Patented Sept. 12, 1933 UNITED STATES 1,926,148 ° PATENT OFFICE 1,926,148, MEHOD OF ACTIVATING CLAY Frederick “W. Huber, Riverside, Calif. No Drawing. 9 Claims. ‘This invention relates to the activation of clays by acid treatment, and particularly to activation of clays of the bentonite or montmorillonite type. ‘These clays, in general, are hydrous aluminum 5 silicates resulting from alteration or decomposi- tion of voleanic clays or feldspar, and in their natural state ordinarily possess little or no ad~ sorbent or decolorizing properties for ‘mineral ofls. ‘The term “activation” is used herein to denote the treatment of such materials by process involving “cooking” or digesting of the clay with aéid, in such manner as to impart de- colorizing or adsorbent properties thereto and render the same suitable for use as decolorizing or bleaching agents for oils, ‘The so-called “activation” of bleaching or de- colorizing earths by treatment with acid ap- parently depends upon the decomposition of a portion of the silicates present therein, result ing in the conversion of oxides of alkali and alkaline earth metals, and of some of the ferric oxide and alumina, present therein, to the form of water soluble salts of the acid used, and the removal of such-salts from the remaining por- tion, including insoluble products formed by the acid treatment. ‘The amount of material to be extracted varies with different earths and with the amount of activation desired. This treat- ment appears to alter the physical structure of the material as well as the chemical composition thereof, or to modify the surface characteristics thereof in some way, 50.as to give it the desired adsorptive properties. ‘The principal object of the present invention is, to provide a more rapid and economical method of converting such clays into decolorizing agents of high efficiency by acid treatment thereof, than the methods heretofore used for that purpose. ‘More specifically, it is an object of the invention to carry out the acid treatment and the subse~ quent washing and separation of the acid treated clay in such manner that the entire operation may be conducted more quickly and economically than has heretofore been done. ‘A particular object: of the invention is to'pro- vide a method of activation, in which the acid treated clay may be quickly and effectively washed, and separated by sedimentation from the washing liquid, thus greatly decreasing the total time required for production of the finished decolorizing agent. ‘A further object of the invention is to provide ‘@ novel and advantageous method for washing activated slay obtained by acid treatment of a raw clay. 10 6 20 30 0 50 5 tion August 27, 1932 Applicat ‘Serial No. 630,701 (CL. 252-2) According to the method now commonly used. for acid treatment of clays of the type above de- seribed, the raw clay is placed in a receptacle, and is mixed with water and with about 7% to 35% of its weight of concentrated sulphuric acid, the amount of water used being sufficient to pro- uce a more or less fluld pulp. ‘The mixing of the clay, acid and water is effected either by adding sufficient water to the clay to forma pulp and then adding the acid, or by first preparing a solution of acid in the desired quantity of water and add~ ing this solution to the clay. This pulp is then cooked or digested for from 5 to 8 hours, at or near boiling temperature, after which it is trans- ferred to suitable sottling apparatus, such as thickeners, where it is diluted with fresh water and allowed to settle. ‘The settled or thickened pulp is then drawn off into a second settling or ‘thickening apparatus, where an additional quan- tity of fresh water is added, and the process is repeated until the insoluble solids remaining after acid treatment are washed substantially free of soluble salts and acids. Although this operation appears comparatively simple, it is quite slow and time consuming when applied to the treat ‘ment of large quantities of material, for the rea- son that a period of several hours (ordinarily from about 4 to 12-hours) is required for each settling or thickening operation, and the total time required for the complete process is ordina- rily about 50 to 75 hours. T have found, however, that by controlling the manner in which the acid and water are mixed with the clay, and by properly adjusting the ratio of water to solids after the cooking is completed, and then allowing the mixture to stand, sedimentation of the activated clay par- ticles’ is caused to occur with relatively great rapidity. If the supernatant liquid is then sep- arated from the settled material, and an addi- tional quantity of fresher water is added and the whole mass agitated for a few minutes, and the ratio of water to solids again adjusted to cer- tain value, rapid sedimentation may again be ob- tained, so that the desired number of washing operations, usually about 4 or 5, may be com- pleted within relatively short period, and the total time of treatment may be reduced to about 5 to 10 hours. Observations made in the treatment of clays of the above described type with water and acid added thereto in different amounts and according to different procedures, indicate that if the mix- ing is effected by feeding the water into the dry clay to form a pulp and then adding the acid, 110 0 6 8 80 95 100 10510 0 30 40 2 or by feeding an aqueous solution of acid into quantity of dry clay to form a pulp, the pulp thickens and becomes more or ess gelatinous, On cooking thio mass, the structure 1s partially broken up into smaller particles but the gelati- nous quality thereof persists. ‘These particles Settle very slowly, particularly when the usual ratios of water to solids are maintained, due to the tend-ney of the material to take up of im- bibe large quantities of water and swell. Fur- thermore, a relatively long time of contact is re- aquired for completely dissolving or washing the Soluble salls and acids trom these gelatinous artictes. Phe procedure of the present, invention 1s such as to prevent of minimize the formation of gels or of gelatinous particles, thus facilitating oth the washing or dissolving of the soluble salts and acids from the insoluble solid, and also the sedimentation of the solids from the result: ing solution, “The clay, for example a clay of the montmoril- Ionite or bentonite type, is preferably fst crushed oF ground to suitable fineness, for example about 10 mesh, and is partially dried, for example by air drying, although the exact degree of dryness obtained ‘prior to the acid treatment is not critical ‘The clay, in divided condition, may then be thoroughly mixed with trom 1 to. 38% of its weight of concentrated sulphuric or hydrochloric acid, 90 as to secure faliy uniform distribution of the acid throughout the clay, and the result- ing mixture may then be fed oF introduced Ito sufficient water to make a fluid pulp, for exanaple, a welght of water approximately equal to that ot the air dried clay. Or, if desired, the clay may be fed or introdueed ‘directly into an ‘aqueous solution containing approximately 7 to 38% of acid by weight of the clay and containing ute ficient water to provide fluid pulp, In this ease also, the weight of water may edvantageounly be approximately equal to the weight of clay, ‘The pulp containing clay, acid and water, ob tained by either of the above methods of pros cedtire, and containing a weight of acid solution preferably somewhat in excess of the welght of Clay, {5 Ue cooked or digested at a suitable ele: ‘vated temperature, and is preferably kept in viow Jent agitation during this operation, “This cooks Ing operation may advantageously be condueied ina conleal tank or vessel into the lower por tion of which live steam is introduced, preferably through pipe extending to near the bottom of the cone. ‘This live steam serves both io heat the mass and also to produce agitation, and the Agitation may be further increased by introduce tion of compressed air either through the same pipe or through a separate pipe. it will be under stood, however, that other means may be em ployed for healing the mass and actively neltat. ‘ng the same, ‘The temperature is preferably Iaintained at 180" F. or higher (for exataple, about 190° F), and this operation ts continaed for such a period as is found to produce the de- sired activation and preferably until the reaction of the acid on the elay is substantially completed, esulting in the formation of soluble salts aad the production of activated clay’ particles as above described. ‘The actual time required for this treatment may vary considerably in difer: ent cases, but Ihave found thet in most cases 4 period of from 1 to hours ts sumelent, ‘The activated olay: particles are then sepa- rated fromthe, liquid ‘containing’ in’ solution 1,926,148 soluble salts formed by the acid reaction, and are subjected to a plurality of water washing and settling operations, either in the same vessel in which the cooking operation was conducted, or after being transferred to another vessel or vessels. For this purpose, the water content of the pulp is first adjusted to provide a liquid-solid ratio of at least 2:1, this adjustment. being effected by dilution with fresher water in suite able quantity. ‘The mass is then brought to rest and allowed to settle for a suitable period of time, ordinarily from about 20 minutes to one hour, to cause fairly complete sedimentation of the activated clay particles, At the end of this sedimentation period, the supernatant layer of substantially clear solution should ordi- narily occupy from one-half to two-thirds of the total depth of the mass, and this supernatant quid may then be removed in any suitable man- ner, as for example by decantation or siphoning. A further quantity of fresher water is then added, in sufficient amount to provide a pulp of suitable ffuidity for thorough agitation. For this purpose, the quantity of water added may, for example, be sufficient to provide a ratio of total solution to solids between one and one- half to one and twa to one, or somewhat greater. ‘This pulp is then agitated violently, as for ex ample by infection of compressed’ air, for a sufficient time to cause a further portion of the soluble salts and acid contained In the clay to be dissolved in the water, for example a period of 10 to 30 minutes, and the temperature is preferably maintained at about 100° F. or higher during this period. ‘The water content is again adjusted, by addition of any necessary quantity of fresher water, to provide a liquid-solid ratio of at least 2:1, and is then again allowed to settle to cause sedimentation of the clay particles, after which the supernatant solution is removed. It will be understood that if the quantity of water added before agitation was sufficient to Provide a liquid-solid ratio of 2 to 1 or greater, itmay be unnecessary to.add any additional water before settling, except such as may be required to compensate’ for evaporation during agitation, ‘The relative amounts of water added before and after agitation, in this and succeeding wash- ing’ operations, may be varied somewhat, the essential requirements being that the water added to the thickened pulp, before agitation, shall be sufficient to provide proper fluidity for effective agitation, and that the pulp shall be caused to have a liquid-solid ratio of at least 2 to Lat the start of the settling operation. ‘These operations of diluting with-water, agi- tating, adjusting the liquid-solid ratio to at least 2:1, settling: and removal of the supernatant Maquid layer are repeated until the pulp is sub- stantially free from soluble salts’ and acids, ‘Ordinarily, four or five repetitions of these oper ations are’ sufficient for this purpose, In each of these operations, the liquid-solid ratio is adjusted to the value above mentioned, and it has been found that if the process is carried out as above described, substantially complete sedi mentation of the clay particles from a superna- tant layer of substantially clear solution may be obtained, in each case, in a relatively short period. for ‘example, about 20 minutes to one 145 hour. 80 85 95 100 105 110 120 125 After removal of the supematant solution ob- tained in the last washing and settling operation, the pulp is de-watered, preferably’ by filtra- tion, and is then dried by heating to a sultable 12210 15 40 50, © temperature, preferably not exceeding 150° C., and finally ground to the desired fineness, for example to a fineness of from 75% to 100% minus 200° mesh, ‘The clay is then ready to bbe used, stored or packed for shipment, ‘As a specific example of the method of this invention, I will now describe the treatment of a clay known as a montmorillonite ‘clay, having approximately the. following analysis: Water (after drying at 100° C) With a clay of this composition, I have found that excellent results are obtained by treatment with about 30%of its weight of concentrated sul- phurie acid. ‘Ten tons of the dry clay are first mixed with three tons of 66° B. sulphuric acid, ‘and this mixture is then fed or introduced into ten tons of water in a conical bottom tank. If desired, this procedure may be varied by feod- ing the ten tons of dry clay into a solution con- taining ten tons of water and three tons of 66" B. sulphuric acfd. . ‘The pulp is then cooked by injection of live steam, and kept in violent agitation by introduc tion of compressed air, for a period of three. ‘hours, the temperature being maintained at about 100° F. ‘Presh water is then added until the total weight of liquid present is at least about 20 tons, thus providing a liguid-solid ratio of at least 2:1. ‘The clay is then allowed to settle for about 20 mitiutes, and the clear supernatant liquid is re- moved by decantation or siphoning. ‘The clay is then subjected to further wash- ing operations, in which-fresh water is added in sufficient amoimt to bring the total weight of ‘the solution up to about 15 tons or somewhat greater, the exact amount of water to be added depending upon the amount of supernatant liq- uuid previously removed, and the pulp is then vio~ ently agitated for about 15 minutes at a tem- perature of at least 100° F. Additional water is ‘then added in sufficient amount to bring the ‘weight of solution up to at least about 20 tons, thus again providing a liquid-solid ratio of at east 2 to 1, ‘The mass is then allowed to settle for about 20 minutes, and the supernatant liquid is removed by decantation or siphoning. This washing operation is repeated four or five times, until the total acidity of the pulp is reduced to about 0.3%, after which the pulp is de-watered, dried and ground as above described, and then packed for shipment. ‘The present invention relates not only to the complete method of acid activation of clays as ‘above described, including the acid treatment and the washing operation, but also to the specific method of washing above described, as applied to activated clay obtained by any process of acid treatment. Telaim: 1, The method of activating clay which com- prises mixing clay with from 7% to 35% of its weight of concentrated acid and with sufficient water to form a fluid pulp, heating and violently agitating said pulp for a sufficient length of time to cause reaction of said acid on constituents of the clay to form soluble salts, adjusting the water 1,996,148 3 content of sald pulp to provide a liauid-solld ratio of at least 2 to 1, then allowing the pulp to Sette to cause sedimentation of the activated clay particles, and separating the supernatant, liquid Containing in solution soluble salts formed by go -said acid reaction. 2, The method of activating clay which com- prises mixing clay with from 7% to 35% of its ‘weight of concentrated acid and with a quantity of water approximately equal to the weight of gg ‘the clay and sufficient to form a fluid pulp, heat- ng and violently agitating said pulp for a suft- lent length of time to cause reaction of the acid ‘on constituents of the clay to form soluble salts, ‘adding water to sald pulp to bring the liguid-solid . 99 ratio thereof up to at Jeast 2 to 1, then allowing the pulp to settle to cause sédimentation of the activated clay particles, and separating the super- natant liquid containing in solution soluble salts formed by said acid reaction. 9% 3. The method of activating clay which com- prises mixing clay with from 1% to 35% of its ‘Weight of concentrated sulphuric acid, then intro- ducing the clay and acid mixture into sufficient ‘water to form a fiuid pulp, violently agitating the 199 pulp and heating the same to a temperature of at least 180° . for a sufficient length of time to cause reaction of said acid on constituents of the clay to form soluble salts, adjusting the water content of the pilp to provide a liquid-solid ratio 195 of at least 2 to.1, then allowing the pulp to settle to cause sedimentation of the activated clay par- ticles, and separating the supernatant liquid con taining in solution soluble salts formed by the seid reaction, . 10 4. The method of activating clay which com- prises introducing clay, in divided condition, into ‘a solution of acid containing from 1% to’ 35% of acid by weight of the clay and sufficient water to form a fluid pulp, violently agitating the pulp 115 and heating the same to a temperature of at least 180° F. for a sufficient length of time to cause reaction of said acid on constituents of the clay to form soluble salts, adjusting the water content of the pulp to provide a liquid-solid ratio of at 120 least 2 to 1, then allowing the pulp to settle to ‘cause sedimentation of the activated clay par- ticles, and separating the supemetant liquid con taining in solution soluble salts formed by the acid reaction. 125 8. The method of activating clay which com- prises mixing a clay with acid and with sufficient ‘water to form a fluid pulp, heating and agitating said pulp for a sufficient time to cause reaction of sald acid on constituents of the clay to form 130 soluble salts, and then removing sald: soluble salts by a plurality of successive water washing and settling operations, each such operation including, addition of water in sufficient quantity to provide 4 liquid-solid ratio of at least 2 to 1 followed by 135 settling to cause ‘sedimentation of the activated clay particles and separation of the supernatant liquid corttaining soluble salts in solution. 6. The method of activating clay which com- prises mizing a olay with from 7% to 359% of its 140, weight of concentrated acid and sufficient water to form a fluid pulp, heating and violently agi- tating said pulp for @ suificient time to cause re- ‘action of sald acid on constituents of the clay to form soluble salts, adjusting the water content of 145 said pulp to provide a Jiquid-solid ratio of at least 2 to 1, allowing the pulp to settle to cause sedimentation of the activated clay particles, sep- ‘rating the supernatant liquid containing in solu- tion soluble salts formed by the acid reaction, 310 6 20 35 40 45 85 60 os 10 ws 4 and then subjecting the settled activated clay particles to plurality of successive washing and settling operations, each such operation including. addition of water in sufficient quantity to provide 4 liguid-solid ratio of at least 2 to 1 followed by settling to cause sedimentation of the activated lay particles and separation of the supernatant liquid containing soluble salts in solution. 7. The method of activating clay which com- rises mixing a clay with acid and with suMelent water to form a fluid pulp, heating and agitating said pulp for a sufficient time to cause reaction of said acid on constituents of the clay to form soluble salts, allowing the mass to settle to cause sedimentation of the activated clay particles, separating the supernatant liquid containing in solution, soluble salts formed by the acid reaction, and then removing a further quantity of soluble salts from the activated clay by a plurality of successive water washing and settling operations, each such operation including the steps of adding sufficient water to form a pulp of sufficient fluidity for agitation, agitating said pulp, adjusting the ‘water content of the pulp to provide a, liquid- solid ratio of at least 2 to'1, settling to eause sedimentation of the activated clay particles, and separating the supernatant liquid containing soluble salts in solution. 1,026,148 8. The method of washing activated clay ob- tained: by acid treatment which comprises add~ ing water to the activated clay in such amount as to form a pulp of sufficient fluidity for agita- tion, agitating the pulp so formed, adjusting the water content of the pulp to provide a liquid- solid ratio of, at least 2 to 1, allowing the pulp to settle to cause sedimentation of the activated clay particles, separating the stpernatant liquid containing in solution soluble salts formed by the acid treatment, and repeating said operations until the desired degree of removal of soluble salts is obtained, 9. The method of washing activated clay ob- tained by acid treatment of a clay of the mont morillonite or bentonite type which comprises subjecting the clay to a plurality of water wash- ing operations each of which comprises the steps of adding water to the clay, agitating the mix- ture, allowing the same to settle to cause sedi mentation of the: activated clay particles, and separating the supernatant liquid containing in solution soluble salts formed by the acid treat ‘ment, the water content of the mixture being. adjusted to provide a liquid-solid ratio of at least 2 to 1 prior to each settling operation. FREDERICK W. HUBER. 85 100 105 110 115 125 40 us