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    US7125432B2

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    (2) 6 sy 0) an @ 6s) Gn (2) (58) (56) United States Patent Huang METHOD FOR MAKING PREC SILICA OR SILICATE. COMPOS PRODUCTS THEREOF TATED TIONS AND Inventor: Yung-Hul Huang, Bel Ait, MD (US) Assignee: J.M. Huber Corporation, Edison, NI os) Notice: Subject to any disclaimer, the tem ofthis pateat is extended of adjusted under 35 USC. 184(b) by 0 days. Appl. Nos 10/898:502 Filed: Jul, 23, 2008 Prior Publication Data eb. 9, 2006 $ 20060027142 A1 Im. Cl, cose 1728 (2006.01), COOK 3/14 (200601) us. cl. ‘31/308; 51/309; 106/482; 1O6IASS; 106/484: 106/485; 106/486; 106/492; 428/335; 423/338; 423/339 Field of Classification Search 51/308, 51/309; 106/35, 482, 483, 484, 485, 486, 106492; 423/335, 38,339; 424/40, 52, 424s ‘See application file for complete search history References Cited US. PATENT DOCUMENTS. SS12271 A * 411996 Meksown oa aw SSATSI4 A 31999 Bele eal Sp00139 A $1999. Bilt ‘USOOT1254 BD (10) Patent No. (4s) Date of Patent: US 7,125,432 B2 Oct. 24, 2006 403059 BL 62002 Manin ta nu Gal0.I74 BL* 72002. MeGil tal ‘asus GoS2611 BL 112003 Huang etal 2ooxioo1st6? A1* "12003 Thing 1307 POREIGN PATENT DOCUMENTS * cited by examinee Primary Esaniner—Michael Marcheschi (74) dutomey, Agent, or Firm William Parks; Caelos Niewes on ABSTRACT [New methods of producing narrower particle size distribu tion precipitated silica andor silicate materials are provide. Such a method pernits a significant redvetion in manufse- turing costs through the wilizaton of more elliient drying! ‘evaporation components, in essence, in one potentially pre- Terred embodiment, production of seh silica andor silicate materials followed diretly by a hydeaulic chamber press filtering. step combined with vacutim dewatering subse- quently Ieading to the neoded resultant particle comm: ‘ion, The resultant precipitated silieas aad sliates pro- ‘duced thereby exhibit greater density prior to eomminution ‘and thus greater propensity for more uniform milling than previously utilized and prevalent spray/lash drying appara ‘uses. Also encompassed within this inveation are the result ant precipitated silica andlor silicate particles. producod, including. those thot surprisingly exhibit extremely i transmittance properties, thereby potentially providing excellent narrow particle distribution silica materials for clear (transparent) end-use 6 Claims, 1 Drawing Sheet US 7,125,432 B2 Oct. 24, 2006 U.S. Patent RIN ATOS H uorpEay IH spear Mey I SSOOOIg BWI /LdI]I1S poyeyidioag MON US 7,125,432 B2 1 METHOD FOR MAKING PRECIPITATED SILICA OR SILICATE COMPOSITIONS AND PRODUCTS THEREOF FIELD OF THE INVENTION [New methods of producing narrower particle size disti= bution precipitated silica andor silicate materials are pro- vided. Suet a method pemnits a significant reduction in ‘manufacturing costs through the utilization of more elicient ‘drying/evaporation components, in essence, in one poten tally prefered embodiment, production of such silica and! ‘or silicate materials followed dieectly by a hydraulic cham= ber press filtering step combined with vacuum dewatering subsequently leading to the neoded resultant particle come minution. The resultant precipitated slicas andor silicates produced thereby exhibit greater density prior to comm tion and thus greater propensity for more wniform milling than previously utilized and prevalent sprays drying ‘apparatuses, Also encompassed within this invention are the 2 resultant precipitated siice andlor silicate particles pro- ‘duced, including those that surprisingly exhibit extremely high transmittance properties, thereby iy providing ‘excellent narrow particle distribution silica materials for ‘lear (transparent) end-uses. BACKGI {OUND OF THE INVENTION Precipitated silicas and/or silicates find use in a broad range of manufactured products ringing Irom eosmetic and ood products to industrial fa ‘example) and elastomeric ms particularly useful in dentitfice products (such as tooth- pastes) where they function as files, abrasives, and thick- ‘ners, a8 Well as anti-caking agents and glans for food and Pharmaceutical ses. Because of this functional versatility, and also because silicas have good cleaning ability, are relatively safe, and have high compatiblity with typical dentiftice ingredients like nmectans, thickening. agents, Favoring agents, and therapeutic agent such as anti-caries agents, there is a strong desire among toothpaste and den~ Ulrice Tormulators to include them in thee products, Si ‘cates are utilized 3s active ingredients, such as oil absorbers ‘and odor absorbers, 2s some examples, as well as additives, {or various physical and chemical purposes, such as viscos- ity modification, agsin, as one example within a number of different formulations, such as personal care compositions, ‘aniperspirunts, and other like produets, and as paper coating agents andlor antcaking agents. Such silicates (for ‘example, sodium aluminosilicate) exhibit effective thicken- ing, absorption, ete, characteristics as well as elfective ‘compatiblity with much the same added ingredients listed above for silicas ‘As known, synthetic precipitstod silicas generally are produced by the de-stabilization aod precipitation of amor Phous silica from soluble alkaline sliete by the edition of ‘2 mineral acid and/or acd gases under conditions in which primary particles initially formed tend to associate with each ‘other to form a plurality of aggreyates (i, discrete clusters ‘of primary particles), but without agglomeration into a ‘hree-dimensional gel siructure. The resulting precipitate is separated from the aqueous fraction ofthe reaetion mixture by filtering, washing. and drying procedures, and then the died procact is mechanically commited in order to pro- vide suitable particle siz. Silicate are prnduced penerally fin the same manner by reacting swim silicate with apro- priate reactants to produce the desired silicate; i. ealeium 0 o 2 hydroxide to produce caleium silicate, magnesiues hydrox: ide to produce magnesium silicate, aluminum sulfate replac- ing the mineral acid 10 produce an aluminosilicate. Mixed ‘etal silicates ean likewise be produced, i.e. sodium mag- nesium aluminosilicate by reeting sodium silicate, mayne- sium hydroxide and alumni sulfate, or calcium magne- ‘ium silicate by reacting sodinm silicate, caleium hydroxide, and magnesium hydroxide, a¢ non-limiting examples. The silica and/or silicate drying procedures are conven sionally accomplished using spray drying. nozde drying (ea, tower or fountain), fash drying, rotary whee! drying. ovenfuid bed drying, and the like, which often require considerable expenditures for equipment and operating costs. The conventional drying procedures tend to reduce the ity to control final prodict physical properties and increase the chance of contamination, similar issue is associated with other synthetically derived polishing agen sch as silica gel and precipitated calcium carbonate (PCC). ‘Additionally, precipitated siliews intended for dentifrices reuire comminution in order to reduce the particle size of the dried precipitated silica product down toa size that does not feel grity inthe mouth ofa deatiftie user, while, on the other hand, not being so smal as to lack suficient polishing ‘or thickening action, That i, in coaventional practice, the ‘median particle size of the silica inthe reactor formed by ‘acidulation of metal silicate is too large for deniice Applications and the like. To comminute silica particulates, arinding and milling equipment are used, sueh 2s @ammer ‘or #pendilum mill used in one or multiple pases, and fine arinding has been performed, for example, by Muid energy fr aj mil It has been found previously that narrow particle size istrbution af eomminuted precipitated silica materials pro- Vides very effective cleaning, polishing, and abrasion ben- clits for dental applications. Prior methods of precipitated silica production have proven effective toa certain extent for producing excellent materials for such purposes: however, it has also been found that such expensive spray’flash drying pracesset podice silica materials prior to comminution that ‘exhibit an appearance and configuration that makes uniform rlling for narrow particle size distribution results poblem- ate. At the very least, such prodiction methods reslt in a Significant and appreciable amount of silica particles that exhibit particle sizes oo great forelfectve utilization within such dental cleaning applications. Hence, not only are costs inflated through incorporation ofthe aforementioned spray flash drying production steps, but the need to separate the ‘unacooptably high particle size silica particles from the resultant precipitated materials also contributes to costs and ‘nelcieney within the overall manufacturing procedure. Funbermore, it has been desirable from a consumer aesthetic perspoctive to provide clear formulations of den- lilices within the pertinent markel, Generally, silica par ticles are opague in appenrance and this ereate difficulty ‘when attempting 10 generate a clear or transparent gel or Jiquid toothpaste composition. It has been found in the past that certsin mannfacturing schemes could facilitate prodne- ‘ion of certain relatively highlight transmittance precipitated silica materials (© permit introduction of such a highly desired clear andor transparent resultant dentiffice within the industry, However, even with such a possibility avai able, the highest transmittance level relisly provided by fbrasive sifieas was found to be at or around 70-75% on & reliable, consistent manufacturing basis. Thos, there rem the potential for significant improvement inthis area with the cident possibilty of providing greater amounts of effective silica particles (preferably exhibiting the above- US 7,125,432 B2 3 discussed narrow particle size range for maximum dental abrasion and cleaning) within clear dentifrice gel, pastes ‘and Fgui ‘Additionally, the provalont mannfcturing methods for abrasive dental siticas have produced resulta materials that ‘exhibit ceriin properties that, although aot damaging oF ‘dangerous, leave room for improvement. Such properties, jnchide a propensity for dust generation from powdered silcas made via a process including atleast one sprayifiash drying step; difulty in providing structural integrity in terms of consistently producing. controlled. low-structure silicas due to the number of process steps required for powdered silica manufaetue; and suspect elablity in tems ‘of reproducible narrow ranges of pellicle cleaning ratios and/or radiation dentin abrasion characteristics without potentially resorting to increased eosts through separa methods of umanted particle size silica materials ‘Other issues that have arisen with such typically and traditionally produced silica andiorsfcate materials include the need to ensure that pre-spray dried materials exhibit sulicently low viscosities (and thas are relatively lowe in solids content) to prevent clogging of atomizers and other spray-drying cuipment. The costs involved with sch asst= ‘ances may ereate increases to the silica andlor siliate manufacturer andor dentiftice (or other type of composition if silicates ae involved) producer that may be passed an t© the consumer. Thus, the ability to overcome atleast some of these issues, as well as provide suitable silica materials in terms of packing density (for storage and. shipment), Alowabilty (to facilitate transfer during incorporation into dentifrice formulations, at leat), and, as noted above, a proper narrow particle size distribution all without incurring Increased manifacturing, additive, and/or scparation costs, ‘are all desirable for an ‘improved production method for silicas and/or silicates, and, in particular, abrasive dental silice materials ‘Therefore, a manufécturing method for precipitated silica andor silicate materials that ean provide not only lower ‘costs and grater production eficiencies to the prodicer and highly effective cleaning and abrasion levels, oe thickening ‘cpabilitis (all due to easily produced narrow particle size ranges without waste particles outside sucha range requiring Sequestration and removal\for silicas), or similar or other properties in terms of silicate materials, with possible highee Fight transmittance properties would be of great benefit bot to the pertinent industry and to the aesthetic tastes of ‘consumers. Unfortunatly, to date, there have been no such advancements within the preipitated silica and/or sliate production industry. SUMMARY OF THE INVENTION ‘The above and other objectives, advantages and benefits ‘are achieved by the prevent invention digested to a method. ‘of making preipitated silica compositions without the need for costly, conventional spray drying, nozzle drying, fish drying, tary wheel drying, oven bod drying, and the ike, preparing 2 precipitated silica composition, comprising the steps of intoducing, into a revetor container, reaction mix- ture contents comprising alkali silicate and acid with inter mixing thereof to form a suspension of precipitated silica; parially dewatering the reaction mixture after forming the precipitated silica by feeding the suspension into a chamber filter press in which the suspension is initially Filtered in @ plurality of chamber filter plates which provide first filter 0 o 4 cake material; further dewatering the frst fter cake under reduced pressure in the interior of the chamber fiter with ‘eating to provide second filter eake material having a solids content of 15 10 95% by weight, preferably from $0 10 90% by weight, and more preferably from 60 1 80% by weight ‘nd milling the precipitated silica of the second filter cake ‘material 19 achieve a dry, free flowing, precipitated silica powder of desired median particle size. These steps are conducted without the intervening step of conventional sitions as well. While the optimal use for this silica is in ‘dentifrices, this silica may also be used in a variety of other ‘consumer products. ‘By “mixture” it is meant any combination of two or more substances, inthe Jarm of, for example without intending to be limiting, « heterogeneous mixture a suspension, a solu- tion, a sol, a gel, a dispersion, or un emulsion, [By “dentifrices” it i meant oral care products such as, without intending to be limiting, toothpastes, ooth powders ‘and denture ereams “The term “erumbles” is intended to encompass a silica andor silicate material that exhibits a product form between that of a slurry and a powder such that the solids content present therein is between 35-85% (and thus moisture ‘content of 15-65%) for low structure silica and the solids ‘content present therein for high structure silica is between, 14.5-88% (with a complementary moisture content of from 15-85.5%), Such a silica andr silicate product funher ‘exhibits, due to amount of moisture present therein, & tendency to remain agglomerated without easly falling apart through Van der Waals forces, hydrogen boading, ete, provided throogh the presence of such moisture. As slurries ‘of sliea particles uenerally exhibit excessively high mois. ture Jevels (and thus very low solids content By weight, at least lower than 30% for low structure silica and below 12% for high stracture silica), and powders are substantially free from any moisture content (the solids content is penerally eater than 98% for either type of stnictured silica). the moisture level and ability fo provide a granular or pasty sila product that does not appreciably fall apart unless ‘excessive physical forces are applied there is one that ‘would be easly understood by the prattione. ‘This invention ates to a method of making precipitated sila compositions, also known as silicon dioxide, of SiO, ‘and more particularly, it relates to a method of making Precipitated silica compositions with postreactr dewater Ing and sizing ofthe slica particles being performed directly vis iydraulc chamber pres fillering combined with vac dewatering, followed by comminution. This invention also relates to products ofthis process scheme. Referring to the sole FIGURE, a generalized processing scheme is illustrated for making a precipitated silica accord- ing toa prefered embodiment ofthe invention. The process includes a reaction step (I); 4 dewatering step (2); and a milling step (3), which are discussed in greater detail below. In the fist step of the processing scheme, an acidulation reaction 1 is performed to precipitate silica, The initial ‘ulation reaction is performed) in a reaction system ‘equipped with suitable heating equipment. In general, the precipitated sileas made in step 1 may be prepared by @ Jesh water, or electyte solution, aeidulation process 0 o 6 wherein silica is precipitated by reaction of an alkali metal silicate and # mineral aid ia aqueous solution, In the fresh Water process, n0 electrolyte such as alum, Na,SO,, or [NaC is present during the acidlation reaction. ‘Sodium silicate solution is charged to a reactor container ‘orchamber including agitator to serve as initiating nce for the silica. The aqueous solution of sodium silicate in the ‘container is then prebetted to temperature inthe range of about 60 to 100°C, more preferably about 7010 95°C. Prior to introduction into the reactor container, any remaining sodium silicate that may be added is preferably preheated 10 ‘about 70 o 95° C. An acid solution is preferably preheated to ahout 30 %0 35° C, Although sodium silicate is ilustrated, it will be under- stood that any suitable alkali metal silicate could be use The term “alkali metal silicate” includes all the conventional forms of alkali silicates, as for example, metal silicates, silicates and the lke, Water soluble potassium silicates and sodium silicates are particularly advantageous with the ater being prefered It should be taken into consideration that the mole ratio ofthe alkali silicate, i.e, the ratio of silica to alkali meal oxide, contributes, depending on other reaction parameters, tothe average pore size of the silica products. In general, seceplable silica products ofthis invention ean be ‘made with silicate molar ratios (SiO,:Na,O) ranging from about 1.0 to 3.5 and preferably from about 2.4 (0 about 3.4 The alkali silicate solution supplied to the reacor vessel during various processing steps in the inventive method, as {eseribed elsewhere herein, generally ean contain between about 8 to 35%, and more preferably between about 8.0% fad 15.0%, by weight alkali metal sicate based on the total ‘weight ofthe alkali meta silicate solution. In onder to reduce the alkali silicate concentation af a source solution of alk silicate tothe above-indicated desired range, dilation water ‘an be added toa source tolution of alkali silicate before the licate solution is fed into the reactor, of, alternatively the ition water can be combined in sitw with the source solution of alkali silicate in the reactor used in the seid tion reaction step 1 with agitation-mixing to formulate the desired concentration of silicate in the alkali metal silicate solution, The acid, or scidulating agent, can be a Lewis acid or sted acid, and prefersbly is strong mineral aid such as sulfuric ack, hydrochloric acid, niteie acid, phosphoric ‘acid, and so forth, and more preferably sulfuric aed, added as a dilute solution thereof (eg, at a concentration of between about 6 t0 35 wi %, more typically about 9.010 15.0 wt %). ‘Once the reactor solution and remaining reactants have reacted the desired temperatures, addition of aci or simul- taneous addition of additional sodium silicate solution and acid into the resctor is commenced. ‘The acid and sodium silicate solutions are metered into the reactor over an add- tion time of about 30 10 0 minutes. Rates of addition ofthe reactants depend upon the mole ratio, addition time and concentration of the silicate ne the concentration of the acid. Generally, 2 moles sodium is neutralized with one mole sulfuric acid. Optionally a water soluble metal salt adduct material such asa water soluble salt of aluminum, caleium, magnesium or ine may be mixed with the aeidulating agent and inteodced ‘nto the reaction mixture along with the aidulating agent At the end of this addition period, most ofthe silica has precipitated. Additional acid is metered nto the rector unt ‘the reactor shy reaches the desired pH. Once the slurry pl eacies about 7.0, x preferable to reduce the acid How ate ‘until the slurry pT approaehes the target pH, at which point US 7,125,432 B2 7 the acid flow can be stopped and manual adjustment used t0 reach the target slurry pil. The preferred slurry pll is ‘approximately 4.0 (0 7.0, and more preferably between 4.5 10 60. At this joneture, the silies has precipitated to provide mixture ofthe precipitated sliea and the reaction liquor. ‘Once the desired shiny pli reached, digestion begins and the reaction temperature is raised to approximately 85-99" (C., and preferably 91 t 97° C., and digestion is continued at the elevated temperature for approximately 5 10 60 ‘nutes, and preferably fr approximately 10 to 30 mites Acid is added during the digestion step to the extent nee- ‘essary to miatin a constant pH, ‘After the digestion step is completed in the reactor used to implement step 1, and any subsequent pH adjustment ‘conducted, the rection batch is discharged from the reactor Although the above-described general protocol are prefered or synthesizing the precipitated silica to be conditioned according to this iavention, it will be appreciated that other trades of precipitated slicas, such as very low to very high Structure syntbetesilcas in aeconlance with the definitions set forth in J. Soe. Cosmet. Chem. 29, 497-521 (August 1978), and Pigment Handbook: Volume 1, Properties and Economics, 2nd ed, John Wiley & Sons, 188, p. 139-159, enerlly can be used in the practice of this invention The resultant silica reaction slurry then requires further processing prior to comminution into suitably sized pare ticles. Generally, such processing would inchude filtering ‘and washing in order to remove by-products of salts and ‘excess water therefiom, followed by the aforementioned ‘expensive sprays deving step. However, again, as noted previously, such a standard procedure as exhibited certain ‘drawbacks. For instance, it has been determined that the ‘comminution procedure, generally underiakea through ham- rer milling, oF similar type procedure, does not provide reliable narrow particle size ranges for such filtered thea sprayflash dried silica materials, Without intending to be bound to any specific scientific theory: it is bolieved thatthe resultant precipitated silias produced through this typical approach exhibit prior comiminution, nonniform appear ‘ances and configurations such that the structure of the pre-milled panicles are “pulled” such that the appearances thereof are nonuniform in structure as wel a density. Sueh particles appear this to be dificult to uniformly introduce within a milling process. Milling apparatuses generally include a milling component within the bollom porioa thereof, with an appreciable amount of headspace above sueh 2 component (although the chamber involved is scaled), When the “paid siliea particles are introduced within such a milling apparatus, some will easily be milled initially, while others will remain within the headspace above the milling component portion. In such a situation, ‘wherein the particles to be milled are nonuniform intro- ‘duced within the milling component itself, aot t mention begin as dliferenty sized and configured materials, the resultant milled silica particles will ikewise exhibit subse- ‘quent differing panicle sizes, albeit smaller than originally provided prior ro milling. Basically during milling, some of the particles will bepin as diferent sized particles, but will be reed ia size wo a uniform size with a large potion of the other particles milled simultaneously; however, since there will exist remainder portions of the milled particles, and since the pre-milled particles were of appreciably dif ‘erent sizes and configurations, these remainders portions of Particles wil create a significant disparity inthe distribution ‘of panicle sizes for the overall esiltant precipitated silica ‘materials. Thus, there was found noed to uilize different procedure to compensate for these diferences and produce 0 o 8 nore uniformity 10 the extent that an aeceptble aarow particle size distribution range could he provided Such mexifeation in the pevipitated silica production scheme is elect in the depiction within the sole FIGURE. 38 one non-limiting hough preferred, example In ep 2 of the New Prvipitted SiieaSlieate Process listrated thorin, dewatering is performed on the reaction mass obtained fom step 1. In one prefered expect, so-clled “J.Nap™ processing, oF similar chamber fier press process- ing, i prefered inthe ixplementation of Sep 2 of the pefene embodiment ofthe invention a iustated in THE SOLE FIGURE, Nowcliiting ihstations of methods sad equipment aangements for condoctig such J-Vap processing that ean be adapted for uss in the practice ofthe Hering/dewateri step of the present invention canbe found, for example, US. Pat No. 8888773 and EP 0 978 304 A2. which descriptions are incorporated. erin by referee. Other tmples of Jap processing equipment include commer Silly available equipment for this purpose, such as that Illusated in the working examples Below. The J-Vap pro- cessing equipment employed must pert reliable and aceu- fate contol over the level of water removal {0 mest the criterion set Forth herein for that parameter ‘The J-Vap processing arrangement penerally includes 9 series of reition chambers in which the washing and dewatering ofthe reaction slays condiced. The redetion chambers are tightly clamped together in the filter press ‘module. An energy conversion module als is included that Supplies heated water forthe pressurization ofthe redtion chmbers and also includes 8 vacuum systems used doing Slowsteing performed fteran initial presbure firing stage Tone exemplary suitable arrangement, the chamber iter press of th -Vap procesingsystom is eiseted as including plurality of eltemating diaphragm squeere plates and fer Plbtes covercd by respective hghid-pemneable fier meme branes, in which the squeeze pats ad fier plates deine slice suspension intociction sad low passages thercbe- tween, wherein the squeze plates include a diaphram tat Jr expandable toward an adjoining filter plate elective to Jngrease slidiquid separation inte silea suspension in Which figuid is tmasmsted through the adjoining Tigh rermeable membrane, andthe filter plats inching respec {ve imei frate drainage chambers for drainage of guid fier from the silica suspension. During the intl fitering and weshing stge of silica slunry supplied fom the reactor air low down commences to remove surface water from the cake. Thereafter, the Giaphraam is expanded by introduction of heated vid effective to expand the diaphragm and heat the abrasive Suspension elective o promote water removal om the fier material, Tha i, shy fom he reactor is pred into the radction chambers where firtion occurs and the Fee liquids drained aay. The silica fier materia then under aes ¢ core blow down and is washed with water Then @ Second ait blow dovsn commences to remove strlace Water from the ake, The digphreum is expanded again fo promote ‘water removal fom the filter mate Aer the initial fitation aod washing stag, vacuum promoted dewatering i performed, For example, the redue- fion chambers are prosurized with hentd water, anda ‘acim i initodved. For example, ina seeond stage ofthe lowatering process as performed in the J-Vap processing System, the drsingge chambers are conpceted toa vacuum source elective to remove vaporized potions ofthe silica suspension US 7,125,432 B2 9 The dewatering time is set to achieve the desied water reduction. Afier the dewatering stages are completed, the reduction chambers are separated from one another and the ‘dewatered filler cake material i discharged and proceeds to the milling step, lstrative, non-limiting conditions for condcting such 4Vap dewatering, when used to perform the dewatering step 2 in the sole FIGURE sceording tothe preferred embod ‘ment ofthe invention, ielude the following general cond Deswater time: 0 10 12 hours Feed Pressure: 10-80 psi (69 S52 kPa); Feed temp: 70-200" F.(21-93° Cs Hot water temp: 120-200° F. 49-33" C.); Blow down air pressure: 10-80 psi (69-552 kPa) System Vacuum: 20-29 in, Hg (68-98 kPa}, Squeeze aie pressure: 10-100 psi (69-670 kPa); and Solids content out of J-Vap: 15-95%, ‘The reaction mass is filtered and washed with water to reduce the Na,S0, level to less than $% aoe preferably less than 2%, by weight. The resulting dowatered crumbles enerlly contains about 15 t0 about 95 wt % solids content. “Altematively, it has been found that similar system, known as the Thermal cake Drying (or TCD) system, may be used as substitute for this J-Vap process. This TCD method is basically a steam pressure dehydration process ‘wherein a steam pocket is formed adjacent to filer cake of the silica when the temperature exposed thereto exceeds the boiling point ofthe water present within the target cake. The ‘cake is present between two plates such that once the steam. pocket (cushion) is formed, it continues to increase in size to squeeze the target filter cake. Thus, in addition to the de-watering sep through » membrane squceze, as noted above, the dewatering is achieved through thermal energy rather than mechanical energy alone. Thus, this may be utlzed as substitute oF ia addition to the primary and prefered J-Vap method. Referring now to the milling step 3 in the sole FIGURE, ‘comminution is needed becaise the particles in the silica suspension drawn from the reactor of step I generally have ‘8 median parle size (MPS) of preter than about 50 jm to about 100 um, ane! more typically about 65 ym to about 85 jum. These particles sizes are unacceptable for applications suei a oral cleaning composions. Namely, smaller sliea particles are neeled so thatthe particles ane not arity ia Texture fo a user, yet the particles must be lame enovgh t0 provide the requisite polishing action on teeth. For oral ‘leaning compositions, sliea panicle sizes between about 1 ‘and about 30-jum are generally required, and a median particle size of between about 3f0 17 ym is preferred in this To comminute the silica particles (typically agalomerates) sep 3, the filter cake revived aller dewatering instep 2 jis fed toa milling station, Preferably, no extraneous organic dispersint is added tothe cake before milling is performed Jn step 3; however, such an added component may be included ifdesied. Fithera single stage mill ora multi-stage milling operation in step 3 can be used. For example, the rmulti-stae milling ston, in one embodiment, can be ‘comprised of two or more separate mills through which the silica is successively progressed, Alternatively, the muli stage milling station can be comprised of a single mill in ‘which the silica is fed through the single mill in multiple passes using recirculation, The amount of energy dissipated into the fee silica at each mill stage, or in each pass through a single mill in a muli-pass form of multi-stage milling, enerlly is kept approximately the same, although this is 0 o 10 not necessarily required. Multistage residence times to be applied, ‘The mill types used as described above can be hammer, pendulum, fluid energy, irjet mill and the like. One pre- ‘ered type of mill used in the practice ofthis invention isa vertical Reymond® mill manufactured by ABE Air Pre- heater, Ine (Lisle, I). The Raymond mill is single state Famer style mil, ‘In one prefered noo-limitng illustration, the mill used to condoct step 3 inthe sole FIGURE penealy 15 operated ‘under the fallowing conditions: ‘Mill configuration: 2(U) and 2(L.) or S(U) and 6(L) whiz- ands. Airlock feeder rate: 1.5-2 rpm ‘In keeping with an objective of this invention of reducing silica particles without the need for conventional deying procedures, the total amount of shearing forces and heat Applied tothe press cake daring milling shouldbe sulicient to reduce the median particle size (MPS) to between sbout 1 to about 30 mierons (um), preferably between about 3 and bout 17 microns, and yield a fee flowing silica powder With less than 12% moisture, preferably less than 9% ‘moist. The abrasive particies in the milled abmasive ‘composition have less than 1.5 wt faction of #325 mesh size particles (greater than about 45 m). Thus, a8 opposed {o the previous production methods including separate fil ‘ering and spray/lash drying steps the particle size range for this novel procedute for silicwslicate production is more controlled within a narrow range for greater effcieney and cost reductions overall t0 the benefit of the producer and, ‘imately, the consumer. ‘The sileas provided in the ahove-llustated compositions fare proferbly characterized as synthetic hydmted amor phous silicas, known a8 silicon dioxides or SiO., These precipitated silicas ean be characterized as very low to high structure synthetic sia Tn alton to the above-described step 1 methodology of precipitating the raw synthetic amomphous sileas in the reactor, the preparation of the raw silica is not accessarily Timited thereto and it also ean be generally accomplished in ceordance with the methodologies deseribed, for example, in prior USS. Pat, Nos. 3,893,840, 3,988,162, 4,038,098, 4.067.746, $340,583, 4420312, 5,225,177 and S891 421 all of which are incorporated herein by reference, as Fong as such methods are appropriately modified to append the post-processing treatments) used in at least steps 2and 3 of the preferred inventive method, as illustrated in the sole FIGURE and discussed above, Likewise, silicates such as alkaline earth metal silicates, particulary, though not nee- essai, calcium and magnesium silistes, as well as other ‘metal and mixed metal silicates, such as. zinc silicate, calcium magnesium silicate, sodium aluminosilicate, sodium magnesium aluminosilicate, and the ike, may be ‘generally produced in aecondance withthe methodologies Seseribed, for example, within prior U.S. Pat. Nos. 2.739 073, 3.228.784, 3,798,046, 3.844.921, 4.557.916, and con pending U.S. patent application Sex. No, 101656,386, all of ‘whieh are incorporated herein by reference, as long as sch methods are appropriately modified to append the post- processing treatment used in at least steps 2 and 3 of the preferred inventive method described herein, AS will be appreciated by one skilled in the art, reaction parameters ‘whieh affect the characteristics of the resultant precipitated silica inelude: the rate and timing at which the various reactants are added: the levels of concentration of the various reactants; the reaction pl he rection temperature andor the rate at which any electrolytes are aed. permits longer US 7,125,432 B2 un The precipitated silica compositions of this inventio enerlly have the ollowing properties: linseed oil bsorp- tions between about 40 10 abot 230 ce/100 g, RDA (Radio- active Dentin Abrasion) values between about 30 t0 about 200, PCR (Pellicle Cleaning Ratio) values of 0 to 200, and 2% Transmittance (% T) greater than about 60. Although Silcas have been illustrated herein as the water insoluble particle compositions being proxloced by this invention, it ‘willbe understood thatthe principles of the present inven= tion are also considered applicable to other water-insoluble particles that can be synthesized in a reactor without the reed for any intervening conventional drying, Other such ‘water-insoluble particles include, for example, siliea pels, calcium phosphate or its dihydrate forms, caleium pyro- Phosphate and precipitated ealeium carbonate (PCC). Examples of use of these optional denice abrasives are ‘deseribed herein andor, for example, in Reissue No. 29.634, and US. Pat. Nos. 5,676,932, 6,074,629, and $,658,$53, and the patents cited therein, all being ineorporated herein by reference. These optional ingredients if used, can be used a Jevels that are customarily seen in dentifie formulations. ‘The precipitated silica compositions of the above-de- scribed inventive product (available at step 3 in the sole FIGURE), whon incorporated into dentifrice compositions such as toothpaste s present ata level of from about 1% 10 about 50% hy weight, more preferably from about 1% to about 35% by weight, depending onthe siliea properties and the intended function of the silica (abrasive or thickening ‘agent in the formulation, Overall denice or oral cleaning ormitlations incorporating the compositions of this inven- tion conveniently can comprise the following possible ingre- dons and relative amounts thereof (all amounts in wt ®): Deaiifiice Pomnulation: Tigi Wai resent ‘oe Thtapesic spss else ape) ‘ic eevee ‘arts ‘storie seme ‘cringe 0825 ‘The presence of other silica abrasives, in addition to the type priced vi the inventive method described herein, as ‘well as two or more silica abrasives made va such a method, ‘are encompassed within the tem “abrasives” within the above Dentifice Formulation. ‘The term ~Therapeutic ‘agents includes materials sueh as, without Himitation, ant microbial szens (cationic, anionic and nonionic) and anti ‘caries apents as well as any other type of typical component Within dentifrice formulations that provide therapeutic celfets to the teeth and/or gums of the user. Suitable ant microbial agents inchude bisguanides, such as alexidino, chlorhexidine and chlorhexidine gluconate, quarternary ammonium compounds, such as benzalkonium chloride (BZK), benzbonium chloride (BZT), cetylpyridininm chloride (CPC), and domiphea bromide; metal salts, such as ne citrate, zine chloride, and stannous Mhuoride; sodium 0 o 12 ponofluorophosphate, stannous Muoride, and the Tike san guinaria extract and sanguinarine; volatile oils, such as evcalypfol, menthol, thymol, and! metiy!salieylate; amine ‘Muorides: peroxides and the like. Therapeutic agents may be used in dentifrice formulations singly oF in combination. “The following examples are presented to illastate the invention, but the invention snot to be considered as Limited thereto, In the flowing examples, parts are by weight inless indicated otherise EXAMPLE 1 Precipitated slices wor prepared in reactor as follows, aunt thereafter were subjevted to cern dewatering an nilling described below, without any conventional spray drying occurring. Two batches of sili, wore prepared cconing to the process below and combined together to provide Fxample silica. "Example I pciptte silica was propared by adding 4 1 of sodium silicate (1.0%, 25 mole ratio of SiOsN2,0; peceated 0 75°C.) 1 a reactor a restion medium. The beach was heated 1 85°C. andthe altar speed Was set at 50 sp. Sodium sicate (13.0%, 28 mole ao of SiO. 1Na.O;prehested 10 75°C.) and sure acid (11.42%) were ‘hen simulaneously added to the reactor Sodium siate auiion rate was 12.8 L/min and acid ation rate was 3.8 ima. The simoltaneoos addition of sodiom slate and sulfuric acl eontinued foe 47 mines, after which time the ‘oui silicate addition was discontinued. The acid low ‘eas continued atl he bath reached pH 5.55.8 at which time the acid flow was stopped. The batch was digested at 93° C. for 10 minutes and the pH adjusted to between 5.5 and $8, as naestary. The batch was then dropped (4 fired from the reactor), Two exaet batches ofthis sibca ‘wore prepared os described above and then combined as Example I slca Example I silica prepared as desribed above was dewa- tered in a J-Vap desttering system (model IVAP 470/100 availble rom US Filter Corporation, Holland, Mich) under ‘the conditions listed in Table! below. Specifically. the silica reaction sluny at about 62% solids Wa apitated and heated tothe desired feed temperutre, then was pumped at 20 psi for about 15-2 mites ito the J-Vap system. Presstre squeeze (SQZ) and blow down (BD) ai Was initiated ad confinved for 1-2 minute. Next, core blow down and ‘washing was initiated. Silica cake was washed with 60° C water for 18-2 mingles while maintaining SQZ at 20 psi lower dn wash water pressure (40 pi). Therafler a second SQZ and BD was ited and continaed for S mines ial the sea eke wos in under Vac (28 ach Fg) aun SQZ for six hours Hot water 80" C) was recirculated {through the I-Vap system to remove excess water Irom the product, Solids content was measured on the dewatered productby drying teresting silica rumbles at 150°C. for 16 ours in an oven, ‘The Example 1 silica was fod into @ 18° vertical Ray swond® mill, manufactured by ABB Ale Preheater, In {Lisl .) The ill configuration and ie sifica feed rate vio tm asiek feeder are ven in Table I below. No hammers ‘were used inthe ilies milling proces. COMPARATIVE EXAMPLE 1 Siliea was prepared according to the silea preipitation process in Example 1 hut for comparison purposes was filtered, spray dried, and milled according to conventional vethods such as thet outlined in the “existing Precipitated US 7,125,432 B2 13 Silica'Siliate Process” within the Sole FIGURE, After ‘digestion, the silica was fitered oa a by 3° rotary drum, vacuum fer (Ametek, Ine, Fast Mofne, I) having a total 128 square fet and washed until the filtrate had ‘s conduetvity of not more than 2000 yanios. The fer cake ‘vas then slatied with water and mixed for § minvtes with Cowles agitator t form a cake slunry having the solids ‘content listed in Table IM, below. The cake slur was the spray dried (at the inlet and outlet temperature shown in ‘Table I, below) ia a Nigo FS wheel atomizer speay dryer (Niro, Inc, Soeborg, Denmark) and milled in a Raymond mill decording tothe conditions listed in Table II, below. EXAMPLE 2 Precipitated slices were prepared in a reactor as follows, ‘and thereaRer wore subjected to the similar dewatering and milling processes described in EXAMPLE 1. Two batches of silica, were prepared according to the process below and 2 ‘combine together to provide EXAMPLE 2 slice, EXAMPLE 2 precipitated silica was prepared by adding 600 L of sodium silicate (13.0%, 2.5 mole ratio of SiO; Na,Or preheated to 7ée1” C.) to a reactor as reaction ‘medi. Sulfur aid (11.486) was then added tothe reactor at 6.2 L/min until the batch pH reached 6.5. At batch pH 6.5 the acid flow rate was reduced to 2.0 Linn until the batch pll ached 5.820.1 and thea he acid low was stopped. The batch was digested at 93° C for 30 minates andthe batch pf ‘adjusted back io 8.84/-0.1, as necessiry. The hatch was then discharged fom the reactor EXAMPLE 2 silica prepared as described above was dewatered in a J-Vap dewatering system and milled in a Raymond mill. The dewatering and milling conditions for EXAMPLE 2 ace listed in Table T and Tl, respectively. EXAMPLE 3 Precipitated silicates were prepared in a reactor as fol- Jows, and thereafter were subjected to similar dewatering and milling. described helow, without any conventional Spray drying occurring, Two batches of silicates were pre- pared according to the process below and combined together to provide Example 3 silicates. EXAMPLE 3 precipitated amomphous sodium magnesium sluminosilcate Was prepared by adding 398 L of 11% ‘aqueous sodium sulfate solution and 3.9 L of S0% aqueous magnesium hydroxide solution to a reactor as. reaction medium and heating w 71° C. Clarified alum 24° Cu $4 g/l) was added ata rate of 29 Limin for 35 minutes and then the ddition was paused for 2 minutes. Next, simulta- neous ation of clarified alum (same rate as before) and sodium silicate (25 mole ratio of SiO-Na,O: 04 kp) at rate of 7.0 Limin began and continued for total of 35 minutes, After 35 minutes, the sodium silieate addition stopped and the alum addition continued for about another 1.5 minutes until the pl! was reduced to 6.5, The alum ition was stopped and the sodium silicate addition was restarted for another 4 minutes to bring the reactor batch pl 109.2. The reactor batch was digested for IS minutes at pll 9.2and’71°C. belore discharging the batch from the reactor EXAMPLE 3 silicate prepared as described above sas dewatered in a J-Vap dewatering system and milled in a Raymond mill. The dewatering and milling conditions for EXAMPLE 3 ace listed in Table I and Il, respectively 14 EXAMPLE 4 Precipitated silicates were prepared in reactor as fol. lows, and thereafter were subjected to similar dewatering and milling described below, without any conventional spray drying occurring. Two batches of silicates were pre- pared according to the process below and combined together fo provide Example 3 silicates, EXAMPLE 4 precipitated amorphovs sodium alumino- silicate was prepared by adding 30S Lo! 11% sodium sullste solution toa reactor as reaction medium and heating to 60° C. Sodium silicate (2.6 mole ratio of SiO,-Na,O: 0.24 ky/t) was then added! at a rate of 11.7 Limin for 4 miutes a8 excess silicate. Next, while sodium silicate addition contin- ‘ved, 0.30 kg/ aqueous solution of alum (aluminum sulfate) Aadtion was commenced ata rate of 4 [asin fora total of '35 minutes. After simultaneous addition was finished, the reaction batch was heated to 71° C. and digested for 15 ‘minutes, "The reaction batch pH was readjusted to between 8.1 and 8.5 and then was discharged from the reactor PXAMPLE 4 silicate prepared as described above was evwatered in a J-Vap dewatering system and milled in a Raymond mill. The dewatering and milling conditions for EXAMPLE 4 are listed in Table I and Il respectively TABLE | sume Feet Ten. oD Pretest 200 2000 Tine. se re Tine, i 0 ‘War Te, tbe Wash en. moo Mer ee Reving eSde 742687 RS an COMPARATIVE EXAMPLE 2 Silica was prepared according to the silica presipitation process in EXAMPLE 2 but for comparison purposes was fier, spray dried, and milled according to conventional sthods such as that outlined in the “existing Precipitated Silica/Siicate Process” within the Sole FIGURE. ARer

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