WO2003064019A1 - Methods for modifying high-shear rate properties of colloidal dispersions - Google Patents
Methods for modifying high-shear rate properties of colloidal dispersions Download PDFInfo
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- WO2003064019A1 WO2003064019A1 PCT/US2003/002882 US0302882W WO03064019A1 WO 2003064019 A1 WO2003064019 A1 WO 2003064019A1 US 0302882 W US0302882 W US 0302882W WO 03064019 A1 WO03064019 A1 WO 03064019A1
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- WIPO (PCT)
- Prior art keywords
- particles
- dispersion
- kaolin
- colloidal
- clays
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000001246 colloidal dispersion Methods 0.000 title claims abstract description 28
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 95
- 239000002245 particle Substances 0.000 claims abstract description 69
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 99
- 239000005995 Aluminium silicate Substances 0.000 claims description 90
- 239000006185 dispersion Substances 0.000 claims description 69
- 239000007787 solid Substances 0.000 claims description 62
- 239000002270 dispersing agent Substances 0.000 claims description 46
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 35
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 27
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 24
- 239000004927 clay Substances 0.000 claims description 17
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 229940094522 laponite Drugs 0.000 claims description 4
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 43
- 229920002125 Sokalan® Polymers 0.000 description 36
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 21
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 239000002002 slurry Substances 0.000 description 18
- 230000003993 interaction Effects 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 230000004044 response Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910052622 kaolinite Inorganic materials 0.000 description 8
- 238000000518 rheometry Methods 0.000 description 8
- 230000008719 thickening Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000000974 shear rheometry Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- -1 poly(acrylic acid) Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005320 surfactant adsorption Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000003341 Bronsted base Substances 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SQEDZTDNVYVPQL-UHFFFAOYSA-N dodecylbenzene;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1 SQEDZTDNVYVPQL-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010993 response surface methodology Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0073—Preparation of non-Newtonian sols, e.g. thixotropic solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Definitions
- Stability and viscosity behavior of concentrated colloidal dispersions of solids is determined by the combined effects of different factors such as Brownian motion of the particles, hydrodynamic interactions, interparticle forces as well as physical characteristics of the particles such as particle size, particle size distribution, and shape of the particles (e.g, Russel, . B., "The Rheology of Suspensions of Charged Rigid Spheres," J. Fluid Mech. 85:209-232 (1978); Russel, W. B., “Review of the Role of Colloidal Forces in the Rheology of Suspensions," J. Rheo. 24:287-317 (1980); Russel, W. B., Saville, D. A., and Schowalter, W. R., Colloidal Dispersions,
- polymers are used as stabilizers or flocculants, which influence the flow behavior and structure of the suspension, depending upon the surface coverage, conformation and orientation of the adsorbed polymer on the particulate surface (e.g, Napper D. H., Polymeric stabilization of colloidal dispersions, Academic Press London 1983; Hashiba M., Sakurada O., Itho
- Dispersions of fine particle kaolins have broad application in various industrial processes (e.g, Murray H. H. "Traditional and new application for kaolin, smectite, and palygorskite: a general overview" Applied Clay Science 17:207-221 (2000); Sjoberg, M., Bergstr ⁇ m, L., Larsson, A. and Sj ⁇ str ⁇ m, E. (1999) "The effect of polymer and surfactant adsorption on the colloidal stability and rheology of kaolin dispersions” Colloid and Surfaces A, 159:197-208).
- the kaolinite crystal consists of altering layers of silica tetrahedra and aluminum octahedra and each particle consists of a stack of about 50 sheets of twin-layers held together with hydrogen bonds (e.g Carty W.M. (August 1999) "The colloidal nature of kaolinite" The American Ceramic
- the primary particles are peusdo-hexagonally shaped platelets and there is a significant difference in the chemical composition of the edges and the basal planes of the particles.
- the clay mineral through the adsorption of exchangeable cations, most notably Na + and K + ions, at levels of about 2-4 meq/100 g.
- exchangeable cations most notably Na + and K + ions
- the kaolin particles have negative surface charge on the basal plane and a pH dependent charge on the edge (e.g, Johnson, S.B. Russell, A.S. and Scales, P.J. (1998)
- Kaolin edges contain both silica and alumina-like sites, which are positively, charged at low pH, but progress through an isoelectric point to possess a negative charge at high pH. This pH dependent behavior is largely due to the Bronsted acid/base behavior of the aluminum hydroxyl groups located at the edges.
- the kaolin face contains only silica-like charge sites and remains negatively charged across the pH range (Johnson, S.B. Russell, A.S. and Scales, P.J.
- Negatively charged polymers are used as common dispersing agents to prepare highly concentrated (as high as 72 % solids by weight) dispersions of kaolin particles for paper coatings.
- FT- IR ATR attenuated total reflection infrared Fourier transfer
- the solids content of the clay dispersion used for formulation can be as high as 72%solid (wt) which often causes severe problems with handling and subsequent application due to dilatancy phenomena under the high speed of paper-coating machines where shear rates between 10 5 to 10 6 s "1 are common (e.g, Ghosh T., (1998) Rheology of kaolin-based pigment slurries and the coating colors they form, Part I, Tappi Journal 81(5), 89-92 and Part II, Tappi Journal 81(5), 123-126).
- the challenge is to create a uniform and defect - free layer of coating of 10-15 ⁇ m thickness from the high shear flow produced under the coating blade of the paper-coating machine.
- the subject invention provides advantageous methods for modifying high- shear rate properties of colloidal dispersions, such as kaolins and clays.
- the subject invention can be utilized to modify the high shear rate properties of colloidal dispersions having particles that need to be dispersed carrying a positive surface charge and/or particles that need to be dispersed having heterogeneous charges.
- a method for increasing the solids content in a colloidal dispersion is a preferred embodiment.
- the present invention provides a method for modifying the rheological properties of colloidal dispersions with positively charged edges, or heterogeneously charged geometric faces and edges.
- the methods of the subject invention can be used to reduce the high shear rheology of high solids colloidal dispersions, such as, for example, kaolin clay slurries.
- high solids colloidal dispersions such as, for example, kaolin clay slurries.
- the colloidal dispersion viscosity decreases at high shear rates.
- the methods of the subject invention can be applied to a variety of dispersions including, but not limited to, dispersions of kaolin clays, calcium carbonates, silica particles, alumina particles, zirconia particles, bentonite clays, laponite clays, and montmorilonite clays.
- two dispersing agents are added as a mixture of a polymer, which adsorbs onto the edges of the colloidal dispersion, and a surfactant.
- a polyacrylate polymer such as sodium polyacrylate
- an anionic surfactant such as sodium dodecylbenzenesulfonate.
- the polyacrylate adsorbs onto the edges of the colloid particles, and the anionic surfactant remains in the colloidal medium.
- the viscosity decreases, and in turn, the shear thickening at the boundary decreases.
- One practical application for modifying these rheological properties is increased solids content in process streams.
- Figure 1 is plot of the adsorption density of sodium polyacrylate onto kaolin as a function of polyacrylate concentration.
- Figure 2 is a plot of the adsorption density of sodium polyacrylate onto kaolin as a function of pH.
- Figure 3 is a plot of the adsorption density of sodium dodecylbenzenesulfonate as a function of sodium dodecylbenzenesulfonate concentration.
- Figure 4 is a plot of the viscosity of 70 %wt solids kaolin dispersion at two different shear rates as a function of sodium polyacrylate dosage.
- Figure 5 is a plot of the viscosity of 70 %wt solids kaolin dispersion at two different shear rates as a function of sodium dodecylbenzenesulfonate dosage.
- Figure 6 is a plot of the viscosity of 67 %wt solids kaolin dispersion dosed with sodium dodecylbenzenesulfonate or sodium polyacrylate as a function of shear rate.
- Figure 7 is a plot of viscosity of 68 %wt solids kaolin dispersion as a function of shear rate for four different sodium dodecylbenzenesulfonate and sodium polyacrylate mixtures.
- Figure 8 is a plot of viscosity of 70 %wt solids kaolin dispersion as a function of shear rate for five different sodium dodecylbenzenesulfonate and sodium polyacrylate mixtures.
- Figure 9 is a plot of 70 %wt solids kaolin dispersion with pre-adsorbed sodium polyacrylate at a shear rate of 100 s "1 as a function of sodium dodecylbenzenesulfonate dosage.
- Figure 10 is a plot of viscosity of 70 %wt solids kaolin dispersion with pre- adsorbed sodium polyacrylate at a shear rate of 5,000 s "1 as a function of sodium dodecylbenzenesulfonate dosage.
- Figure 11 is a plot of viscosity of 70 %wt solids kaolin dispersion with pre- adsorbed sodium polyacrylate at a shear rate of 20,000 s "1 as a function of sodium dodecylbenzenesulfonate dosage.
- Figure 12 is a plot of Smoluchowski zeta potential for 5 %wt solids kaolin dispersion with a fixed dosage of sodium polyacrylate as a function of pH.
- Figure 13 is a plot of Smoluchowski zeta potential for 5 %wt solids kaolin dispersion with a fixed dosage of sodium polyacrylate as a function of sodium dodecylbenzenesulfonate and pH.
- Figure 14 is a surface plot of viscosity of 70 % wt solids kaolin dispersion at a shear rate of 100 s "1 as a function of sodium dodecylbenzenesulfonate and sodium polyacrylate dosages.
- Figure 15 is a contour plot of the viscosity of 70 wt% solids kaolin dispersion at a shear rate of 100 s "1 as a function of sodium polyacrylate and sodium dodecylbenzene dosages.
- Figure 16 is an interaction plot for the effects of sodium polyacrylate and sodium dodecylbenzenesulfonate on the viscosity of 70 %wt solid kaolin dispersion at a shear rate of 100 s "1 .
- Figure 17 is a surface plot of the viscosity of 72 %wt solid kaolin dispersion at a shear rate of 100 s "1 as a function of sodium polyacrylate and sodium dodecylbenzenesulfonate dosages.
- Figure 18 is a contour plot of the viscosity of a 72 %wt solids kaolin dispersion at a shear rate of 100 s "1 as a function of sodium polyacrylate and sodium dodecylbenzenesulfonate.
- Figure 19 is an interaction plot for the effects of sodium polyacrylate and sodium dodecylbenzenesulfonate on the viscosity of 72 %wt solid kaolin dispersion at a shear rate of 100 s "1 .
- Figure 20 is a surface plot of the viscosity of 72 %wt solid kaolin dispersion at a shear rate of 5000 s "1 as a function of sodium polyacrylate and sodium dodecylbenzenesulfonate dosages.
- Figure 21 is a contour plot of the viscosity of 72 %wt solids kaolin dispersion at a shear rate of 5000 s "1 as a function of sodium polyacrylate and sodium dodecylbenzenesulfonate.
- Figure 22 is an interaction plot for the effects of sodium polyacrylate and sodium dodecylbenzenesulfonate on the viscosity of 72 %wt solid kaolin dispersion at a shear rate of 5000s "1 .
- the subject invention provides advantageous methods for modifying high- shear rate properties of colloidal dispersions, such as kaolines and clays.
- the subject invention can be utilized to modify the high shear rate properties of colloidal dispersions having, particles that need to be dispersed carrying a positive surface charge and/or particles that need to be dispersed having heterogeneous charges.
- the high-shear rate properties of colloidal dispersions can be modified in accordance with the subject invention by the addition of a dispersing composition to the colloidal particles wherein the dispersing composition comprises both an adsorbing polymer and an anionic surfactant.
- adsorbing polymer refers to a polymer that adsorbs to the particles of the colloidal dispersion.
- the polymer is a polyacrylate. Specifically exemplified herein are low molecular weight (3,000 - 4,000) polyacrylate polymers such as, for example, Colloid-211 available from Vinings.
- Anionic surfactants are well known to those skilled in the art and typically are characterized as being negatively charged surface-active agents.
- SDBS sodium dodecylbenzene sulphonate
- Colloidal dispersions for which the high shear rate properties can be modified in accordance with the subject invention include, for example, kaolines, calcium carbonate, silica particles, alumina particles, zirconia particles, and clays such as bentonite, laponite, and montmorilonite.
- Specific examples of the subject invention can utilize amounts of the dispensing agent and the ratios of Na-PAA-to-SDBS described in the following Examples and Figures.
- kaolin dispersions fine particle, narrow distribution coating clays
- Clay dispersions exhibit a maximum in viscosity at high shear rates responsible for failures in coating processes.
- the high shear flow properties of electrosterically stabilized kaolin dispersions of neutral pH can be improved through the addition of a small amount of a negatively charged surfactant to the system. While samples prepared using a low molecular weight Na-PAA can exhibit shear thickening behavior at high shear rates, the magnitude of shear thickening can be reduced in dispersions prepared using Na-PAA anionic surfactant as mixed dispersing agents.
- the viscosity behavior of kaolin dispersions can be optimized with respect to the total dispersing agent dosage and the ratio of the two dispersing agents.
- rheological behavior and the onset of shear thickening of Huber kaolin dispersions as a function of dispersing agents dosage, and ratio of the dispersants can be controlled in accordance with the subject invention. Accordingly, the subject invention relates to optimizing the formulation for kaolin slurries under a variety of extreme conditions.
- the methods of the subject invention can be practiced by simultaneous or sequential addition of the dispersing agents to the colloidal dispersion.
- the agents may be separate or already combined.
- the subject invention provides a kit having both agents.
- the agents are in separate containers.
- the agents are pre-mixed.
- the kit preferably includes instructions regarding the use of the agents (the polymer and surfactant) to increase solids content of a colloidal dispersion, or otherwise modify the rheological properties of a dispersion.
- the subject invention relates to the use of a mixture of surfactant, preferably an anionic one, and a sodium polyacrylate dispersant for the purpose of reducing the high shear rheology of high solids kaolin clay slurries.
- the process involves dispersing the neutralized clay slurries of pH 7.0 +/- 0.5 with sodium polyacrylate dispersants, such as Colloid-211 manufactured by Vinings.
- sodium polyacrylate dispersants such as Colloid-211 manufactured by Vinings.
- Sodium polyacrylate dispersants of low MW (3,000 - 4,000) are already commonly used as secondary dispersants in kaolin clay processing. Neutralization of the clay slurry is commonly achieved through the addition of soda ashe.
- an anionic surfactant such as Sodium Dodecylbenezenesulfonate; denoted SDBS
- SDBS Sodium Dodecylbenezenesulfonate
- a preferred dispersant/surfactant mixture seems to be about 2mg dispersant/g of dry clay with 2 - 5 mg surfactant/g of dry clay.
- the acid-dried kaolin material used in this example was acquired from the
- the kaolin powder was delivered with a primary dispersing agent, sodium silicate, as needed to process the kaolin crude through its various water wash beneficiation steps.
- the beneficiaated clay was then mechanically dewatered using a vacuum filter employing a combination of sulfuric acid and alum as filtration aides where after the clay filter cake material, in acid form, was dried for subsequent use.
- the BET nitrogen-specific surface area of the supplied kaolin powder was measured using a Quanta Chrome NOVA 1200 instrument and found to be 16.9 m 2 .g " l . Density of the powder was measured using a Quanta Chrome Ultrapycnometer and found to be 2.67 g.cm "3 while the kaolin's median particle size was 0.5 microns as determined by sedimentation from the application of Stokes Law using a
- SDBS Sodium Dodecylbenzenesulfonate
- the ultra pure water (Millipore) of specific resistively greater than 18 M ⁇ cm "1 was used to prepare the solutions in this example. All experiments were performed at a pH of 7.5 and an industrial grade
- Na CO 3 was used as the pH modifier.
- the supernatant was allowed to sit overnight in a refrigerator to allow the settling of any remaining particles, as testing had shown that a few particles could still be present after the centrifugation process, the presence of which could adversely affect subsequent analysis.
- the residual Na-PAA concentration was then determined using a Tekmer-Dorhmann Phoenix 8000 Total Organic Carbon (TOC) analyzer. The experimentally measured nitrogen BET surface area was used in conducting the adsorption isotherms.
- the viscosity of the kaolin slurry samples was determined using a Paar Physica UDS 200 rheometer with cone-and-plate and parallel-plate geometries. All experiments were performed at 25 °C and the sample temperature was controlled to within + 0.1 °C using water as the heat transfer fluid.
- the cone-and-plate geometry was employed to measure the viscosity of the samples of solids contents lower than 50 %wt solids and the parallel-plate geometry was employed for samples of higher solids content.
- a cone of radius 3.75 cm with a cone angle of 1.0° (a gap size of 50 ⁇ m) and a plate of radius 2.5 cm were used to perform the viscosity measurements.
- the second type is cooperative adsorption meaning one of the components adsorbs on the surface and the second component on the top of first one.
- the third one is independent adsorption, which occurs if the two components adsorb to different adsorption sites, for example in the case of kaolin; one adsorbs on the basal planes and the second one adsorbs on the edges of the particles independently.
- the polymer and surfactant used in this example are both negatively charged implying that these dispersing agents will compete for the same adsorption sites at the surface of the particles.
- the maximum adsorbed amount is nearly equal to 0.09 mg.m 2 which appears to be larger than the results of Sj ⁇ berg and co- workers (Sj ⁇ berg, M., Bergstr ⁇ m, L., Larsson, A. and Sj ⁇ str ⁇ m, E. (1999)
- Figure 2 is a plot of adsorption density of PAA on the surface of the kaolin particles as a function of pH. Aspect ratio of the particles, purity of the powder, and the concentration of multivalent ions are other factors that significantly affect the adsorption of the polymer on the surface of the kaolin particles.
- Adsorption of SDBS anionic surfactant Adsorption of the anionic surfactant sodium dodecylbenzene sulphonate
- SDBS in the absence of Na-PAA
- the maximum adsorbed amount of SDBS on this grade of kaolin is approximately equal to 0.24 mg.m " .
- Sjoberg et al. (Sj ⁇ berg, M., Bergstr ⁇ m, L., Larsson, A. and Sj ⁇ str ⁇ m, E. (1999) The effect of polymer and surfactant adsorption on the colloidal stability and rheology of kaolin dispersions.
- Colloid and Surfaces A, 159 197-208) has reported a value of 0.18 mg.m "2 for the saturation adsorption of SDBS on the surface of kaolin particles at a pH level of 8.5. Their results indicate that when Na-PAA is present in the system, both polymer and surfactant will compete for the same adsorption sites on the surface of the kaolin particles.
- Example 2 Effects of Na-PAA and SDBS dosases on the viscosity of kaolin dispersions Effect of Na-PAA and SDBS dosages on the viscosity of dispersions of Huber kaolin particles at 70 %wt solids is shown in Figures 4 and 5 which represent viscosity as a function of polymer and SDBS dosages respectively at shear rate levels of 100 s "1 and 316 s "1 .
- the viscosity of the suspensions initially decreases to a mi mum with increasing the polymer and surfactant dosages and then starts to increase gradually with further addition of polymer or surfactant to the suspension.
- Critical concentrations of the polymer and surfactant that need to be added to the dispersion to yield minimal viscosities are equal to 2 mg/(g solids) and 4 mg/(g solids) respectively.
- Figures 7 and 8 represent the viscosity data as a function of shear rate, dosage, and ratio of Na-PAA/SDBS for dispersions of Huber kaolin at 68 %wt solids and 70 %wt solids respectively.
- the viscosity of the dispersion is highly affected by both dosage and the ratio of the two dispersing agents used to prepare the slurry. Results indicate that by changing the dosage and the ratio of the two dispersing agents one can control the viscosity behavior of kaolin dispersions.
- the onset of shear thickening is shifted to higher shear rates when the dosage of the polymer and surfactant is increased in the system. From the data given in these figures it appears that there are several combinations of Na-PAA/SDBS for which the dilatancy of the dispersion is significantly reduced.
- Example 3 Colloidal Stability and Electrokinetic Properties
- Figure 14 is a plot of adsorption density of Na-PAA on the surface of kaolin as a function of the pH of the slurry.
- the low and high levels of the design were: 1) solids content: 68 and 72 %wt solids; 2) Na-PAA dosage: 0.5 and 2.0 mg/(g solids); and 3) SDBS dosage: 0.5 and 4.0 mg/(g solids).
- the range of independent variables was set to include the optimal dispersants dosages for minimal viscosity and the solids content that is used commercially.
- Y is the estimate for the dependent variable (viscosity)
- Xj's are independent variables that are known for each experimental run.
- the constants ⁇ 0 , ⁇ i, ⁇ ij, and ⁇ ⁇ are the regression parameters.
- Xj's are the linear (main) effect terms for each of the independent variables, X; X j 's account for the two variable interactions, and the Xj 2 terms indicate quadratic effects.
- the above model consists of three linear terms, three two variable interactions, three quadratic terms, and the constant ⁇ 0 , a total often parameters.
- the data presented in these Figures are for kaolin dispersions at 70 %wt solids and 72 %wt solids at shear rates of 100 s "1 and 5000 s "1 as a function of Na- PAA and SDBS dosages. Over the range of independent variables studied, results indicate that at a fixed level of SDBS dosage, addition of Na-PAA to the dispersion reduces the viscosity of the system in general, but the level of viscosity reduction varies with the level of SDBS in the system.
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