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    US8663518B2

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    Quang VA
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    © All Rights Reserved
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    (2) oy os) my o a @ 6s) oy 2) 658) 66) United States Patent Panjnani et al. METHODS OF PRODUCING 4 TITANIUM DIONIDE PIGMENT AND IMPROVING THD PROCESSABILITY OF TITANIUM DIONIDI PIGMENT PARTICLES Inventors: Kamlesh G. Panjnani, Edmond, OK (Us); David F, Marshall, Edmond, OK (US), Jeffrey D. Elliott, Oklahoma City OK WS) Assignee: ‘Tronex LLC, Oklahoma City, OK (US) Notice: Subject to any disclaimer, the team ofthis pateat is extended or adjusted under 35 USC. 154(b) by 81 days. Appl. Now 13/937,839 Filed: Des. 27,2011 Prior Publication Data US 2010161856 A1 Jun, 27,2013, Int. Cl 298 9708 (2006.01) us.cl. SPC osu 26417; 28913 Ry 29/913 Ps 1061436: 106447; 425/610, Field of Classification Search None Se application file for complete search history. References Cited USS. PATENT DOCUMENTS 82538 A 7974 Hiney oa ysooad6 A 1075 Femignn 4113660 4 91978 Abel 4810908 8 198) Benn cal Smss748 A TA9OL Burow et SSI819R A $1995 Conors Se eal SS0L732 A + 3996 Niedena etal Losss7 Sst0g08 A * 411906 Parmenter aout SGI258 A 31999 Iguchistal 'US008663518B2 (10) Patent No. 4s) Date of Patent: US 8,663,518 B2 Mar. 4, 2014 565379 A 81997 Weberetal S897.00 A 111908 Walon eta 310739 A "82000. Maca tal S199 A 112000 Hallet 63020926 BL* 102001 Ansan etal. un 28313 8 Se202¢ BI 92003 Rostlnkec al Fosiou Bl* 72006 Oretal 425924 750407 B2 72009 Bobach eal F986 BE 112010 Pred eta Fst6489 B2 122010 Gist. Josie Bo A2011 Bothast at aoovbi96st7 AL 102003 Harada ea 2ov7007e78) AL '32007 yan Sorio24es AL 23011 Stgiyama ct Souuo1sow22 AL 62011. Nalamun etl FOREIGN PATENT DOCUMENTS BP £:250290 4 wo 20100078394 a2 (OTHER PUBLICATIONS 111996 772010 International Search Report and swrten opinion sod Fob. 25,2013 Jn corresponding PCTUS2012071668, ied Des, 262012, Tomax Lie Delwel, Francois et al, Continuous Grasultion of Sodium Triphosphate in a Pan Granulator, Ind. Eng. Chem, Povcss Des Dev, 197%, pp. 261-254, American Chesncal Society ‘Wright De Scot eal, Process improvement for Piste Processors Resulting fom a Modied Form of Tani Dixide, 67" Annual Techaical Coferenceofthe Society of Pasties Eagives, 2009, yl 5.2000. pp. 1473-1476, Society of Plastics Enginces * cited by examiner Primary Examiner (4) Attornes Mary F'Theisen Agent, or Firm — McAfce & Taft on ABSTRACT A method of producing a titanium dioxide pigment is pro- Vided. Also provided is « method of improving the provess- ability of titanium dios particles without adversely affect ing the cheological properties of the titanium dioxide particles 47 Claims, 6 Drawing Sheets U.S. Patent Mar. 4, 2014 Sheet 1 of 6 US 8,663,518 B2 7 TiO2 “| PRODUCTION PROCESS TiO2 PARTICLES SOURCE OF TiO2 PARTICLES v > FEED < MECHANISM, 74—~] SOURCE OF ae TREATING ae™~ REMOVER AGENT 46 a AGGLOMERATOR “Te —< SCREEN ~110 APPARATUS a BULK 120 CONTAINER (~ < ——— —" U.S. Patent Mar. 4, 2014 Sheet 2 of 6 US 8,663,518 B2 1 TiO BULK CONTAINER(S) PARTICLES SOURCE OF TiOg PARTICLES |—~12 14 ¥ > FEED ‘ MECHANISM MP 74) SOURCE OF - TREATING REMOVER REATIN 6 ¥ AGGLOMERATOR a) —< ——_¥ __ 72 SCREEN 110 AppaRATUS [~ ¥ BULK 120 CONTAINER [~ Se lo U.S. Patent Mar. 4, 2014 Sheet 3 of 6 US 8,663,518 B2 SOURCE OF |/'—5-— Tz TiO2 v1 PRODUCTION 20 L J particles |\ PARTICLES | "process 12 —14 ‘SOURCE OF TREATING. AGENT 120 —_ re - U.S. Patent Mar. 4, 2014 Sheet 4 of 6 US 8,663,518 B2 SoUREOF |/—Tro-—] rios aux mt J paitzeg {PARTICLES | CONTAINER(S) 12. = 1 - 14 24 4 25 1D ele SOURCE OF % & 32 TREATING AGENT “ 2—-T 12—F = 120—~ | U.S. Patent Mar. 4, 2014 Sheet 5 of 6 US 8,663,518 B2 ~74 ‘SOURCE OF TREATING AGENT 66 68. Ss SE U.S. Patent Mar. 4, 2014 Sheet 6 of 6 US 8,663,518 B2 US 8,663,518 B2 1 METHODS OF PRODUCING A TITANIUM DIOXIDE PIGMENT AND IMPROVING THE PROCESSABILITY OF TITANIUM DIOXIDE PIGMENT PARTICLES BACKGROUND OF THE INVENTION Titanium dioxide (150,) s manufactured around the world for use in a variety of applications. For example, titanium dioxide is commonly use asa pigment in polymer compo- sitions, paint formulations, paper produets, and other prod- Titanium dioxide pigments are generally prxlueed in paws ‘der form with certain properties and performance character- istics (for example, a certain particle size, shape and Iatice structure and certain heological properties when dispersed i polymer compositions). The pigment particles are typically ‘coated with one or more materials to modify or enhance the properties and characteristics of the pigment for particular applications. For example, the pigment particles are often 2 ‘coated with compounds that funetion to improve the opacity, brightness, durability and rheological properties of the pig= Titanium dioxide pigments can be manufactured by ether the sulfite processor the chloride process In some eases, the > particular manufaeturing method utilized can impact the properties and characteristics of the pigments and the end ‘pplication sssociated therewith inthe sulfate process for mantafacturng titanium dioxide, titanium slag ore, usually an ilmenite, is dissolved in sufi Ficacid to fom amixturcof sulfates, including titanyl slate Tron is removed from the solution, The tanyl sulfate i thea hydrolyzed in solution to yield insoluble, hydrated titanium ‘dioxide, The hydrated tittium dioxide is heated ina caleinee to evaporate the water and decompose the sulfuric acid in the solid. The solid i then converted into titanium dioxide seed ‘enstals which can be milled tothe desited size Inthe chloride process for manuficturing titanium dioxide, dry titanium dioxide ore is fed into @ chorinator together ‘with coke and ehlorine to make a titanium halide (such as tanium tetrachloride). Steams of gascous titanium halide (uch as titanium tetrachloride) and oxygen are heated and ‘introduced at hig flow rates into an elongated vapor phase ‘oxidation reactor conduit. A high temperature (approxi mately 2000° F.102800° F.) oxidation reaetion takes place in the reactor conduit whereby particulate sold titanium dioxide ‘and gaseous reaction products are produced, The titanium dioxide and gaseous reaetion produets are then cooled, and the titanium dioxide particles are recovered ‘In typical titanium dioxide production process, the tt: nium dioxide is prodiced inthe form of fine powder, wick tends to be very Hull. The fine parle size and uiness of the praduoed titanium dioxide powder ean cause problematic ‘dust to form when the pigment is transported, bagged and unloaded from bags. Additional. the fine particle sizeof the titanium dioxide procict ean result in significant bridging of the pigment particles which ean make dificult to convey the product and prohibit the produc fom easily flowing through hoppers and other transfer equipmeat subsequently used t© incomporate the titanium dioxide into ater products In onder to reduce the problematic dust and improve the ‘lowabilty of the pigment, the titanium dioxide powder can be formed into agglomerates. Unfortunately, however, agglomeration of the powder can decrease important perfor mance characteristics of the pigment in end applications thereof: For example, the fine particle sizeof the ttaninm dioxide is very beneficial with respect to performance char. 2 acteristics ofthe titanium dioxide such as the ability ofthe ‘itanium dioxide be dispersed in polymer compositions and the rheological characteristics ofthe pigment in such compo- sitions. Thus, efforts to reduce the dastiness and improve pigment flow charoctersties of the tianium dioside tend to ‘ome a a sacrifice to important performance characteristics ofthe titanium dioxide, [BRIE SUMMARY OF THE INVI TION In a fest aspect, the invention provides a method of pro- ducing a titanium dioxide pigment, This aspect of the iven- ‘ion comprises the following steps (1) producing titanium dioxide particles: and (2) forming the titanium dioxide particles into titanium dioxide agglomerates hy a method that includes the following steps: (@) feding the titanium dioxide pa ‘erator, (b) admixing a hydrophobic, organi treating agent with the titanium dioxide particles by spraying the trating ‘agent om the titanium dioxide particles in the agglom- ‘erator and (©)operating the agalomeratorto form the titanium dioxide particles into titanium dioxide agglomerates. In-a socond aspect, the invention provides a method of improving the processability of titanium dioxide pigment particles without adversely affecting the rheological proper- tics of the titanium dioxide pigment The inventive method of this aspet of the invention comprises the following steps: (@) feoding titanium dioxide particles nto an agglomerstr (b) admixing a hydrophobic, organi treating agent with, the titanium dionide particles by spraying the eating agent ‘on the titanium dioxide particles inthe agglomerator, (C)operating the agglomeratoro form the titanium: particles into titanium dioxide agglomerates; and (@) transferring the titanium dioxide agglomerates out of the agglomerator. “The titanium dioxide pigment agglomerates produced in cordance with the inventive methods are suitable for use in ‘variety of applications. The titanium dioxide agglomerates frerelatively free-flowing andlor dusting yet lao have good theological properties and other performance characteristics. Infact, the rheological properties othe pigment particles can be enhanced by the inventive methods The titanium dioxide Pigment agglomerates are particularly suitable for use in ner compositions including, but not Himited o polyole- fin, polyvinyl chloride (PVC), and polycarbonate (engineer ing pastes) compositions cles into an agglom- oxide BRIBE DESCRIPTION OF THE DRAWINGS. PIG. 1s a flow diagram illustrating the fist aspect ofthe invention, namely, the inventive method of producing a ti nium dioxide pigment. PIG. 2is a Mw diugram illustrating the second aspect of ‘he invention, namely, the inventive method of improving the processability of titan dioxide pigment particles without adversely affecting the cheologial properties ofthe titanium oxide pigment FIG. 3 is schematic low dingram illustrating the first faspeet of the invention and examples of equipment used therein. FIG. 4 schematic flow diggram illustrating the second aspect of the invention and examples of equipment uscd therein, US 8,663,518 B2 3 FIG, § illustrates the inventive methods, including the ‘agglomerator and stepsof admixing the hydrophobic, onganic treating agen with the titanium dioxide partieles and operat- ing the agglomerator to form the ttaniim dioxide particles Jno titanium dioxide agglomerates FIG. 6 illustrates an alternative configuration and alterna tive location of the spray nozzle used (0 spray the teting gent on the titanium dioxide partieles in the agglomerator DETAILED DESCRIPTION OF THE INVENTION Ina fist aspect, the invention is a method of producing a titanium dioxide pigment. na secon aspect, the invention is ‘amethod of improving the processability of ttanium dioxide pigment particles without aversely’affecting the rheological properties ofthe tani dioxide pigment. Referring now to the drawings and specifically to FIGS. 1 and 3, the fst aspect ofthe invention will be described. The inventive method of producing a titanium dioxide pigment ‘ean be carried out oa a batch or & continuous basis. AS ‘described in this detailed description, the inventive process is ‘arti out on continuous bass, The ttm dione pig ‘ment produced by the inventive method has impmoved pro- ‘cessbilty. As used herein ancl in the eppended claims, “improved. processability” means reduced dusting and improved flow properties during processing. ‘In accordance with first step, titanium dioxide particles ‘are produced by 8 titanium dioxide production process 10, ‘The exact nature ofthe titanium dioxide production process 10 not critical, Processes for producing titanium dioxide particles are well known in the af. For example, the ttaninm ‘dioxide production process can be a chloride process for producing titanium dioxide ora slate process for producing ‘itanium dioxide. In this aspect of the invention, tbe titanium dioxide production process 10 is a source 12 of titanium dioxide particles “The titanium dioxide particles are then formed ino tt nium dioxide agglomerates in accordance with the method described below. The ttanium dioxide particles are trans {ered from the titanium dioxide produetion process 10 (he source 12 of itanim dioxide particles) toa feed mechanism |M4-For example, ifthe titanium dioxide production process is chloride proces, the particles 10 can be continuously con- veyed from a cooler used to cool the particles following & ricronization step to the feed mechanism 14 ‘The feed mechanism 14 operates 1o continuously feed the titanium dioxide panicles downstream ata controlled rte ‘The particular feed rate depends on the scale ofthe overall, method including the ate at which the titanium dioxide pa ticlesare fed by the source 12 titanium dioxide panicles (in this aspect, the titanium dioxide production process 10), and the capacity of the agglomerator (described below). “As shovvn by FIG. 3, the feed mechanism 14 isu serew feeder, The screw fester 14 inchades @ hopper 18 having an inlet 20 for receiving tianium dioxide particles from the source 12 of titanium dioxide particles (in this aspect, the titanium dioxide production process 10) and an outlet 22. The ‘outlet 22 of the hopper 18 is connected to the inlet 24 of 2 housing 28 containing a rotating auger 26. The housing 25 ‘containing the rotating auger 26 also inclodes an outlet 28. ‘The rotaion speed of the auger 26 controls the rate at whieh, the titanium dioxide particles are conclicted through the out- Je( 28. Examples of ther mechanisms that can be utilized as the feed! mechanism I include rotary or star valve feeders, pneumatic feeders, and helt or bucket conveyors, “The titanium dioxide particles are continnousy fed fom the outlet 28 of theauper housing 25 ofthe serew feeder 1410 0 o 4 ‘lump remover 32 which processes the particles to remove Timp therclrom. Lumps ofthe titanium dioxide particles can be formed, for example, duet compaction ofthe particles in large bulk containers or bags, AAs shown by FIG. 3, the lump remover 32 includes a housing 34 having an inlet 36 for receiving the ttaninm sioxide particles, ad an outlet 38. The housing 4 is divided by am upstream vibrating sereen 40 which is vibrated by @ ‘motor 42, The titanium dioxide particles are conveyed from the outlet 28 ofthe suger housing. 25 into the inlet 36 of the housing 34 of the lump remover 32 and onto the vibrating sereen 40, The vibraing screen 40s coatinuously vibrated by the motor 42 to sereen any lumps of the titanium dioxide particles sufficiently to allow the particles to passthrough the ‘Screen. Any lumps of the titanium dioxide particles that are ‘ot sufficiently sereened tallow the particles to passthrough the vibrating Sereen 40 are receculated through a recteule- tion outlet 44 ofthe housing 34 ofthe hump remover 32 back ‘othe inlet 200f the sere fesder 14. The screen 40 preferably has a U.S. mesh sizein the mingeof from about 719 about 16. ‘More preferably, the sersen 40 has a U.S. mesh size in the range of from about § (0 about 12. “The titanium dioxide particles are continuously fed from the outlet 38 of the housing 34 ofthe lamp remover 32 (0 an agglomerator 46, Prior to being fed into the agalomerator 46, the titanium dioxide particles are in the form of a powder hhavinga primary particle size inthe range of from about 0.1 {o about 0.5 microns. Preferably, the titanium dioxide par- ticles are inthe form of » powder having a primary particle size in the range of from about 0.15 mirons to about 0.3 ‘Lumps of te titanium dioxide particles ean interfere with theagelomeration sep ofthe inventive process. However, the Jump removal step and lump remover 32 are optional. For example, ifthe titanium dioxide panicles do not have any problentatic lamps or the poreatil therefor as they come out ff the serew feeder, the hump removal step and hump remover ‘32 canbe eliminated. ‘As best shown by FIG. §, the agglomerator 46 forms the titanium dioxide particles (as designated by the reference ‘numeral 48) into titanium dioxide agglomerates (as desig- ‘ated by the reference numeral 0). As used herein and inthe appended claims, “titanium dioxide apglomenstes” means plurality of titanium dioxide particles bound together into a bull, cluster or other mass. Por example, the titanium dioxide ‘agglomerates 50 can be in the form of pellets or pails. The agglomerator 46 i preferably a rotary mixer. ‘As shown in detail by FIGS. 35, the agglomerator 46 is 3 pan pelletzer. The pon plletizer 46 includes a rotating pan $2 havin a bottom 54, circumferential wall 56 perpendicularly extending Irom the bottom, and an open top 60 opposing the bottom. As shown by FIG. 3, the eitcunferential wall has an Upper end 62 anda lower end 64, Titanium dioxide particles 48 are transferred from the outlet 38 ofthe housing 34 ofthe Jump remover 32 into the pan pelletizer 46 through the open ‘op 60 thereof for example, through a portion 63 of the open {op 60adjacentto the upper end 62 ofthe circumferential wall 56). Similarly, the agglomerates 50 formed inthe pan pellet- jer 46 are transfer out ofthe pan pelletizer 46 through the ‘open top 60 thereof (for example, through portion 68 ofthe ‘open op 60 adjacent to the lower endl 64 ofthe eicumieren- tial wall 86). “The rotating pan 82 is downwardly inlined at an angle ‘with respect to the horizontal plane. As used herein and inthe appended claims, “downwardly inclined at an angle with ‘respect to the horizontal plane” means dawnwandly inclined tan angle with respect othe horizoatal plane ofthe room US 8,663,518 B2 5 hich the pan pelletizer 463s located. As shownby FIOS. 3-5, the horizontal planes designated by the relerence number 66 “The angle of inclination of the downwardly inclined rotating pan $2 can vary. ‘A motor 68 rotates the rotating pan 82 ineithera clockwise. s ‘ora counterclockwise direction. Preferably, the rotating pan 52 isrotated in aclockwise direction. As discussed below the speed at which the rotating pan 82 is rotated ean vary. ‘A hydrophobic, organi testing agent 70 is aximixed with the titenium dioxide particles 48 by spraying the treating ‘agent on the titanium dioxide panicles in the agglomerator 46, As used herein and in the appended claims, spraying the treating ageat on the titanium dioxide particles “in the ‘agglomertoe” means that the treating agent is sprayed onto the titanium dioxide particles within the actual eanfines ofthe ‘agglomerator (for example, within the confines ofthe rotating pan 52) oras the panicles are falling into or otherwise being transferred into the agglomerate. ‘The treating agent 70 isin lig form and pumped by 3 pump 72 from a source 74 of the eating ageat through & 2 Series of spray nozzles 78 positioned in the rotating pan 52 through the open top 60 adjacent tothe upper end 62 of the reumferental wall 6. The treating agent 70 i continuously sprayed on the lanium dioxide particles 48 as the particles ae transfered ino the rotating pan 82. The agglomerator 46 js operated to form the ttaninm dioxide particles 48 into titanium dioxide agglomerates 50 ‘The manner in which the treating agent 70 is sprayed onto the ttium dioxide particles 48 in the agglomerator 46 can vary. For example, as shown by FIG, 6, in an altemative 30 ‘embodiment, a single spray nozzle 78 is utilized. Also, as, shown by FIG. 6, the spray nozzle or nozzles can be posi tioned through the open top 60 of the rotating pa $2 closer ‘or even adjacent (0 the lower end 64 ofthe circumferential wall 56 Examples of compounds suitable for use a the hydropho= bic onganic treating agent 70 used in association with the invention inelnde silanes, poysiloxanes, saturated faty acid salts, unsatursted fatty acid salts, phosphonic acids and derivatives thereof, and combinations thereo Silanes suitable for use as the treating agent 70 preferably have the formule: ‘where R isan alkyl group (including funetionaized alkyl sg0up), an aryl group (including a functionalized aryl group) oranalkylaryl group (ineludinga Functionalized alkylaryl group); X isa halogen, hydroxy or alkoxy group: and nis from 1103, resentative silanes having the above formula include alkyl teichlorosilanes, dialkyl dichlorosilanes, wialky! chlor rosilanes alkyleimethoxysilanes, dialkyl dimethoxysilanes, trialkylmethoxysilanes, —alkyltrcthoxysilancs, dialkyl iethoxysilanes, and talkylethoxysilanes, where the alkyl ‘group ean range from C, t0 C,, or higher (methy, ethyl, propyl, isopropyl, butyl, isobutyl, ter-buyl, pentyl, hexyl, 0 ‘ety, decyl dodecyl, ee) and combinations thereof. theabove formula Additional representative silanes havi Jude phenylti-chlorositane, phe teiphenylehlorosilane, phenylrimethoxys methoxysilane, eiphenyltrimethoxysilane, alkylphenyldi chlorosilanes, dialkylphenylehlorosilanes, alkyldiphenyt- chlorsilanes, alkylpheny!dimethoxysilanes, dialkylphenylehloroslanes, and” alkyldiphenylmethoxyst. lanes, where the alkyl group can range from C, t0 Cy, OF higher, and combinations thereof 6 Preferred silanes for use as the treating agent 70 include hexyltrchlorosilane, bexylmethyldichlorsilane, —cty- ‘ichlorsilane, —oetylmethyldichlorosilane, propyl rmethoxy-silane, hoxyltrimethoxysilane, octyhrimethoxys Jane, hexyltiethoxysilane, —_octylrithoxysilane, berylmethyldimelhoxysilane, cotylimethyldimethonyilane, hexylmethyldiethoxysilane, octyl-methyldithoxysilane, aminopropyltrimethonysilane, aminopropylricthoxysiane, And mixtures there. For example, octyl trethoxysilane is very suitable for usc as the treating agent 70 Polysiloxanes suitable for use at the tating agent 70 preferably have the formula: where R, and Ry are a hydrogen, an alkyl group or an ary! ‘group: X is hydmgen or a hydroxyl group, alkoxy group, alkyl ‘ou (including functionalized alkyl groups), or aryl ‘grup (including functionalized ay] groups). ‘Yisabydrogen oran alkyl group (including functionalized alky/ groups), oran aryl goup (including funetionalized aryl groups) and nis from 1 to 2000. Representative polysiloxanes having the above formula include polyhydrogen-methylsiloxane,_polydimethylsilox- ‘ae, polyalkylsiloxanes where the alky group can range © Cys oF higher, polyphenylmethylsiloxane, polydiphe- nybiloxane, and misturs thereof Preferred polysiloxanes for use as the trating agent 70, include polyhydrogen-methylsiloxane,_polydimethylsilox- ane, polyhexylmethylsiloxane,polyoctylmethylsilaxane, ora ‘combination thereof. For example, poly(hydrogenmethyl Joxane), poly(dimethylsiloxanc), and mixtures thereof are very suitable for use as the teating agent 7 ‘Saturated fatty aed salts suitable for use as the treating ‘agent 70 preferably have the formula: @ @ where M isan alkali metal alkaline eat metal, oF tans tion metal; and ss ranges fom 11-17 Representative saturated fatty acid salts having the above ‘formula include sodium laurate, sodium myristate, sodium palmitate, sodium stearate, potassium laura, potassium ‘iyrstte, potassium palmitate, potassium stearate, eleinm Javrate, calcium myristate, calcium palmitate, caleum stea- ate, zine lauate, zine myristate, zine palmitate, zine stearate ‘magnesium laurate, Magnesium myristate, mognesinm palmitate, and magnesium stearate. referred saturated fatty acid salts for use as the eating ‘agent 70 include calcium stearate, zine stearate, magnesinza Stearate or a combination thereat. ‘Unsaturated fy acid salts suitable for use us the eating ‘agent 70 preferably have the formula ME00C Ce) @ ‘where M isan alkali metal, alkene earth metal or transi- tion metal ranges from 11-17; and ‘ranges fom 1 10 13 Representative unsaturated Llty acid salts having the above formla include, sodium oleate, sodium linoleat sodium myrstofete, sodium palmitoleate, potassium oleae, potasium finoleate, potassium myristoleate, potasinm palmitoleate, calcium oleate, caleium Tinoleate, caleinm ‘myfitoleate, calcium palmitoleate, zine oleate, zinc Tinoleate, zine myristolete, and zine palmitoleate, US 8,663,518 B2 7 Preferred unsaturated fatty seid salts for use as the treating agent 70 include one or more of the olates andor linoleates ‘of sodium, potassium, ealeium and zinc. Phosphonic acids and derivatives thereof stable foruseas the trating agent 70 preferably have the formal Ry POOR, NOR where R, isan alkyl aryl, or alkylaryl group: and RR, and Kt, are eoeh a hydrogen, an alkyl group, an aryl ‘group o an alkylaryl group, Representative phosphonic acids and derivatives thereof that have the above formula include n-hexyiphosphoaic acid, roctylphosphonie acid, 2-thylhery! phosphonic acid, 2-methyloctyl phosphonie acid, nelecy! phosphonic acid, nedodecyiphosphonic acid, n-tetradecyl-phosphonie acid hexadecyphosphonic acid, n-octadeeyiphosphionie acid, benzylphosphonic acid, and methyl esters, ethyl esters, m= ‘thy esters, diethyl esters, and methylethylestersof allot the ‘above phosphonic acids Preferred phosphonic acids and derivatives thereof for use ‘9 the treating agent inclde n-hexylphosphonie seid, 2-00 ‘ylphosphonic acid, 2-thylhexylphosphonic acid, 2-methy- Joctyl-phosphonic acid, ora combination there. The onic tenting agent 70 is preferably selected from > silanes, polysiloxanes, and mixtures thereof. More prefer ably the organic treating agent 70 js selected from n-octyl teiethoxysilane, poly(hydrogenmethylsiloxane), poly ‘thylsloxane), and mixtures thereof. Most preferably, the ‘organie treating agent 70 is poly(hydrogenmethysiloxane) “The onganic treating agent 70is preferably sprayed on the titanium dioxide particles 48 in the agglomerator 46 in 9 ‘manner that results i a substantially uniform distbntion of the treating agent on the particles, For example, if the treating agent sprayed from the spmiy nozzles 78 is too coarse, a ‘uneven distribution ofthe treating agent on the particles may result. Overswetting one portion of the particles 48 with respect to another partion of the particles can cause the sizeof someagalomerates $010 be oo large. Accordingly, inorderto avoid these ypes of processing problems, the treating agents preferably sprayed on the titanium dioxide particles in the form ofa spray having a mean droplet sizeof no greater than 100 microns, more preferably no greater than 50 microns. Most preferably, tbe treating agent is sprayed on te titanium dioxide panicles te form ofa spray having a mean droplet size of no greater than 30 microns, The treating agent is preferably ani with the titanium dioxide pariles i the ‘agglomerator 46 in an amount in the range of from about (0.1% by weight io about 2.0% by weight, more preferably in, the range of from about 0.4% by weight to about 0.8% by ‘weight, based on the weight ofthe tanium dioxide particles The size ofthe tianium dioxide agalomerates 80 formed by the agglomeration step of the inveative process is depen-

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