordance with my in vention. Figure 1u is a fragmentary diagrammatic viev of a modification of Figure 1. Fi'gure 2 is an enlarged central vertical section of one of the mixing mills shown in Figures 1 or 20 `la. « » . Figure 3 is an enlarged section of Figure 2 on theline 3-3 thereof. _ Figure‘l: is an enlarged central vertical section of sulphonation completion vessel shown in Fig ures 1 and 1a. 25 l. In the drawings like numerals refer to like parts. My invention relates to the sulphonation of fatty compounds. The sulphonating agent may 30 be, for example, concentrated sulphuric acid, oleum, fuming sulphuric acid, sulphur trioxide vapor. Various fatty compounds may be treated. For example, fatty acids such as oleic acid may be sulphonated in accordance with my invention. 35 Fatty oils, such as castor, oilve, rapeseed, teaseed rate the sulphonated fatty compound from the__ and- neatsfoot, may also be treated in accordance neutralization and washing products. with my invention. These fatty oils are glyceryl A further purpose is to pass-a fatty compound esters of unsaturated fatty acids, but 1 am not and sulphuric acid or another sulphonating agent restricted to glyceryl esters, but may sulphonate 40 through a mixing mill containing a relatively thin esters of fatty acids with mono-, di- or poly envelope of liquid, sol that a thin lfilm of'fatty hydric alcohols, for example glycol esters._ compound and sulphuric acid are mixed and cool sulphonation of fatty compounds, such as ani ing of the mixture is facilitated by the thinness of mal or ‘vegetable oils, is commonly resorted to the envelope and the nearness of metallic cooling to change the properties of the oils, as to change surfaces'to all parts of the mixture. . A further purpose is _to subject a mixture of a the viscosity or surface tension, or to render the fatty compound and a sulphonating agent to a. oils soluble in water. For example, castor oil is slow mixing action in a sulphonation completion sulphonated to form turkey red oil, primarily to the reaction products quickly and intimately with a neutralizing and washing agent, to complete the neutralizing reaction and to centrifugally sepa 5 vessel after initially relatively violently intermix ing the fatty compound and sulphonating agent. A further purpose is-automatically to propor tion the neutralizing or washing agent to the ex render the oil soluble. i When a fatty oil, for example glyceryl trioleate 50 ` or olein, istreated with concentrated sulphuric acid, a. series of complicated reactions takes place, cess sulphonating agent in continuous apparatus depending upon the temperature, concentrations, for sulphonating fatty compounds. etc. At low temperatures the primary reaction 55 2 2,129,896 appears to be the addition of Sulphuric acid at neutralized, the lower the free 'fatty acid content. points of unsaturation. Hydrolysis of the reaction products to form free fatty acid continues as long as the reaction mix ture is in the acid condition. One of the impor tant advantages of this invention is to shorten the - n. total time required for sulphonating glyceride oils, Olein from the initial mixture of the oil and sulphonat - H S 04H ing agent to the final yseparation and ñnishing, and particularly from the neutralization or wash ing to the ñnal separation and finishing. Sulphuric acid also tends to dehydrate and oxi dize the glycerides and the albuminous matter 10 ciaooo(camcncmcnmom ' H s 04H Sulphonated olein or acid sulphate 15 There is authority (Hyddleton and Barry, Fats: Natural and Synthetic, pages 56-60) for the opin ion that a true sulphonic aci‘d, for example 20 H0 B OaH CHzOOC(CH2)7CH¿}H(CH:)1CH: ' Ho s om of Sulphuric acid, which is thus present at a given point in excessive concentrations, and by unduly high localized temperatures. Mere thorough mixing of the fatty oil and Sulphuric acid, without more,J does not solve the problem, because, while it , H000 (CHMIEHbmCHmCH: 4H This is known in the trade as both favored by the presence of unmixed masses cmoocwnijfcncmonmom 25 present in the oil. “charring" or “burning," and is accompanied by the development of an undesirable dark color and by the odor of sulphur dioxide which is produced when Sulphuric acid is reduced by the material oxidized by the acid. Temperature is undoubt edly a factor in charring of the oil. Hydrolysis and charring of the fatty oil are SOaH results at higher temperatures, for example above breaks up the masses of Sulphuric acid and homo genizes the mixture, it does not take care of the 100° C. heat developed when the fatty oil and sulphuric This reaction takes place to some extent 30 at lower temperatures, or sulphated olein gradu acid react. ally changes to the sulphonic acid. Simultaneously with the sulphonation, some of the fatty oil is hydrolyzed or partially hydrolyzed. For example, if one> molecule of olein -were hy 35 drolyzed by one molecule of water, the result would be conductivities, and, while the heat conductivity of Sulphuric acid is higher than that of the fatty oils, The fatty oils have quite low heat CD it is still relatively low. The heat conductivity of the reaction mixture is of the same order of mag nitude as those of the reacting components. This explains the reason for the'diñiculty en CHaOH cmooC(CH,)1CH=CH(CH,)1CH» Oleic acid Glyeeryl dioleate The presence of sulphonic acids catalyzes the hydrolysis (i. e., Twitchell reagents) and the result is that, unless precautions are taken, the content countered when fatty compounds are sulphonated of free fatty acid may build up to an undesirable mass of oil containedwithin a vat or kettle. extent during sulphonation. though the stirring may be vigorous enough and ' The matter is complicated by the fact that the products of the hydrolysis may react with sul 50 phuric acid. Thus glyceryl dioleate mayform a mixed ester in a conventional apparatus in which Sulphuric acid is dropped slowly into a stirred and cooled Even the introduction ofthe sulphonating agent slow ' enough to prevent large masses of unreacted sul phuric acid from becoming localized, the develop .ment of localized temperature rises, with conse quent hydrolysis and charring, is diflicult to pre- ' vent. And of course, slow application of acid ' increases the cost. 55 Even when continuous streams of the fatty which may in turn be sulphonated at one of the double bonds. And the oleic acid may react with Sulphuric acid at the double bond in one of the manners referred to above, to form either sul phated oleic acid or oleic sulphonic acid. Sul phated oleic acid may be hydrolyzed to replace the (SOiH) group by an (OH) group. The sulphonic acid already contains an (OH) group. Either hydrolyzed sulphated oleic acid or the sulphonic 65 acid may condense, with molecular rearrange ment, with the (COOH) or acid group to form a lactone. , Thus it is'seen that the consequences of hy _ compound and Sulphuric acid fiow together in the presence of a blast of air, as in Dutch Patent No. 27,274, issued July 15, 1932, and the mixture is ledthrough a cooling coil, the danger of hy drolysis and charring because of incomplete mix ing and localized temperature elevations is notcompletely eliminated. And of course the air blast favors oxidation and renders heat conduc tion less efficient by reason of the frothing of the reaction mixture. , A I have discovered that sulphonation of a fatty compound may be greatly improved by spreading the fatty compound as a ñlm over a cooling sur drolysis are disastrous from the standpoint of face, suitably 'of' some; highly heat conducting obtaining a pure sulphonated glyceride. . material such as metal, `by mixing the sulpho „ From the standpoint of obtaining finished sul nating agent with the film on the cooling surface, phonated glyceride oils of low free fatty acid con and causing continuous motion of Ithe film t0 ' tent, the time consumed in the processes is a vital 4 homogenize the mixture. The film is preferably factor, and, in general, the more quickly the sul moved by a'rotor. l Du'e to the thinness> ofthe 'phoriation is completed and the Sulphonated oil is film, the distance of heat travel through the re en, 3 2,129,896 action mixture to the cooling surface is very small, and serious localized> elevations in tem perature are not possible. 'I'he motion of the rotor tends to cause the fatty compound and sulphuric acid to unite into a homogeneous film. The high velocities attained 4favor homogenization. After the initial mixing, the reaction mixture is carried by me to a reaction completion vessel, where the sulphonation is completed while the mixture is being slowly stirred and cooled. 'I‘he complete sulphonation requires some time, and instantaneous contact between the fatty com pound andthe sulphuric acid is not` enough. 15 After the eflicient mixing which takes place in the sulphonation mixing milll and the end of the primary reaction, the dangers due to high tem perature are Vno longer serious.Y solution, from 10% in the evening to 18% the next morning. My centrifuge separation avoids this difiiculty by virtue of the rapidity of its action., Where I refer throughout the specification and claims to neutraliaztion, I mean to include partial „ neutralization. In fact, in the art neutralization is normally not completed until separation of the sulphonated fatty compound from the neutral izíng and washing liquid, and the‘completion of 10 the neutralization is commonly known as “finish-_ ing”. Washing, for example with an aqueous salt solution, is similar >in its effect to neutraliza tion,v as it lowers the acidity of the reaction mix ture, and I intend to include it when I refer to the neutralizing step. >Onen of the factors which, according to my ex- ’ .periments, assists in obtaining sulphonated fatty I next spread the mixture of the fatty com 20 pound and excess sulphonating agent in a film upon a cooling surface and introduce an aqueous developed in the neutralization or washing is readily‘carried to the cooling surface. I preferably further mix the reaction products compounds of low free fatty acid content is the shortness of the elapsed time from the neutrali 20 zation (or washing) of the sulphonation reaction mixture to the separation of the sulphonated fatty compound from the neutralizing (or washing) liquid. It will be‘noted that, in the conventional practice and in the processes according to my 25 invention, the neutralized (or washed) reaction mixture is still slightly acid and is considerably diluted-and therefore much more susceptible to and neutralizing or washing solution to insure lhydrolysis than the more concentrated acidic re neutralizing or washing solution into contact with the film of fatty compound and excess sul , phonating agent. The ñlm is turbulently mixed 25 and, due to the thinness of the film, the heat 30 removal of the excess sulphuric acid, and then centrifugally separate the sulphonated fatty com pound and the neutralization products or wash action mixture. 30 « I have observed that. where the neutralized reaction mixture is allowed to stand for. an ex ing solution. Careful tests with my novel method of sulpho nation of fatty compounds have shown that I can produce continuously a lighter colored or less charred product than that of the prior art, and can safely allow- the sulphonating temperature to rise to higher values than those at which prior 40 Aart sulphonators have been successfully operated. In normal sulphonating operations upon ‘fatty oils, the oil is charred if the temperature rises tended ‘length of time before separation from the neutralizing (or washing) liquid, or where a sepa rating process such as settling is used which en 35 tails extended delay, considerable increase in the free fatty acid content results and the free fatty acid content may even double in an ordinary case. To avoid this diiilculty I find that very rapid separation of the neutralizing (or washing) liquid 40 from the sulphonated fatty compound is» desirable and that the neutralizedfor washed) reaction above about 35° C., but I have obtained extremely mixture should pass to the separating mechanism - light colored sulphonated fatty oils when the almost immediately after neutralization. Where „temperature rose to as high‘as about 66° C. This is, of course, an exceptionally high temperature and the sulphonation will desirably be carried out at lower temperature. One explanation of the fact thatcharring does not occur at tempera tures as high as 66° C_. is that localized‘tempera ture elevations present in prior art sulphonators, but never accurately measured in them, are avoided in my sulphonator. Another explana tion is that cooling is very rapid in my sulpho 55 nator, so that the fatty oil is subject to the high temperature for a very short time. ^ Thus by my process the fatty oil is' never subjected simultaneously to any appreciable localized excess of free sulphonating agent'and 60 high temperature. I also ñnd that I‘ can produce sulphonated fatty oils of lower free fatty acid content than the . commercial methods of the prior art. This I attribute partly to the decreased hydrolysis dur ing sulphonation, and partly to the continuous and relatively rapid separation of the sulpho nated oil from the neutralization products or washing solution. I have observed that, if a vmixture of sulphonated oil, excess sulphuric acid and salt solution be allowed to stand indefinitely, for example over night for settling purposes,- the» content of free fatty acid increases markedly. For example. I have found that the free fatty acid of the ñnishedoil, increased in one ‘instance 75 after standing over >nlghi: in contact with salt ’ the elapsed time from neutralization (or wash ing) to separation is less than 15 minutes, the increase in free fatty acid is very slight, and good results are obtained even when the elapsed time is as great as 30 minutes. vLonger times produce marked increase in free fatty acid content. I may by my method sulphonate any quantity of fatty compound, from a few gallons up. The proportions of fatty compound and sulphonating agent are under full control at all times. The sulphonator of my invention is'not to be confused with devices intended to refine pe troleum by treating it with sulphuric acid to re move unsaturated compounds, sulphur com pounds and other impurities as a sludge. The reaction here is instantaneous, and merely in 60 volves direct addition to the unsaturated com pounds at the double bond. As the bulk of the - petroleum `consists of saturated compounds which are inert to sulphuric acid even at rather high temperatures, the need for accurate temperature 65 control does not exist in the case of petroleum. Hydrolysis and charring are not to be feared where petroleum is concerned. ‘.The reaction mixture of fatty oils and sulphuric acid is a single phase. Petroleum and sulphuric acid form distinct immiscible phases. Separation is a much less difiicult problem in the case of petroleum than with fatty compounds; it can even be «accomplished without neutralizing or y washing. . 2,129,896 In the drawings I illustrate a typical fatty com Ul cold Water. The fatty compound leaves the tank 20 through`a pipe 2t to a fatty compound feed pump 25 which may be a centrifugal pump. As later explained, all of the pumps used in tion from the fatty compound. The rotor 53 is preferably of uniform cylin `:my apparatus may desirably have a common tion to have the clearance space 5l so small that drive, so that the rate of production of sulpho nated fatty compounds may readily be controlled. I illustrate an electric motor 26 driving a cone pulley 2l, which in turn drives a cooperating cone pulley 2B through a belt 29, suitably guided by means not shown. The cone pulley 25 is on a common drive shaft 3il,‘which rotates in suitable ' bearings, not shown. By varying the position of the belt 29 on the cooperating cone pulleys 2l and 2t, any suitable speed of rotation of the common drive shaft 3@ may be obtained. The common drive shaft 50 carries suitable 25 sprockets 3 l, 32 and 33, the latter of which drives the sprocket till on the fatty compound feed pump 25 by a chain 35. From the fatty compound feed pump 25, the fatty compound passes by the pipe 35 to the sul 30 phonation mixing mill 35. A suitable sulpho nating agent, for example concentrated sulphuric acid, is held in a corrosion resistant tanlr. 5l. It will be understood that all parts of my apparatus which come in contact with corrosive chemicals 35 are made of suitable corrosion resisting material, such as stainless steel or lVIonel metal. From the tank 3l, the sulphonating agent is withdrawn though a pipe 35 by a sulphonating agent feed pump 39 which passes measured quantities of sul 40 the clearance space 5l between the cooling sur pound sulphonator constructed in accordance face t8 and the rotor 53-at the bottom through with my invention. The fatty oil, fatty acid, etc.„ the pipe 35, and courses upwardly. The sul phonating agent enters through the pipe ¿l0 which is to undergo treatment in contained with in a tank 20 cooled by a cooling coil 2l having slightly above the fatty compound inlet, thus suitable inlet and outlet connections 22 and 23 protecting the bearing 56 somewhat from the sul to a source of cooling medium such as brine or phonating agent, and insuring it perfect lubrica phonating agent to the sulphonation mixing mill through a pipe élu. The sulphonating agent feed pump 35 is driven by a chain All from the common drive shaft sprocket 32 to a sprocket t2 of a variable speed transmission t3, which in turn drives the sul phonating agent feed pump 39 by a sprocket Mi, drical cross section for a substantial part of its axial length. It is of importance in my inven the fatty compound and sulphonating agent spread out in a thin ñlm against the cooling sur face. Experiment indicates that the distance from the surface of the rotor 53 to the cooling surface ¿3_8 should be less than one-quarter of an inch and that best results are obtained with a distance of less than one-eighth of an inch. I have found a clearance of about one-tenth of 20 an inch to be very desirable. During the axial travel of the fatty compound and sulphonating agent in the mill, the ñlms of fatty compound and sulphonating agent are tur bulently mixed and the heat developed during 25 the reaction is extracted by the cooling surface. To obtain rapid and intimate mixing the rotor is preferably operated at high peripheral speed, desirably in excess of 500 feet per minute. The peripheral speed is of course .a function of the speed of rotation and of the rotor diameter. While I am not prepared to explain in full detail the reasons for the' very efficient turbulent mixing obtained in the sulphonation mixing mill, I believe that one of the powerful factors in procuring this . turbulent mixing is the hydraulic shear between ñlms respectively adhering to the stationary cool-‘ ing surface and to the rotor. One effect of the turbulent mixing is to cause the reactants to dis perse in a molecularsense and another effect is 40 constantly to re-orient the reactant molecules with respect to each other and thus greatly in crease the probability of molecule to molecule contact while the molecules are oriented in that Position most favorable for chemical interaction. When the mixture of partially sulphonated through a chain :i5 to a sprocket ¿i6 on the pump. fatty compound and excess sulphonating agent The speed of the sulphonating agent feed pump 39 with respect to the c_ommon drive shaft Si@ reaches the top of the sulphonation mixing mill, 50 may be varied infinitely within any chosen range by the speed change lever @l in well known manner. ` It will be evident that the fatty compound and the sulphonating agent are supplied to the sul phonation mixing mill under pressure from' the respective pumps. The sulphonation mixingmill 35 is shown more in detail in Figures 2 and 3. In the form shown its axis is vertical, to avoid the necessity of 60 having a tight packing between the mill and the motor at the top, but, subject to the need of proper packings, the axis of the mill may be in any direction. The mill comprises a preferably stationary cooling surface which in this case is 65 outside and a moving surface, in close proximity, which in this case is inside. The cooling surface it is received in the space 58, thrown centrifugal 1y to the outside, and discharged through a pipe 50 59 to a reaction completion vessel, as shown in Figure 1, or, by modification of the apparatus, discharged through a pipe lill to another sul phonation mixing mill as shown in Figure 1a. The shaft 53 is reduced in diameter at the top at Sil, and the reduced shaft is surrounded by a cap Gi, which prevents any travel of the reaction mixture up the shaft and into the motor 56. The reaction completion vessel 62 is shown in detail .in Figure 4. In the case of sulphonating 60 fatty` compounds, the reaction is not instan taneous, Yalthough it is by no means so slow as prior art .intermittent methods would indicate. lI do not intend to indicate that the size of the reaction completion vessel with respect to the 65 other parts of the apparatus will necessarily be as indicated in the drawing, since the reaction completion vessel will be of a suitable size for the particular sulphonation, so that the reaction -will be substantially complete when the reac 70. ¿i8 is a tubular metallic casing which is main tained at a low temperature by a cooling jacket 59, through whose hollow interior 50 a cooling medium, suitably brine or cold water, flows from an inlet 5l to an outlet 52. f tion mixture leaves the reaction completion ves Within the annular cooling surface a rotor 53, sel. After the mixing of the fatty compound and sulphonating agent has taken place in one or rotatably supported on a bottom bearing 5t se cured to the base 55 of the mill, is driven at high more sulphonation mixing mills, the reaction mix 75 speed by a motor 5t. The fatty compound enters ture enters the hopper 63 of the reaction comple 75 2,129,896 tion vessel through the pipe 59, and, while in the reaction completion vessel, is stirred at rela tively low speed by the stirrer 64 on the shaft 65, journalled at the base 66 in a bearing 61. 'I‘he shaft 65 is driven by the motor 68 through speed reduction gearing 69, of well known character. The wall 10 of the reaction completion vessel is surrounded by a cooling jacket 1|, having inlet 'and outlet at 12 and 13 for a cooling medium, such asbrine or cold water. 'I‘he rate of withdrawal of reaction mixture from the reaction completion 'vessel 62 through the pipe 14 is controlled by the reaction mixture pump 15, which discharges a volume roughly equal to the total volume of fatty compound and liquid sulphonatlng agent added te the sul phonation mixing mill. The reaction mixture 5 the neutralizing agent, and also allows time for some slight localization of globules of the respec tive phases in the emulsion. From the mixing trough |0| the emulsion ñows by gravity through 'a pipe |04 to a centrifugal separator |05, preferably entering the bottom of the separator. 'I‘he heavy sodium sulphate solu tion is separated from the lighter sulphonated fatty compound in the centrifugal separator, the washing liquid passing by the pipe |06 from the centrifugal separator to the sump |01, and the sulphonated fatty compound flowing by the pipe |08 to the tank |09, in which suitable ñnishing may be carried out, preferably at once. While I prefer to use a liquid sulphonatlng 15 agent, a gaseous sulphonatlng agent may be sup pump 15 is driven from common shaft sprocket 3| by ~a chain 16 to a sprocket 11 of the variable plied if desired. Figure 1a is similar to Figure l except in certain features., mentioned below. Fatty compound supplied as explained in con speed transmission 18, equipped with the speed change lever 19 which permits infinite speed nection with Figure 1 passes through a plurality ot 20 variation within the chosen range. The variable speed transmission 18 drives two sprockets 80 and 8| at the same speed and preferablyÍ on the same sulphonation mixing mills 36' and 362 connected by a pipe | l0. Gaseous sulphur trioxide' from a suitable source conventionally illustrated at ||| is fed to the respective sulphonation mixing mills shaft, and the latter sprocket drives the reaction mixture pump 15 by a chain 82 to the pump through pipes 00' and 402 having valves H2 and 25 sprocket 08. phonation mixing mill. The through-put of the sulphonator may be ' t From the reaction mixture pump 15, the mix ture of sulphonated fatty compound and excess sulphonating agent passes to a neutralizing mill 84 through a pipe 8_5 which isdesirably surrounded for part of its length by a cooling jacket 86 which H3 to control the proportional feed to each sul controlled by'the speed of common drive shaft 30. In experimental work I have found a through 30 put of one gallon of fatty compound per minute' to be entirely satisfactory for continuous opera tion, with a clearance of about 0.1 inch and a rotor receives a cooling medium through an inlet 81 and discharges it through an outlet 88. If de i diameter of about 1.5 inches.` 'I'he proportion of sulphonatlng agent to fatty „.1. sired, the cooling jacket 86 may be omitted, as shown in Figure 1a. The neutralizing mill 84 re compound may be varied by shifting the speed ceives a neutralizing agent, for example sodium change lever'41 of the variable speed transmission hydroxide solution, from a tank 89 through a pipe 43 in Figure l. The extent of neutralization may 90, a neutralizing agent pump 9| and a pipe 92. be controlled in Figure 1 by shifting the change The neutralizing agent pump 9| is driven from speed lever 98 of the variable speed transmission sprocket 80 of .variable speed transmission 18 95. This is conveniently done by taking samples through chain 98 to sprocket 94 of variable Speed at the sample tap ||4, and adjusting the >neu transmission 95, which in turn drives pump ~ tralization until the samples 'show neutrality to sprocket 96 by chain 91 from sprocket 98. Speed congo red paper, or a pH of about 4. change lever 99 permits inñnite change in the . . If desired, the neutralization or washing may be speed of neutralizing agent pump 9| with re automatically controlled by any suitable auto spect to common drive shaft 30 within the chosen matic hydrogen ion control mechanism, the detail ^ range. The speed of neutralizing agent pump 9| i's9 of course also affected by speed change lever 'I'he neutralizing mill 84 may be desirably ex actly like the sulphonation mixing mill 30 already described. The same' advantages of thorough mixing and eiilcient heat removal already de scribed in the case of the sulphonation mixing mill are also true of the neutralizing mill. The ñlm of sulphonated fatty compound and excess sulphonatlng agent is mixed with the neutralizing agent, and the heat of the reaction is extracted, in the neutralizing mill. ` of which is no part of my invention. For ex ample, I may use an antimony electrode cell hy drogen ion controller of the type now generally 50 'available on~ the market. In Figure la I show an antimony cell ||5 continuously measuring the hydrogen ion concentration in the mixing trough |0| and continuously regulating the feed of neu tralizing or washing agent bythe controller ||6, connected electrically at -||1 with the antimony cell and changing the speed of the variable speed transmission 95 to vary the feed of neutralizing or washing agent. 55 - While I generally prefer to introduce the 60 If desired, the neutralizing mill 84 may be used A smaller volume of liquid into a moving ñlm of the purely as a washing mill, in which case the tank larger volume of liquid, that is, to introduce the 89 will desirably contain sodium chloride or other sulphonatlng agent into a moving film of the salt solution. The use of the mill 84 for neutraliz»` fatty compound or the neutralizing (or washing) liquid into a moving ñlm of the reaction mixture, ing is the preferable use, however, so that else where I refer generally to the neutralizing use, the procedure may to somewhat less advantage be although where I refer to neutralizing I mean to reversed, introducing the fatty compound into a moving ñlm of the sulphonatlng agent or intro include, the introduction of aqueous solutions gen erally, for example for washing. As already ducing the reaction mixture into a moving ñlm noted, neutralization is not really- complete until ~ ñnishing. if then. The effluent from the neutralizing mill 84 passes *of neutralizing (or washing) solution. It will be evident that other forms of control may be supplied by persons skilled in the art. by a pipe |00 to a mixing trough |0|, where a In view of my invention and disclosure varia stlrrer |02 driven by a motor |03 equalizes any tions and modifications to meet individual whim slight momentary inequalities in distribution of ` 91' particular need will doubtless become evident 70 - ß ' 2,129,896 to others skilled in the art, to obtain all or part of the benefits of my invention without copying the structure shown, and I, therefore, claim all such in so far as they fall within the reasonable spirit and scope of the following claims. Having thus described my invention, what I claim as new and desire to secure by Letters Pat ent is: 1. rIi'he method of sulphonating a fatty com pound, which comprises continuously progressing 10 the fatty compound as a film between relatively moving adjacent surfaces and introducing a sul phonating agent into the continuously moving film of fatty'compound. 15 agentl to complete the reaction, continuously progressing proportioned quantities of the reac tion mixture'and a neutralizing agent as a mixed film between relatively moving adjacent surfaces, one of which is a second cooling surface, with drawing heat formed through the second cooling surface, homogenizing the mixture and centrif ugally separating the sulphonated fatty com pound from the remainder of the mixture. 9. The method of sulphonating a fatty com pound, which comprises continuously mixing a fatty compound and a proportioned quantity of 2. The method of sulphonating a fatty com a sulphonating agent as a film between relatively pound, which comprises continuously progressing moving adjacent surfaces, the thickness of the mixed film not exceeding one-_quarter of an inch, the fatty compound as a film of less than one quarter of an inch thickness between relatively moving adjacent surfaces and introducing ‘a 20 sulphonating agent into the continuously moving ñlm of fatty compound. 3. The method of sulphonating a fatty com pound, which comprises continuously progressing ` the fatty compound as a ñlm between adja 25 cent surfaces, relatively moving the surfaces, cooling one of the surfaces and adding a sul phonating agent to the continuously moving film v of fatty compound. 4. The method of of sulphonating a fatty com 30 formed through the first cooling surface, slowly mixing thel fatty compound and sulphonating pound, which comprises continuously progressing the fatty compound as a film‘of less than one quarter of an inch thickness, between relatively moving adjacent metallic surfaces, adding a sul» phonating agent to the continuously moving film 35 of fatty compound and withdrawing the heat developed through one of the metallic surfaces, whereby the thinness of the film facilitates with drawal of the heat and assists in avoiding char rîng of the fatty compound. 40 5. The method of sulphonating a fatty com pound, which comprises continuously progressing the fatty compound as a iilrn, adding a sul phonating agent to the continuously moving film of fatty compound, shearing the film between re 45 latively moving walls separated not more than one-quarter of an inch and concurrently with-v drawing the heat formed, whereby the thickness of the film facilitates withdrawal of the heat and assists in avoiding charring of’ the fatty com 50 adjacent surfaces, the thickness of the mixed film not exceeding one-quarter of an inch, and concurrently withdrawing heat formed. 25 l0. The method of sulphonating a fatty com pound, which comprises continuously mixing a fatty compou'nd and a proportioned quantity of a sulphonating agent as a film between relatively moving adjacent surfaces, the thickness of the 30 mixed film not exceeding one-quarter of an inch, concurrently withdrawing heat formed, con tinuously stirring the mixture for reaction completion, continuously mixing the stirred re action mixture and a proportioned quantity of a ‘ 35 neutralizing agent as a film between relatively moving adjacent surfaces, the thickness of the mixed film not exceeding one-quarter of an inch, concurrently withdrawing heat formed, and con tinuously centrifugally separating the sulphon- n ated fatty compound from the remainder of the mixture. 11. In a sulphonator for fatty compounds, rela tively rotatable cooperating members having a clearance space of. film thinness between them through which the fatty compound and sulpho nating agent may ñow means for rotating one of the members, means for cooling one of the mem bers, means for pumping a fatty compound, conduit means communicating from said means which comprises continuously progressing the ance space, meansl for pumping a sulphonating agent proportionally to the means for pump ing the fatty compound and conduit means com municating from said means for pumping the sulphonating agent to the clearance space. 6. The method of sulphonating a fatty oil, acid to the whirling film of fatty oil,u shearing 55 the- film between relatively rotating metallic sur faces and withdrawing heat through one of the metallic surfaces, whereby a sulphonated oil of reduced free fatty acid content is produced. 7. The method of neutralizing the excess sul 60 phonating agent in. a reaction mixture resulting from the sulphonation of a fatty compound, which comprises continuously progressing the reaction mixture as a film between relatively moving adjacent surfaces, introducing a neutral izing agent into the film, shearing, the neutraliz ing agent and reaction mixture between the sur faces and concurrently withdrawing the heat formed from the mixed film through one of the surfaces.' 8. The method of sulphonating a fatty com pound, which comprises continuously progressing proportioned quantities -of the fatty compound and a sulphonating agent as a mixed film be tween relatively moving adjacent surfaces, one of 75 which is a ñrst cooling surface, withdrawing heat 20 ture and a proportioned quantity of a neutraliz ing agent as a film between relatively moving pound. fatty oil as a whirling nlm, adding sulphuric 70. œncurrently withdrawing heat formed, continu ously stirring the mixture for reaction completion, continuously mixing the stirred reaction mix for pumping the fatty compound to the clear ' l2. In a sulphonator for fatty compounds, a casing having an annular interior, means for cooling the casing, a rotor within and cooperat ing with the casing having a slight clearance from’the casing for a substantial axial length, a plurality of inlet conduits adjacent one endv of the rotor and communicating with the clear ance space, an outlet conduit adjacent the oppo site end of the rotor and means for driving the rotor. 13. A tubular mixing mill for the sulphona tion of fatty compounds comprising a tubular casing, means for cooling the casing, a rotor of substantially uniform cross section for a sub 70 stantial axialdistance within and cooperating with the casing, having a clearance from the casing of less than one-quarter inch, means for turning the rotor, an inlet to the clearance space adjacent one end of the rotor and an outlet 75 7 2,129,896 from the clearance space adjacent the other end. 14. A mixing mili for use in the sulphonation of fatty compounds comprising cooperating rela tively rotatable circular members having a clear `ance of less than one-quarter of an inch for a substantial axial distance, means for rotating one of the members, means for cooling one of the members, means for introducing the reaction in 10 gredients adjacent one end and passing them through the mill and means for withdrawing the reaction mixture adjacent the other end of the mill. ` 15. A mixing mill for use in the sulphonation 15 of fatty compounds comprising a tubular ver tical casing, cooling means for the casing, a cylin drical vertical rotor within and cooperating with the casing, leaving a clearance'space between the casing and the rotor of less than one-quarter of 20 an inch, inlet and outlet conduits to and from ing one wall with respect to the opposing nearly adjacent other wall and means for concurrently progressing streams of the fatty compound and of the sulphonating agent into the conduit at parts of the conduit toward one end thereof and for delivering the resulting stream of sulphonat ing compound out of the conduit from a part of the conduit toward the other end thereof, 19. In a device for sulphonating a fatty com pound by a sulphonating agent, a mixing mill 10 having an annular conduit of ñlm thinness pro vided With angularly relatively movable nearly adjacent inner and outer walls, means for an gularly rotating one wall .with respect to the opposing nearly adjacent other wall, means for 15 cooling one of the walls, and means for con~ currently progressing streams of the fatty com -poundi'and of the sulphonating agent into the conduit at parts of the conduit toward one end thereof and for delivering the resultant stream 20 of sulphonated compound out of the conduit from the clearance space adjacent the ends thereof, and means at the top of the rotor for driving ' a part of the conduit toward the other end the rotor at a peripheral speed in excess of 500 thereof, the sulphonating agent being progressed into the conduit at a point longitudinal of the feet per minute. conduit between the part at which the fatty 25 16. A sulphonation mixing mill for fatty com 25 pounds comprising a tubular vertical casing, compound is introduced and the part at which cooling means for the casing, a cylindrical ver tical rotor within and cooperating ing, having a clearance from the 30 than one-quarter of an inch for axial lengtn, a bearing for the with the cas casing of less a substantial rotor at the bottom, means for introducing -a fatty com the sulphonated stream is delivered, whereby the stream‘of sulphonating agent is delivered into a stream of fatty compound, as distinguished from delivering the stream of fatty compound into a 30 stream of sulphonating agent. ` 20. In a device for sulphonating a fatty com pound under pressure adjacent the bearing, pound by a sulphonating agent, a mixing mill means for introducing a sulphonating agent un having an annular conduit of film thinness pro 35 der pressure above the point of introduction of the fatty compound, means for withdrawing the reaction mixture adjacent the top of the rotor and means for1 driving the rotor at the top, whereby the fatty compound under treatment 40 serves to lubricate the bearing. 17. In a sulphonator for fatty compounds, a sulphonation mixing millhaving a cooling sur face and having a rotor providing a clearance space of not more than one-quarter inch between 45 the surface and the rotor, in which space tur bulent mixing takes place, means for continu ously introducing a fatty compound to the space and means for continuously introducing sulphur trioxidey to the space. ` 18. In a device for sulphonating a fatty com pound by a sulphonating agent, a mixing mill having an annular conduit of film thinness pro , vided with angularly relatively movable nearly adjacent inner and outer walls, means for cool 55 ing one of the walls, means for angularly rotat vided with angularly relatively movable nearly 35 adjacent inner and outer walls, means for angu larly rotating the inner Wall about its longi tudinal axis, means for cooling one of the walls, a bearing for the inner wall near one end of the conduit and means for concurrently pro gressing streams of the fatty compound and of the sulphonating agent into the conduit at parts o1" the conduit toward the end having the bear ing and for delivering the resulting stream of sulphonated compound out of the conduit from a part of the conduit toward the other end thereof, the fatty compound being progressed into the conduit at a part of the conduit located longitudinally of the conduit between the bear ing and the said part into which the sulphonat 50 ing agent is progressed, whereby the stream of fatty compound protects the bearing from the stream of sulphonating agent. DANIEL S. WHITEMAN.