CONTINUOUS PROCESS FOR PREPARATION OF AQUEOUS DISPERSIONS OF METAL SOAPS

Abstract: The invention is a process for preparing an aqueous dispersion of a metal soap by reacting a metal oxide or hydroxide with an organic acid in the presence of a dispersing agent in a media mill.

Description: CONTINUOUS PROCESS FOR PREPARATION OF AQUEOUS DISPERSIONS OF METAL SOAPS FIELD OF THE INVENTION The Invention 1s a continuous process for the production of aqueous dispersions of insoluble metal salts of organic acids and particularly (herein after noted as metal soaps) insoluble metal salts of higher fatty acids. The dispersions of the metal soaps can 5 be utilized as prepared or they can be dried to produce finely divided partlculate metal soaps. Background of the Invention: 1. Metal soaps have found many uses 1n industry. They generally possess many of the desirable properties of the acids from which the metal soaps are manufactured. Some applications of the 10 metal soaps require that they be prepared 1n a form of a stable aqueous dispersion. The aqueous dispersions generally comprise the metal soap, water and dispersing agents for the metal soap. The dispersing agent 1s generally a surfactant or mixture of sur¬ factants which are generally of the anlonlc and the nonlonlc type. 15 DESCRIPTION OF RELATED ART Metal soap dispersions are available commerlcally at solid con- , tents of from about 35 to about 75 percent by weight. The aqueous dispersions typically containabout 30 toabout 60percentmetal soap, f the remaining solids comprisingemulsiflers, dispersionaidsandother 20 processing aids. The additives are Included to enhance the pro¬ duction process for the metal soap or the end-use of the product. Aqueous dispersions of metal soaps have been prepared 1n the past by three methods. One of the oldest methods comprises reacting the organic add with an oxide or hydroxide of the metal, 1n the presence of a small amount of water, to form a solid metal soap of the add, grinding the metal soap and dispersing the ground material 1n water by means of a dispersing agent. More recent processes prepare the dispersion of the metal soap by reacting a fatty add with an oxide or hydroxide of the metal in the presence of a dispersing agent and the water in which the metal soap of the fatty add is to be dispersed. The pro¬ cesses are generally batch processes and require several hours to complete the reaction. The dispersions prepared by the known methods generally require that the dispersion be milled to pro- vide a stable dispersion having particles within a required particle size range. The metal soaps have been prepared by a double decomposition method wherein the metal soap is precipitated from an aqueous solution by reaction of an alkali metal salt of the fatty acid with an add salt of the metal used to form the metal soap. The metal soap precipitates as a fluffy material, can be recovered from the aqueous medium washed free of the alkali metal salts then dispersed in an aqueous medium to form a dispersion. The known processes are generally batch processes and require milling of the dispersion to provide a stable product having dispersed therein metal soap of a small particle size. There are many patents which disclose processes for preparing metal soaps and dispersions of metal soaps. Patents such as U.S. 2,660,568, U.S. 3,803,188, U.S. 4,060, 535, U.S. 4,307,027, Japanese Kokal 51/34904 (March 25, 1976), Kokai 54/8606 (January 23, 1979), Kokal 59/51236 (March 24, 1984) disclose processes for preparing metal soaps and aqueous dispersions of metal soaps. In particular U.S. 3,803,188 discloses the three general methods used to prepare metal soaps. u — ~ Er. fC~M~_ E. fc i A batch process 1s disclosed 1n East German Patent 106629, Patented June 20, 1974. The patent discloses a process for making dispersions of metal soaps such as caldum, zinc or lead stearate. The process comprises preparing a mixture of water, a dispersing agent and the hydroxide of the metal with acetic add at a tem¬ perature above the melting point of the fatty acid 1n a Cowles Disolver and introducing the fatty acid Into the mixture at a tem¬ perature above its melting point. A continuous process for preparing dispersions of metal soaps 1s disclosed in East German Patent 241900. The process discloses continuously Introducing a suspension of the metal oxide cr metal hydroxide into a cascade of stirred reactors. The fatty add is introduced into each of the stirred reactors depending upon the concentration of the fatty acid at that point of the process. The process is relatively complex in that the concentration of the fatty acid in a plurality of reactors must be monitored and the addition of the fatty acid into each of the series of reactors must be controlled. The pro¬ cess provides a relatively long residence time of the dispersion in the system. BRIEF DESCRIPTION OF THE INVENTION The invention 1s a continuous single step process for the production of aqueous, metal soap dispersions which comprises con¬ tinuously Introducing an aqueous suspension of an oxide or hydroxide of the metal, at least one dispersing agent and a molten organic add into a media mill and removing a dispersion of the metal soap from the media mill. The process of the present Inven¬ tion 1s carried out at a residence time 1n the range of 1 to 55 minutes and produces a dispersion having a low-free fatty add content. The process does not require additional milling to pro¬ vide an aqueous dispersion. The dispersion 1s stable has a small particle size and substantially no oversized material. BRIEF DESCRIPTION OF THE DRAWINGS F1g. 1 1s a schematic representation of a typical prior art process for preparing aqueous dispersions of metal soaps. F1g. 2 1s a schematic representation of the process of the present Invention. DETAILED DESCRIPTION OF THE INVENTION The advantages of the process of the present Invention can be better understood by comparison with a batch process which 1s known 1n the prior art. F1g. 1 1s a schematic represen¬ tation of a prior art batch process for preparing a calcium fatty add soap dispersion. A dispersing agent or mixture of dispersing agents is prepared in tank 1 and introduced into the reactor 6 through line 2. A suspension of lime in water is prepared in tank 3 and introduced into reactor 6 through line 4. Reactor 61s a well agitated reactor. After the dispersing agent and the lime suspension had been introduced into reactor 6, the aqueous mixture is heated to a temperature near the melting point of the fatty acid. Molten fatty add is then introduced through line 5 into the agi¬ tated suspension of the calcium hydroxide and the agitation con¬ tinued until the fatty acid is substantially reacted to the desired metal soap. The reaction generally requires about 1 to about 10 hours to complete * The temperature in the reactor is controlled by cooling means in the reactor jacket. After the reaction is completed, the dispersion is passed from the reactor 6 through line 7 to holding tank 11. Holding tank 11 is necessary to permit the reactor to again be filled with reactants and another batch of the dispersion of the metal soap prepared. The dispersion from holding tank 11 is then introduced through line 12 Into a milling or grinding means 13. The grinding means 13 can comprise one or more grinding means which reduces the particle size of the metal soap dispersion to the required particle size range. Suitable grinding means are known 1n the art. The ground dispersion then passes through line 14 through heat exchanger 15, and line 16 to size separating means 17. In size separating means 17 the oversize particles 1π the dispersion are separated from the dispersion and can be returned to the grinding means. The dispersion of the required particle size passing through size separating means 17 passes through line 18 to production holding tank 21. The dispersion 1s mixed 1n holding tank 21, sampled and 1f It meets specifications can be transferred to a storage tank (not shown) through line 22 or transferred for use. As can be seen from the schematic diagram of a conventional process, the process 1s a batch one which requires reacting and milling steps and requires a substantial amount of process equip¬ ment to accomplish the process. In contrast to the conventional processes for preparing metal soap dispersions, F1g. 2 1s a schematic representation of the pro¬ cess of the present Invention. As shown in Fig. 2, a dispersing agent or a mixture of dispersing agents is introduced into the fatty acid in feed tank 34 and into the metal oxide or hydroxide aqueous suspension in tank 36 through line 47 and mixed therewith. The fatty acid, in fatty acid holding tank 34, is in a molten condition. The molten fatty add 1s continuosly introduced Into the reactor 41 through line 35 and the aqueous suspension of the metal oxide or hyoroxide in holding tank 36 is continuously introduced through line 37 into reactor 41. Reactor 41 is a media mill. The temperature in the media mill can be controlled by circulating cooling fluid in the jacket or internally arranged cooling means. In the mill, a media is caused to move about and contact the particles of the fatty add and the metal oxide or hydroxide to cause them to react and to provide dispersed particles in a suitable particle size range. The residence time in the media mill 1s relatively short and ranges from about 1 to less than about 55 minutes. Preferably from about 2 to about 20 minutes. The dispersion then passes from the media mill 41 through line 42 through heat exchanger 43 and line 44 to holding tank 45. In holding tank 45, the dispersion 1s sampled to determine 1f 1t meets the proper particle size, visco¬ sity, free add and other specifications and 1s then passed to a storage tank (not shown) through line 46. The particle size at the outlet of the media mill reactor 1s uniform and generally no screening or sizing operation 1s required. However, as a safety measure, should something malfunc¬ tion 1n the system, a sizing means can be Introduced Into line 44 between heat exchanger 43 and holding tank 45. As can be seen from a comparison of the schematic of the pro¬ cess of the present invention and the schematic for the batch pro¬ cess, the process of the present Invention is simplier, requires less equipment and- can be operated at a lower cost than the known processes. Soaps of metals such as aluminum, barium, caldum, cadmium, cobalt, copper, iron, lead, lithium, magnesium, manganese, nickel, strontium and zinc can be prepared by the process of the present invention. Generally, the process of the present invention can be adapted to provide dispersions of the metal soaps which can be prepared by the batch processes of the prior art. The fatty adds which can be utilized to prepare metal soap dispersions, by the process of the present invention generally contain from about 8 to about 30 and preferably about 10 to about 24 carbon atoms. The acids can be saturated or unsaturated, straight chain or branched chain. Dispersions of metal soaps of fatty adds such as octanoic add, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecaπoic acid, hexadecanoic acid, heptadecanolc acid, octadecanoic acid, nonadecandc acid, eicosandc add, hencosanoic acid, docosanoic acid, and their isomers can be prepared by the process of the invention. Dispersions of soaps of the unsaturated fatty adds such as the octenoic acids, nonenoic adds, decenolc adds, undecenolc adds, dodecendc adds, tr1deceno1c adds, tetradecenoic adds, pentadecenolc adds, hexadecenoic adds, hep- tadecenolc adds, octadecenolc addes, nonadecenolc adds, elcose- noic adds, docosenoic adds, tetracosenoic adds, and their Isomers can be prepared by the process of the eventlon. Dispersions of metal soaps of dlenolc, trienolc and, tetraenolc adds having from about 8 to about 24 carbon atoms can be prepared by the process of the Invention. Dispersions of metal soaps of hydroxy substituted fatty adds having from about 8 to about 30 carbon atoms can be prepared by the process of the Invention. Dispersions of water Insoluble soaps of alicyclic and aromatic adds can also be prepared by the process of the Invention. Useful surfactants or dispersing agents Include anolnlc surfac¬ tants such as ethoxylated alkyl phenol sulfates and sulfonates, fatty add sulfates and sulfonates, petroleum sulfates and sulfonates, alcohol sulfates, ethoxylated alcohol sulfates, fatty acid ester sulfates, alkyl benzene sulfonates, alkyl napthalene sulfonates, sulfosucdnates, taurates, betaines, carboxylated alcohol ethoxyla- tes and the like. Nonionic surfactans such as ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated amines or amides, ethoxy¬ lated fatty acid esters, propylene oxide-ethylene oxide, random and block copolymers, fatty esters, polyethylene glycol ethers and the like can be used as dispersing agents in the practice of the inven¬ tion. The dispersing agents are present in a sufficient amount to provide a stable dispersion. Generally, the dispersing agent or mixture of dispersing agents 1s in the range of from about 0.5 to about 20% by weight of the dispersion and preferably in the range of about 1.5 to about 10% by weight of the dispersion. The amount and type of dispersing agent is not critical except that it must be capable of providing a stable dispersions. Special user require- ments may require the use of special dispersing agents. The process can also be utilized to prepare dispersions of metal soaps from aromatic and alicyclic adds. The process can be utilized to prepare metal soaps of aromatic adds such as naphthenlc acid and the like. Process of the present Invention can be generally utilized to prepare dispersions of metal salts of adds which provide water Insoluble metal salts (metal soaps). The dispersing agents used 1n the process of the present inven¬ tion are conventional and well known 1n the art. Both anlonic and nonionlc surfactants can be used to prepare aqueous dispersions of metal soaps. Mixtures of anionlc and nonionlc surfactants are preferred since the advantageous properties of each of the surfactants 1s retained 1n the mixture. However, some applications require special dispersing agents to meet special end use require¬ ments. In the process of the present Invention, the dispersing agents can be added to the aqueous suspension of the metal hydroxide or oxide, can be added to the, molten fatty add, can be added to each of the reactants or can be added directly Into the reactor along with the suspension of the metal oxide or hydroxide 1n water and the fatty add. However, It 1s preferred that the dispersing agents be introduced in admixture with at least one of the suspension of the metal oxide or hydroxide 1n water or with the molten fatty acid. The premixing of the dispersing agent with the reactants permits the Introduction of the dispersing agent into the reactor 1n a metered amount without the requirement that an additional stream of reactants be metered into the reactor. For special requirements, additional dispersing agents or surfac¬ tants can be introduced into the dispersion leaving the media mill reaction zone. However, at least part of the dispersing agent should be introduced into the media mill reactor alone or pre¬ ferably mixed with at least one of the fatty acid or the metal hydroxide or oxide dispersion. The proces of the present Invention generally uses about a stoichiometric amount of multivalent metal compound to neutralize the fatty acid. A small excess or deficiency of metal hydroxide or oxide can be used to meet user requirements. Generally a small excess of about 1 to about 10% on an equivalent basis of the metal hydroxide or oxide 1s used. The dispersion generally contain from about 25% to about 65% by weight water preferably from about 30 to about 55% by weight water based on the weight of the dispersion. The process can be operated over a broad temperature range. A temperature of fpom about 25-100 β C can be used. However a tem¬ perature 1n the range of about 35 β C to about 95 β C 1s preferred and most preferred 1s temperatures 1n the range of about 50°C to about 95 β C. Temperatures above 100 β C can be used but require spe¬ cial pressure equipment and product handling. Temperatures 1n the range of about 50*C to about 95 P C provide for a rapid reaction and produce a dispersion with low fatty add content. Higher te - peratures are not required. The reaction temperature does not have to be above the melting point of the add or soap. The media mill utilized as the reaction zone 1n the process of the present Invention comprises a vessel containing partlculate material which tumble or move 1n the vessel. The partlculate material can be moved 1n the vessel Interior by rotating or vibrating the vessel or by providing means which stir the media. When the media or partlculate material 1s moved by vibrating or stirring, the vessel can be arranged horizontaly or vertically. Due to the flexibility 1n arranging the feed Introduction and product discharge means, a horizontally arranged media mill reaction zone is preferred. Media mill as used herein refers to grinding and milling devices which utilize the movement of solid particles known as media within the aparatus to impart energy to the material being milled. Movement of the media can be achieved by rotating or vibrating the vessel containing the media. Movement of the media can also be provided by stirring means provided in the vessel or reaction zone. A combination of stirring and vessel movement can also be used. In a preferred embodiment, a horizontaly arranged media mill manufactured by Premier Mill Corporation, charged with glass or ceramic beads is used as the reaction zone for the process of the invention. The mill is charged with media, with a particle size in the range of from about 1 to about 3 mm in diameter. The media can be glass, ceramic or metal particles or the like. The process of the present invention has been found to achieve excellent results uti¬ lizing media comprising glass beads of about 1.5-2.5 mm In diameter. The void volume 1n the mill 1s generally filled from about 50 to about 95 percent with the grinding media. Preferably the mill 1s charged with from about 62 to 90 percent of the void volume with the grinding media. A preferred aparatus, the Premier Mill comprises a hori¬ zontally arranged vessel with a rotating means for stirring the media. The rotating means generally rotates at from about 1000 to about 3000 revolutions per minute. Lower or higher rotation speeds may be utilized and 1s dependent upon the media being used, and the size of the aparatus. The rotating device contacts the media and SUBS ' h i U 11 fcnEt I causes the media to move within the reaction zone. The Impact of the media with the particles of the fatty add and the metal oxide or hydroxide and the precipitated metals soap causes the reaction to proceed at a rapid rate and to produce a dispersion with a small particle size. , The following examples are presented to Illustrate the process of the invention. The examples are for Illustration only and are not Intended to be a limitation to the invention. The process is Illustrated by an embodiment for production of calcium stearate but other metal soaps can be prepared by the process. In the examples, a suspension of caldu hydroxide in the water for the dispersion was prepared. A portion of the dispersing agents was added to the suspension. The suspension of caldum hydroxide was maintained at 20 to 30 degrees centigrade. A portion of the dispersing agent was mixed with molten stearic acid at a temperature of 80 to 85 degrees centigrade. The reaction zone was a horizontally arranged Premier Super Mill™ with a free volume of 15 liters charged with 1.5 or 2 millimeter diameter glass beads or 1.7 or 2mm diameter zirconium silicate beads or 1.7mm zirconium oxide beads. The mill comprised a shell with a removable end closure which carried a rotating milling shaft. The milling shaft carried discs which when rotated imparted energy and movement to the beads. The rate of rotation of the milling shaft was varied from 1100 to 1650 r.p.m. The mill was heated to 50 to 55 β C by passing hot water through the mill. When the mill temperature reached 50 to 55° centigrade, the flow of hot water was stopped, the milling shaft was started rotating and the flow of calcium hydroxide suspension and molten fatty add was started into the mill. The temperature of the dispersion leaving the mill was controlled by flow of cooling water through the mill sJiell. The examples show the composition of the feed streams, the feed rate, retention time, and product temperature. The table presents a summary of the data and the properties of the dispersions. The examples were carried out according to the process illustrated in F1g. 2. SUBSTITUTESHEET Example 1 Lime Slurry Feed 702 Lbs Water 92 Lbs Hydrated L1me (MV300/M1ss1ss1ppi L1me Co.) 2.5 Lbs Ethoxylated Nonyl Phenol (Hyonic ® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Wltconate® 1238/Witco) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 650 Lbs Ci8 fatty add (Industrene« 7018/Witco Chemical) 37 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Henkel Corp.) 3.5 Lbs C36-C54 dimer/trimer fatty acid (E pol® 1022/Emery Chemicals) The vessel was heated until the chargewasmolten. Agitationwas started and the temperature adjusted to 80-85 c C. The Premier Mill was charged with 2πτn glass beads to 90% of the available volume. The mill was preheated to 55°C by passing hot waterthroughthemill chamber. Simultaneouly, themill shaftwas started at 1650 RPM, lime slurry feed was started at 0.96 lb/min., andmolten fatty acid feed was started at 0.76 Ib/min. rate. The average retention time (ART) in themill was 8.9min. The temperatureoftheexitingmaterial was controlledat70 β Cby cooling waterapplied to thejacket of themill. Theproductwas cooled to room temperature. Example 2 Lime Slurry Feed 750 Lbs Water 92 Lbs Hydrated L1me (MV300/Miss1ss1pp1 Lime Co.) 2.5 Lbs Ethoxylated Nonyl Phenol (Hyonic ® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Witconate® 1238/Witco) 48 Lbs Peg 600 Monolaurate (Nopalcol®6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Add Feed 650 Lbs Ci8 fatty add (Industrene® 7018/Witco Chemical) 37 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Henkel Corp. 3.5 Lbs C36-C54 dimer/trimer fatty acid (Empol® 1022/Emery Chemicals) The vessel was heated until the chargewasmolten. Agitationwas started and the temperature adjusted to 80-85°C. The Premier Mill was charged with 2mm glass beads to 60% of the available volume. Themill was preheated to 55 β C bypassing hot waterthroughthemill chamber. Si ultaneouly, themill shaftwas started at 1100 RPM, lime slurry feed was started at 1.01 Ib/min. , and molten fatty acid feed was started at 0.76 Ib/min. rate. The average retention time (ART) in themill was 12.4min. Thetemperatureoftheexitingmaterial was controlledat85 β Cby cool1ngwater applied to the jacket of themill. The productwas cooled to room temperature by passing through a heat exchanger. SUBZTITUTB SH Example 3 Lime Slurry Feed 750 Lbs Water 92 Lbs Hydrated Lime (MV300/Mississippi Lime Co.) 2.5 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Heπkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Wltconate® 1238/Witco) 48 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp. Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 650 Lbs Cj8 fatty acid (Industrene® 7018/Witco Chemical) 37 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Henkel Corp.) 3.5 Lbs C36-C54 dimer/trimer fatty acid (Empol® 1022/Emery Chemicals) The vessel was heated until the chargewasmolten. Agitationwas started and the temperature adjusted to 80-85°C. The Premier Mill was charged with 2mm glass beads to 60% of the available volume. The mill was preheated to 55°C by passing hot waterthroughthemill chamber. Simultaneouly, themill shaftwas started at 1650 RPM, lime slurry feed was started at 2.00 lb/m1n. , and molten fatty add feed was started at 1.53 lb/min. rate. The average retention time (ART) in the ill was 5.2 1n. Thetemperatureofthe exitingmaterial wascontrolledat85°Cby cool1ngwaterappl1ed to the jacketof themill. The productwas cooled to room temperature by passing through a heat exchanger. SUBSTITUTESHEET Example 4 Lime Slurry Feed 750 Lbs Water 92 Lbs Hydrated L1me (MV300/H1ssisslppi L1me Co.) 2.5 Lbs Ethoxylated Nonyl Phenol (Hyonic ® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Witconate® 1238/Witco) 48 Lbs Peg 600 Monolaurate (Nopalcol ® 6-L/Henkel Corp. Agitation was started and the temperature adjusted to 20-30°C. Fatty Addy Feed 650 Lbs Ci8 fatty acid (Industrene ® 7018/Witco Chemical) 37 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Henkel Corp.) 3.5 Lbs C36-C54 dimer/trimer fatty add (E pol® 1022/Emer.y Chemicals) The vessel was heated until the chargewasmolten. Agitationwas started and the temperature adjusted to 80-85°C. The Premier Mill was charged with 2mm glass beads to 60% of the available volume. Themill was preheated to 55°C bypassing hot waterthroughthemill chamber. Simultaneouly, themill shaftwas started at 1100 RPM, lime slurry feed was started at 2.10 lb/min., ffdmolten fatty add feed was started at 1.53 Ib/min. rate. The average retention time (ART) in themill was 6.1 min. The temperatureoftheexitingmaterial was controlledat 55°Cby cool1ngwaterapplied to the jacket of theml11. The productwas cooled to room temperature by passing through a heat exchanger. .SUBSTITUTESHEET Example 5 Lime Slurry Feed 750 Lbs Water 92 Lbs Hydrated L1me (MV300/Miss1ss1pp1 L1me Co.) 2.5 Lbs Ethoxylated Nonyl Phenol (Hyonic ® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Witconate® 1238/Witco) 48 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 650 Lbs Cj8 fatty add (Industrene ® 7018/Witco Chemical) 37 Lbs Ethoxylated Nonyl Phenol (Hyonic ® PE-100/Henkel Corp.) 3.5 Lbs C36-C54 dimer/trlmer fatty acid (Empol® 1022/Ert.ery Chemicals) The vessel was heated until the chargewasmolten. Agitationwas started and the temperature adjusted to 80-85°C. The Premier Mill was charged with 2mm glass beads to 60% of the available volume. Themill was preheated to 55°C bypassing hot waterthroughthemill chamber. Simultaneouly, themill shaftwas started at 1100 RPM, lime slurry feed was started at 3.58 Ib/min., and molten fatty acid feed was started at 2.32 lb/min. rate. The average retention time (ART) in themill was 3.6min. The temperatureoftheexitingmaterial was controlledat80°Cby cool1ngwaterapplied to the jacket of themill. Theproductwas cooled to room temperature by passing Through a heat exchanger. sussπτuτ≥ SHEET Example 6 Lime Slurry Feed 750 Lbs Water 92 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 L1me Co.) 39.5 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Wltconate® 1238/WUco) 48 Lbs Peg 600 Monolaurate (Nopalcol® 6-1/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 650 Lbs Cχ8 fatty acid (Industrene® 7018/Witco Chemical) 3.5 Lbs C36-C54 dimer/trimer fatty acid (E pol® 1022/Emery Chemicals) The vessel was heated until charge was molten. Agitation was started and the temperature adjusted to 80-85°C. The Premier Mill was charged with 2mm glass beads to 60% of the available volume. Themill was preheated to 55°C by passing hot waterthroughthemill chamber. Simultaneouly, themill shaftwas started at 1650 RPM, lime slurry feed was started at 3.03 lb/min. , and molten fatty acid feed was started at 2.16 Ib/min. rate. The average retention time (ART) in themill was 4.0min. The temperatureof theexitingmaterial was control1edat60°Cby cool1ng water applied to the jacket of themil1. The productwas cooled to room temperature by passing through a heat exchanger. Example 7 L1me Slurry Feed 725 Lbs Water 92 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 Lime Co.) 39.5 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (WUconate® 1238/Witco) 22.5 Lbs Peg 600 Monolaurate (Nopalcol®6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 650 Lbs Ciβ fatty add (Industrene ® 7018/Witco Chemical) 3.5 Lbs C36-C54 dimer/trimer fatty acid (Empol® 1022/Emery Chemicals) The vessel was heated until the chargewasmolten. Agitationwas started and the temperature adjusted to 80-85°C. Additive Feed 22 Lbs Water 22 Lbs Peg 600 Monolaurate (Nopalcol 6-L/Henkel Corp.) The Premier Mill was charged with 2mm glass beads to 60% of the available volume. The mill was preheated to 55°C by passing hot waterthroughthemill chamber. Si ultaneouly, themill shaftwas started at 1650 RPM, lime slurry feed was started at 3.30 lb/m1n. , and molten fatty acid feed was started at 2.16 Ib/min. rate. The average retention time (ART) 1n themill was 3.8m1n. Thetemperatureoftheexitingmaterial was controlledat70 β Cby coolingwater applied to the jacket of themill. The productwas cooledtoroomtemperaturebypassingthroughaheatexchanger. The productfromtheheatexchangerwaspostblendedw1ththeaddltive feed as follows: 97 Lbs of heat exchanger output 3 Lbs of the additive feed The blending was done at 20-30°C. Example 8 L1me Slurry Feed 560 Lbs Water 92 Ls Hydrated L1me (MV300/M1ssiss1pp1 L1me Co.) 39.5 Lbs Ethoxylated Nonyl Phenol (Hyonic ® PE-100/Henkel Corp.) 4.0 Lbs sodium salt of an Alkyl Aryl Sulfonate (Wltconate® 1238/Witco) 22.5 Lbs Peg 600 Monolaurate (Nopalcol®6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Add Feed 650 Lbs Ci8 fatty add (Industrene® 7018/Witco Chemical) 3.5 Lbs C36-C54 dimer/trimer fatty acid (Empol® 1022/Emery Chemicals) The vessel washeated until thechargewasmolten. Agitationwas started and the temperature adjusted to 80-85°C. The Premier Mill was charged with 2mm glass beads to 60%of the available volume. Themill was preheated to 55°Cbypassing hot waterthroughthemill chamber. Simultaneouly,themill shaftwas started at 1650 RPM, lime slurry feed was started at 2.56 lb/min., andmolten fattyacid feedwas started at 2.18 lb/min. rate. Theaverage retention time (ART) in themill was4.2min. Thetemperatureoftheexitingmaterial wascontrolledat70°Cby coolingwaterappliedto thejacketofthemi11. Theproductwas cooled to room temperature by passing through a heat exchanger. Example 9 Lime Slurry Feed 404 Lbs Water 69 Lbs Hydrated L1me (MV300/M1ss1ssipp1 Lime Co.) 27.5 Lbs ethoxylated nonyl phenol (Hyonic® PE-100/Henkel Corp.) 1.6 Lbs sodium salt of an Alkyl Aryl Sulfonate (Witconate® 1238/Witco) 5.0 Lbs Peg 600 Monolaurate (Nopalcol®6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 444 Lbs Cis fatty acid (Industrene ® 7018/Witco Chemical) 2.3 Lbs C36-C54 dimer/tri er fatty add (Empol® 1022/Emery Chemical) The vessel was heated until the charge was molten, agitation was started and the temperature adjusted to 80-85°C. Additive Feed 16 Lbs Water 30 Lbs Peg 600 Monolaurate (Nopalcol®6-l/Henkel Corp.) 0.5 Lbs Benzisothiazolin-3-0πe (Proxel®GXL/ICI Americas) The components were charged and mixed at 20-30°C. The Premier Mill was charged with 2mm glass beads to 65% of the available volume. Themill was preheated to 55°Cbypassing hot waterthroughthemill chamber. Simultaneouly, themill shaftwas started at 1650 RPM, Hme slurry feed was started at 2.70 lb/m1n. , and molten fatty add feed was started at 2.53 lb/m1n. rate. The average retention time (ART) in themill was 3.8m1n. The temperatureoftheex1tingmaterial was control1edat75°Cby coolingwaterapplied to thejacket of themill. As thematerial exited themill 1t was passed through a static mixer where 0.20 lb/m1n. of the additive feed was added. The product was then cooled to room temperature by passing through a heat exchanger. SUBST IT UTESHEET Example 10 Lime Slurry Feed 410 Lbs Water 74 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 L1me Co.) 1.6 Lbs sodium salt of an Alkyl Aryl Sulfonate (Witconate® 1238/Witco) 5.2 Lbs Peg 600 Monolaurate (NoDalcol®6-L/Henkel Corp.) Agitation was started and temperature adjusted to 20-30°C. Fatty Acid Feed 436 Lbs C 18 fatty acid (Industrene ® 7018/Witco Chemical) 27.5 Lbs Ethoxylated Nonyl Phenol (Hyonic® PE-100/Hεr.kel Corp.) 2.2 Lbs C36-C54 dimer/trimer fatty acid (E pol® 1022/Emery Chemical) The vessel was heated until charge was molten, then agitation was started and temp adjusted to 80-85°C. Additive Feed 16 Lbs Water 30 Lbs Peg 600 Monolaurate (Nopalcol®6-L/Henkel Corp.) 0.5 Lbs Benzisoth1azolin-3-0ne (Proxel®GXL/ICI Americas) The components were charged and mixed at 20-30°C. The Premier Mill was charged with 2mm glass beads to 65% of the available volume. The ill was preheated to 55 β C bypassing hot water thru the ill chamber. Slmultaneouly, the ill shaft was started at 1650 RPM, Hme slurry feed was started at 2.71 lb/m1n., and molten fatty add feedwas started at 2.53 lb/m1n. rate. The average retention time (ART) 1n themill was 3.8 1n. The temperatureoftheex1tingmaterial wascontrol1edat75°Cby cool1ngwaterapplled to thejacket of theml11. As thematerial exited the mill 1t was passed thru a static mixer where 0.24 lb/m1n. of the additive composition was added. The product was then cooled to room temperature by passing thru a heat exchanger. SU B STITUTESHEET EXAMPLE 11 Lime Slurry Feed 627 Lbs Water 107.4 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 Lime Co.) 7.5 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Add Feed 725 Lbs Ci8 fatty acid (Industren ® 7018/Witco Chemical) 51.OLbsEthoxylatedNonyl Phenol (Hyonic®PE-100/Henkel Corp.) 3.9 Lbs C36-C54 dimer/trimer fatty acid (Empol® 1022/Emery Chemicals) 2.7 Lbs sodium salt of an alkyl aryl sulfonate (Witconate® 1238/Witco) 15.5 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) The vessel was heated unti1 the chargewasmolten, agitation was started and the temperature adjusted to 80-85 c C. Additive Feed 56.2 Lbs Water 47.4 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) 0.7 Lbs Benzisothiazolin-3-one (Proxel® GXL/ICI Americas) The components were charged and mixed at 20-30°C. ThePremierMi11 was chargedwith2mmzirconiumsilicatebeads to 90% of the available volume, the mill was preheated to 55 β C by passing hotwaterthrough themill chamber. Simultaneously, the mill shaft was started at 1650 RPM, lime slurryfeedwas started at 2.16 lb/min., and molten fatty acid feed was started at 2.36 lb/min. rate. The average retention time (ART) in the mill was 3.3 in. The temperature ofthe exitingmaterial was controlled at 85°C by cooling water applied to the jacket of the mill. As thematerial exited themill 1twaspassed througha statlcmlxer where 0.33 lb/m1n. of the additive feed was added. The product was cooled to room temperature by passing through a heat exchanger. EXAMPLE 12 Lime Slurry Feed 627 Lbs Water 107.4 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 Lime Co.) 7.5 Lbs ;Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 725 Lbs Ciδ fatty acid (Industrene® 7018/Witco Chemical) 51.0LbsEthoxylatedNonyl Phenol (Hyonic®PE-100/Henkel Corp.) 3.9 Lbs C35-C54 dimer/trimer fatty add (E pol® 1022/Emery Chemicals) 2.7 Lbs sodium salt of an alkyl aryl sulfonate (Witconate® 1238/Witco) 15.5 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) The vessel was heated until the chargewasmolten, agitationwa-s started and the temperature adjusted to 80-85 c C. Additive Feed 56.2 Lbs Water 47.4 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) 0.7 Lbs Benzisothiazolin-3-one (Proxel® GXL/ICI Americas) The components were charged and mixed at 20-30°C. The PremierMill was chargedwith 1.7mmzirconiumoxide beads to 80% of the available volume. The mill was preheated to 55°C by passing hotwater through themill chamber. Simultaneously, the mill shaft was started at 1650 RPM, lime slurry feedwas started at 2.18 lb/min., and molten fatty acid feed was started at 2.33 lb/min. rate. The average retention time (ART) in the ill was 3.8m1n. The temperatureof theexitingmaterial was controlled at 95°C by cooling water applied to the jacket of themill. As thematerial exited themill Hwaspassed througha staticmixer where 0.33 lb/m1n. of the additive feed was added. The product was 'cooled to room temperature by passing through a heat exchanger. S UBSTITUTESHEET EXAMPLE 13 Lime Slurry Feed 542 Lbs Water 92.7 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 L1me Co.) 6.5 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 648.5 Lbs Ciβ fatty acid (Industrene ® 7018/Witco Chemical) 45.6 Lbs Ethoxylated Non Phenol (Hyonic® PE-100/Henkel Corp.) 3.5 Lbs C36-C54 dimer/tri er fatty acid (Empol® 1022/Emery Chemicals) 2.5 Lbs sodium salt of an alkyl aryl sulfonate (Witconate® 1238/Witco) The vessel was heated until the chargewasmolten, agitationwas started and the temperature adjusted to 80-85°C. Additive Feed 64.8 Lbs Water 54.4 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) 0.8 Lbs Benzisothiazol1n-3-one (Proxel® GXL/ICI Americas) The components were charged and mixed at 20-30°C. The PremierMi11 was chargedwith2mmzirconiumsilicatebeads to 80% of the available volume. Themill was preheated to 55°C by passing hotwater through themill chamber. Simultaneously, the mi11 shaftwas started at 1350 RPM, 1ime siurry feedwas started at 2.17 lb/min., and molten fattyacid feed was started at 2.32 lb/min. rate. The average retention time (ART) in the mill was 3.8min. The temperature of the exitingmaterial was controlled at 85°C by cooling water applied to the jacket of the mill. As thematerial exitedthemill, 1twaspassedthroughastat1cm1xer where 0.33 lb/m1n. of the additive feed was added. The product was cooled to room temperature by passing through a heat exchanger. SUB S T IT U T ESHEET EXAMPLE 14 L1me Slurry Feed 542 Lbs Water 92.7 Lbs Hydrated L1me (MV300/M1ss1ss1pp1 L1me Co.) 6.5 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) Agitation was started and the temperature adjusted to 20-30°C. Fatty Acid Feed 648.5 Lbs Ci8 fatty add (Industrene ® 7018/Witco Chemical) 45.6 Lbs Ethoxylated Non Phenol (Hyonic® PE-100/Henkel Corp.) 3.5 Lbs C36-C54 dimer/trimer fatty add (Empol® 1022/Emery Chemicals) 2.5 Lbs sodium salt of an alkyl aryl sulfonate (Witconate® 1238/Witco) 15.5 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) The vessel was heated until the chargewasmolten, agitationwas started and the temperature adjusted to 80-85°C. Additive Feed 64.8 Lbs Water 54.4 Lbs Peg 600 Monolaurate (Nopalcol® 6-L/Henkel Corp.) 0.8 Lbs Benzisothiazoliπ-3-one (Proxel® GXL/ICI Americas) The components were charged and mixed at 20-30°C. The Premier Mill was charged with 1.5mm glass beads to 80% of the available volume. The mill was preheated to 55°C by passing hotwaterthrough themill chamber. Simultaneously, the mi11 shaft was started at 1350 RPM, 1ime siurryfeedwas started at 2.16 lb/min., and molten fatty acid feed was started at 2.36 lb/min. rate. The average retention time (ART) in the mill was 3.8min. The temperature ofthe exitingmaterial was controlled at 95°C by cooling water applled to the jacket of the mill. As thematerial exitedtheml11, 1twaspassedthroughastaticmlxer where 0.33 lb/min. ofthe composition in theaddditives tankwas added. Theproductwasthencooledtoroomtemp.bypassingthrough a heat exchanger. SUBSTITUTE SHEET TABLE : I . 5 ALK-ALKALINITY EXPRESSED AS %KOH, MEASURED 1-24 HRS AFTER REACTION % SCREEN - % OF METAL SOAP RETAINED ON A 325 mesh SCREEN ART-AVERAGE RETENTION TIME MINUTES ZIR SIL = ZIRCONIUM SILICATE BEADS ZIR OX = ZIRCONIUM OXIDE BEADS ALL OTHER BEADS ARE GLASS ALK = ALKALINITY EXPRESSED AS % KOH, MEASURED 1 - 24 HRS AFTER COMPLETION

Claims: CLAIMS 1. A continuous process for preparing an aqueous dispersion of a metal soap which comprises: forming a mixture by continuously introducing at least one carboxylic add having from about 6 to about 30 carbon atoms, at least one oxide or hydroxide of a metal, which forms a metal soap with the at least one car¬ boxylic acid, water and at least one dispersing agent into a media mill, wherein water comprises at least about 25% by weight of the mixture and reacting the mixture in the media mill for from about 1 to about 55 minutes to form an aqueous dispersion of the metal soap. 2. A process of claim 1 wherein the at least one carboxylic acid is selected from the group consisting of 10 to 22 carbon atom monocarboxylic acids. 3. A process of claim 1 wherein the at least one oxide or hydroxide of a metal is selected from the group consisting of oxides and hydroxides of aluminum, baruim, calcium, cadmium, cobalt, copper, iron, lead, lithium, magnesium, magnese, nickel, strontium and zinc. 4. A process of claim 1 wherein the reaction is carried out at a temperature of from about 25°C to about 100°C. 5. A process of claim 1 wherein the water, at least a portion of the dispersing agent and the oxide or hydroxide of the metal are introduced into the media mill as a mixture. 6. A process of claim 1 wherein at least a portion of the dispersing agent is introduced into the media mill admixed with the carboxylic add. 7. A process of claim 1 which comprises: forming a feed mixture comprising the oxide or hydroxide of the metal, water and at least a portion of the dispersing agent; continuously Intro¬ ducing the feed mixture and molten carboxylic acid into the media mill to form the mixture; and reacting the mixture 1n the media mill at a temperature from about 35 β C to about 95 β C for from about 1 to about 20 minutes to form the aqueous dispersion of the metal soap. 8. A process of claim 7 wherein a portion of the dispersing agent 1s mixed with the carboxylic add before the carboxylic add 1s Introduced Into the media mill. y. A process of claim 8 wherein the dispersing agent comprises from about 0.5% to about 20% by weight of the mixture. 10. A process of claim 1 wherein the acid is stearic acid and the metal hydroxide 1s caldum hydroxide. 11. A process of claim 1 wherein the temperatures of the material 1n the media mill is above the melting point of the carboxylic add. 12. A process of claim 1 wherein the temperature of the material in the media mill is below the melting point of the carboxylic acid. 13. A process of claim 1 wherein the media mill is a horizontal stirred media mill. 14. A process of claim 13 which comprises; a) forming a mixture of water, dispersing agent and metal oxide or hydroxide; b) forming a mixture of a fatty acid having from about 8 to about 30 carbon atoms and dispersing agent at a temperature at which the mixture is molten; c) continuously introducing a) and b) into the media mill, maintained at a temperature of from about 35°C to about 95°C and reacting a) and b) of from about 1 to about 20 minutes; and d) recovering as aqueous metal soap dispersion. 15. A process of claim 14 wherein the temperature in the media mill is below the melting point of the fatty acid dispersion agent mixture. 16. A process of claim 14 wherein the temperature in the media mill is above the melting point of the fatty acid dispersion agent mixture. EET

Inventors: KOENIG H STEVE, SPEENBURGH GARY L, KOENIG, H., STEVE, SPEENBURGH, GARY, L.
Applicants: HENKEL CORP, HENKEL CORPORATION
Application year: 1990
Main classification: C07C57
IPC codes: C07C51, C07C53, C07C57