WO1996021618A1 - Process for treating kaolin clays for pitch control and the treated clays - Google Patents
Process for treating kaolin clays for pitch control and the treated clays Download PDFInfo
- Publication number
- WO1996021618A1 WO1996021618A1 PCT/US1996/002025 US9602025W WO9621618A1 WO 1996021618 A1 WO1996021618 A1 WO 1996021618A1 US 9602025 W US9602025 W US 9602025W WO 9621618 A1 WO9621618 A1 WO 9621618A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- clay
- treated
- kaolin
- aluminum chlorhydrate
- process according
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S162/00—Paper making and fiber liberation
- Y10S162/04—Pitch control
Definitions
- This invention relates to an improved method of treating or beneficiating kaolin clay to improve its ability to adsorb pitch and thus control the deposition of pitch during the process of making paper.
- the invention also involves the chemically treated clay, as well as the utilization of said treated clay to control pitch deposition or to remove anionic trash during the process of making paper, and a process for preparation of the treated clay.
- Pitch is the sticky, resinous substance of varying composition which originates from the extractive fraction of wood in the papermaking process. Pitch is reported to be composed of fatty acids and rosin acids and their corresponding calcium, magnesium, and sodium salts. The pitch exists in its dispersed state until chemical changes in the paper furnish cause it to agglomerate and deposit on screens, belts or other paper machine surfaces. This results in holes or breaks in the sheet and expensive down time for clean-ups.
- talc is expensive because of the price of talc, so there is a need to increase efficiency of such pitch deposition controls, while at the same time increasing cost savings in operation of the process.
- the aluminum chlorhydrate treated clays of the invention act to control pitch by adsorbing the fatty and rosin acids comprising pitch residues via electrostatic attraction.
- the fatty and rosin acids contain negatively charged carboxylate groups while the aluminum chlorhydrate treated-clays exhibit cationic charge properties. This ionic reaction produces a clay-pitch complex that ultimately becomes a filler pigment in the sheet.
- the cationic charge properties of these treated clays is therefore of paramount importance to their ability to adsorb pitch in wet-end paper systems.
- the magnitude of their positive surface potential and the point of zero charge are both important charge characteristics for the products of this invention.
- the treatment chemical, aluminum chlorhydrate has the active oxide formula Al 2 (OH) 5 C1 «2H 2 0, is sold commercially under the name Chlorhydrol ® by Reheis Chemical, as Sumachlor * 50 by Summit Research Labs, and by other suppliers.
- Chlorhydrol ® is a clear, colorless 50% active solution and is preferably used in that form in this invention, although other physical forms of the chemical agent may also be used to treat the kaolin.
- the pitch control clay is equivalent in terms of control at the same chemical dosage. This process provides a more uniform surface coverage of the clay by the treating chemical, aluminum chlorhydrate. In other words, better mixing between the clay and the treating chemical is achieved.
- a further object of the invention is to employ a solids/liquids mixer in which the degree of mixing is controllable in a manner independent of the clay throughput rate.
- the mixing technique involves use of a piece of mixing equipment which will produce a clay with equivalent pitch control without using added moisture to effect good mixing. Thus, starting with crude clay, which contains 18 to 22 wt.% moisture when mined, no additional water needs to be added during processing.
- a still further object of the instant invention relates to mixing the treatment chemical with a clay in a manner compatible with other processing steps necessary to achieve other product properties.
- the ultimate product has a grit specification which must be satisfied by a step or technique to remove a predetermined amount of grit present in the crude clay as mined.
- Grit is defined here as plus 325 mesh residue which is largely quartz.
- An important object of the invention is the provision of a process which will avoid the use of any processing chemicals having, or suspected of having, a negative or neutralizing effect on the aluminum chlorhydrate's ability to aid kaolin clay in its role as a pitch control agent.
- anionic dispersants are commonly used in processing water washed clays, but ionically react with aluminum chlorhydrate and render it ineffective by neutralizing its cationic charge.
- the instant process however allows the aluminum chlorhydrate to independently modify surface charge without interference and thereby yield a high positive zeta potential or surface charge on the clay particles.
- a further object of the invention is to provide a method to produce cationic clay products, via aluminum chlorhydrate treatment of crude kaolin clay, which have a more positive zeta potential at pH 4-5 as well as exhibiting a higher pH value at its point of zero charge than the treated clays of the prior art.
- An even further object is to provide a method to produce a treated, cationic clay product having the ability to control pitch under acidic as well as under neutral or slightly alkaline wet-end paper conditions. Pitch control under neutral or slightly alkaline papermaking conditions was not provided by the treated clays of the prior art because of their negative surface charge properties at these pH's.
- a still further object of the invention is to provide treated clay products of high cationic charge that are capable of removing anionic trash from the white water systems present in paper mills.
- anionic trash commonly consists of latex and other binders, that originate from coated broke in the papermaking process.
- the removal of this anionic trash is provided in much the same way by which the treated clays of this invention adsorb pitch.
- the instant invention involves an improvement upon the combination of several U.S. patents.
- U.S. Patent No. 3,807,702 to Grillo et al. the subject matter involves apparatus denominated "a pin mixer” .
- the present invention concerns itself with a process, rather than just said piece of equipment.
- pin mixer is employed in the preferred embodiment of the current invention, there are other aspects of the process which comprise the novelty of the invention. It is the combination of the pin mixer with these other aspects, such as the use of essentially undried lump crude clay, which represents the novel features of the invention. Also, there are other mixers besides the pin mixer which may be used. For example, a person skilled in the art of solids mixing would consider a paddle mixer, a Bepex Turbulizer or a ribbon blender as a suitable substitute for the pin mixer.
- treated clay products having increased positive surface charge are produced by the process of the instant invention.
- This surface charge is measured in millivolts as a zeta potential, which is the electrical potential that exists across the interface or surface of all solids and liquids.
- Hyder et al. claims a method for adsorbing pitch in a papermaking process using an aluminum chlorhydrate-treated kaolin clay or a hydrotalcite- treated kaolin clay.
- the present invention applies to using undried lump crude clay as the starting material, whereas the referenced patent covers using dry or slurried clay.
- a minimum amount of anionic dispersant (0.1- 0.15% CalgonTM) is added to the clay prior to the addition of the aluminum chlorhydrate.
- the present invention requires no dispersant.
- the claims in the two Hyder et al. patents limit the amount of aluminum chlorhydrate to the range of between 0.5 to 1.5 active wt.%.
- the method of processing the clay allows a broader useful range of aluminum chlorhydrate treatment.
- the examples support the indicated broader range, which is reflected in the claims.
- Figure 1 shows the zeta potential in millivolts (mv) plotted against pH for a very dilute slurry of an airfloat, fine particle, hard clay having an aluminum chlorhydrate active treatment level of 0 - 5%;
- Figure 2A shows the zeta potential in millivolts
- Figure 2C shows East Georgia fine particle clay, as both crude and waterwashed examples, with zero and with 2.0% active aluminum chlorhydrate treatment
- Figure 3 depicts a comparison of the zeta potentials of the airfloat, South Carolina, hard clay (AF hard) and the waterwashed, fine particle, East Georgia clay (W
- Figure 4 is a flow sheet of a preferred process for preparation of a treated clay, of the invention. Description of Preferred Embodiments
- the present invention concerns 1) a method of improving the chemical modification of kaolin clay; 2) the beneficiated clay; 3) the employment of said modified clay as an agent for controlling pitch or removing anionic trash in the papermaking industry; and 4) a process for preparation of the modified clay.
- kaolin clay has previously been improved by reaction with a double bond hydroxide of magnesium and aluminum (Hyder et al. '465) , and has been modified with either aluminum chlorhydrate (Chlorhydrol) or hydrotalcite
- the invention herein provides an improved modified kaolin as compared with those previously disclosed.
- kaolin clays are mined and processed for use in various industries.
- the particular clay is identified by the region from which it is obtained, such as Middle Georgia cretaceous clays and East Georgia tertiary clays.
- the present invention relates to improving the pitch control properties of all such clays.
- the process for preparing an improved kaolin clay for pitch control in the present invention involves treating crude fine particle kaolin clay in lump form, with a moisture level such that the mineral can be transported by belt and/or screw conveyors.
- the lump clay is broken into small particles by means of a mechanical comminute or pulverization mill.
- the so pulverized mineral is conveyed into a mixer in a controlled manner simultaneously with the addition of the treatment chemical, aluminum chlorhydrate, to said mixer. It is then thoroughly mixed to blend the clay with the treatment chemical so as to obtain uniform surface modification.
- the treated mineral is further dried, if necessary, to a moisture level suitable for shipping and/or to achieve product specifications.
- the dried treated mineral is further pulverized to a controlled degree of fineness, undesirable coarse particles being removed from the dried and pulverized mineral using an air classification type of separation.
- a controlled level of coarse particles are permitted to remain in the product.
- the process is preferably conducted on a continuous basis, starting with lump crude mineral.
- the rate at which the mineral and chemicals enter the mixing equipment is essentially the same as that at which the treated mineral exits from the mixer.
- this may be accomplished by using drying equipment, such as a rotary dryer.
- a hammermill or a chain mill is the apparatus of choice.
- a pin mixer is preferred, although, as previously mentioned, a paddle mixer, a Bepex Turbulizer, or a ribbon blender may also be used.
- a loss-in-weight feeder or a weigh belt feeder is generally employed.
- the concentration of moisture in the lump crude material is controlled by using an in-line moisture instrument, installed at a point between the pulverizer and the mixer, as described above.
- the treated material may be further dried by utilizing a rotary dryer and/or a flash dryer.
- the drying equipment, the pulverization equipment and the air classification equipment are all combined into a single piece of apparatus, such as a Raymond Roller Mill or a Raymond IMP Mill.
- the selected starting mineral for the process is kaolin clay in an as-mined, crude form. It is desirable that this clay feed have a TAPPI brightness of at least 70% and more preferably above 80%, since the resulting clay-pitch complex will ultimately become part of the filled sheet and can affect paper brightness. Said clay is preferably partially dried to a moisture level between about 12 and 18 wt.%. In addition, this crude clay preferably exhibits a zeta potential equal to or more positive than -10 mv at pH 5.
- the treating chemical is a water- based solution of aluminum chlorhydrate.
- the solution employed contains above about 25 wt.% and preferably is about 50wt.% of aluminum chlorhydrate, the concentration in the commercial product, Chlorhydrol ® .
- the treating chemical is added to the kaolin by means of a metering pump in an amount equal to between about 0.5 and 5 active wt.% of said clay on a dry basis, preferably between about 2.0 and 5.0 active wt.%.
- Figure 1 there is shown the zeta potential in millivolts against pH for a very dilute slurry of an airfloat, fine particle, hard clay, having selected treatment levels of 0 to 5 active wt.% aluminum chlorhydrate.
- the zeta potential measurements of an extremely dilute aqueous clay slurry were made as a function of pH on a Malvern Zetasizer 4 instrument that determines particle surface charge by electrophoretic mobility.
- the varying levels of aluminum chlorhydrate treatment on the airfloat, hard clay of Figure 1 lead to the following conclusions:
- the treated clay product have a +30 mv or greater potential at pH 4 for purposes of pitch control.
- Cationic potential equates to pitch control capability as described in the Hyder and Kunkle patent (U.S. Patent 5,037,508) .
- the treated product have a point of zero charge that occurs at pH 7.5 or above. The higher the pH value for zero charge, the greater the clay's potential for pitch control in neutral or alkaline papermaking systems.
- C. The typical desirable aluminum chlorhydrate treatment level is about 2.5 active wt.% for resulting pitch control in acid wet end paper systems. The useful level is 0.5 - 5.0 active wt.%; the most preferred level is 2.0 - 3.0 active wt.%.
- D It is obvious from the point of zero charge observed in Figure 1 that a higher aluminum chlorhydrate treatment is required for alkaline papermaking pitch control. The treatment level should be 3.0 - 5.0 active wt.% for neutral or alkaline papermaking wet end systems.
- Clays that can be used as starting materials to produce a pitch control product are identified as follows:
- the clays presented in Figure 2A were then surface treated with 2.0% active aluminum chlorhydrate for zeta potential measurements. All the clays except for the waterwashed East Georgia clay (WW EGa) were chemically treated in crude form using a bench scale Hobart * mixer by a procedure where the aluminum chlorhydrate solution was added to the crude lump clay (having 15 to 20% moisture content) while the clay was being well mixed. After mixing, the wet clay was dried and pulverized. In contrast, the aluminum chlorhydrate solution was added to the waterwashed East Georgia clay in slurry form (which contained Calgon dispersant) and the slurry subsequently spray dried in accordance with the teachings of Hyder et al.
- WW EGa waterwashed East Georgia clay
- the zeta potential of these clays after surface treatment with 2.0 active wt.% aluminum chlorhydrate are shown in Figure 2B.
- the zeta potentials of the treated clays show the same relative charge profiles as the untreated clays of Figure 2A. Those untreated clays with the higher potentials also have the higher zeta potentials when treated with aluminum chlorhydrate.
- the treated airfloat and crude clays are cationic over a considerably wider pH range than the treated waterwashed clay. With respect to the fine particle East Georgia clay shown in Figure 2C, this involves both crude and waterwashed examples with zero and 2.0 active wt.% aluminum chlorhydrate treatment. Both the crude samples, untreated and treated, have much higher zeta potentials over most of the pH range than do their waterwashed clay counterparts.
- crude kaolin lump clay from source 10 containing 20 TPH clay, wet, 21 wt.% water, and 2.5 wt.% grit, is passed by line 11 to be comminuted into small particles by a mechanical comminuter or pulverization mill such as hammer mill 12.
- a mechanical comminuter or pulverization mill such as hammer mill 12.
- the clay feed Prior to introduction into hammer mill 12, the clay feed is dried in rotary dryer 14 via lines 13 and 13' so that the clay feed to hammermill 12 contains about 15 wt.% water.
- the aluminum chlorhydrate-treated clay is then partially to a moisture level of about 12 wt.% water, via line 19 to rotary dryer 20.
- the partially dried treated clay is then conveyed via line 25 to roller mill 26.
- There the clay is pulverized to a controlled degree of fineness, undesirable coarse particles being removed from the dried and pulverized mineral using an air classification type of separation. Grit and the like is removed at 27.
- a controlled level of coarse particles is permitted to remain in the product which is recovered at 28.
- the treated clay is further dried to a moisture level suitable for shipping.
- the product recovered at 28 is a kaolin clay containing a 2.0 active wt.% treatment level of aluminum chlorhydrate, and also contains about 0.5 wt.% grit and about 2.0 wt.% water.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9603815A BR9603815A (en) | 1995-01-13 | 1996-01-11 | Process for treating kaolin clays for controlling resin and treated clays |
DE19680103T DE19680103T1 (en) | 1995-01-13 | 1996-01-11 | Processes for treating kaolin clays for resin control and the clays treated |
CA002185139A CA2185139C (en) | 1995-01-13 | 1996-01-11 | Process for treating kaolin clays for pitch control and the treated clays |
AU49246/96A AU690016B2 (en) | 1995-01-13 | 1996-01-11 | Process for treating kaolin clays for pitch control and the treated clays |
JP8521888A JP2963770B2 (en) | 1995-01-13 | 1996-01-11 | Kaolin clay treatment method for pitch control and treated clay |
GB9618233A GB2301584B (en) | 1995-01-13 | 1996-01-11 | Process for treating kaolin clays for pitch control and the treated clays |
MXPA/A/1996/004070A MXPA96004070A (en) | 1995-01-13 | 1996-09-12 | Procedure to treat caolin clays for brain control and arcillas trata |
FI963595A FI963595A0 (en) | 1995-01-13 | 1996-09-12 | Process for treating kaolin clays to control resin and treated clays |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/372,081 | 1995-01-13 | ||
US08/372,081 US5534057A (en) | 1995-01-13 | 1995-01-13 | Process for treating kaolin clays for pitch control and the treated clays |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996021618A1 true WO1996021618A1 (en) | 1996-07-18 |
Family
ID=23466644
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/002025 WO1996021618A1 (en) | 1995-01-13 | 1996-01-11 | Process for treating kaolin clays for pitch control and the treated clays |
Country Status (9)
Country | Link |
---|---|
US (1) | US5534057A (en) |
JP (1) | JP2963770B2 (en) |
AU (1) | AU690016B2 (en) |
BR (1) | BR9603815A (en) |
CA (1) | CA2185139C (en) |
DE (1) | DE19680103T1 (en) |
FI (1) | FI963595A0 (en) |
GB (1) | GB2301584B (en) |
WO (1) | WO1996021618A1 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001004417A1 (en) * | 1999-07-09 | 2001-01-18 | Naintsch Mineralwerke Gmbh | Use of talcum in the manufacture of paper and a method for the same |
US7303654B2 (en) * | 2002-11-19 | 2007-12-04 | Akzo Nobel N.V. | Cellulosic product and process for its production |
JP2006506549A (en) * | 2002-11-19 | 2006-02-23 | アクゾ ノーベル エヌ.ブイ. | Cellulose product and method for producing the same |
US7172651B2 (en) * | 2003-06-17 | 2007-02-06 | J.M. Huber Corporation | Pigment for use in inkjet recording medium coatings and methods |
US20080022940A1 (en) * | 2003-07-11 | 2008-01-31 | Bradley Kirsch | Composite Absorbent Particles with Superabsorbent Material |
US20090217882A1 (en) * | 2003-07-11 | 2009-09-03 | Dennis Jenkins | Dry Bed Agglomeration Process and Product Formed Thereby |
US20080251027A1 (en) * | 2003-07-11 | 2008-10-16 | Bradley Kirsch | Shaped Absorbent Particles |
US20080029039A1 (en) * | 2003-07-11 | 2008-02-07 | Dennis Jenkins | Dry Bed Agglomeration Process and Product Formed Thereby |
US20050257909A1 (en) * | 2004-05-18 | 2005-11-24 | Erik Lindgren | Board, packaging material and package as well as production and uses thereof |
US7449086B2 (en) * | 2005-09-21 | 2008-11-11 | Nalco Company | Use of synthetic metal silicates for decreasing the deposition of contaminants during a papermaking process |
US7776110B2 (en) * | 2007-06-21 | 2010-08-17 | The Clorox Company | Agglomerated animal litter |
US8202585B2 (en) * | 2008-07-31 | 2012-06-19 | Eastman Kodak Company | Inkjet recording media with cationically-modified clay particles |
EP2402503A1 (en) * | 2010-06-30 | 2012-01-04 | Akzo Nobel Chemicals International B.V. | Process for the production of a cellulosic product |
US11447914B2 (en) * | 2017-12-07 | 2022-09-20 | Thiele Kaolin Company | Removal of stickies in the recycling of paper and paperboard |
US11339229B2 (en) * | 2020-01-27 | 2022-05-24 | Formosa Plastics Corporation, U.S.A. | Process for preparing catalysts and catalyst compositions |
CN115023446A (en) * | 2020-01-27 | 2022-09-06 | 台塑工业美国公司 | Process for preparing catalyst and catalyst composition |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4927465A (en) * | 1987-10-19 | 1990-05-22 | J. M. Huber Corporation | Kaolin clays for pitch control |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3807702A (en) * | 1971-06-21 | 1974-04-30 | Huber Corp J M | An improved apparatus for encapsulating a finely divided clay within an organic polymeric material |
US4186224A (en) * | 1971-06-21 | 1980-01-29 | J. M. Huber Corporation | Record member and encapsulated clay for use therein |
US4913775A (en) * | 1986-01-29 | 1990-04-03 | Allied Colloids Ltd. | Production of paper and paper board |
US5037508A (en) * | 1987-10-19 | 1991-08-06 | J. M. Huber Corporation | Aluminum chlorohydrate or hydrotalcite treated kaolin clays for pitch control |
US4964955A (en) * | 1988-12-21 | 1990-10-23 | Cyprus Mines Corporation | Method of reducing pitch in pulping and papermaking operations |
NZ227526A (en) * | 1988-01-07 | 1990-04-26 | Cyprus Ind Minerals Co | Reduction of pitch in papermaking furnish by addition of particle composites comprising soluble cationic polymer adsorbed on insoluble particles |
US5368692A (en) * | 1992-01-22 | 1994-11-29 | Vinings Industries Inc. | Method for controlling pitch |
US5368694A (en) * | 1992-11-25 | 1994-11-29 | W. R. Grace & Co.-Conn. | Pitch reduction on paper machine forming fabrics and press fabrics |
-
1995
- 1995-01-13 US US08/372,081 patent/US5534057A/en not_active Expired - Fee Related
-
1996
- 1996-01-11 AU AU49246/96A patent/AU690016B2/en not_active Ceased
- 1996-01-11 DE DE19680103T patent/DE19680103T1/en not_active Withdrawn
- 1996-01-11 WO PCT/US1996/002025 patent/WO1996021618A1/en active Application Filing
- 1996-01-11 CA CA002185139A patent/CA2185139C/en not_active Expired - Fee Related
- 1996-01-11 JP JP8521888A patent/JP2963770B2/en not_active Expired - Lifetime
- 1996-01-11 GB GB9618233A patent/GB2301584B/en not_active Expired - Fee Related
- 1996-01-11 BR BR9603815A patent/BR9603815A/en not_active Application Discontinuation
- 1996-09-12 FI FI963595A patent/FI963595A0/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4927465A (en) * | 1987-10-19 | 1990-05-22 | J. M. Huber Corporation | Kaolin clays for pitch control |
Also Published As
Publication number | Publication date |
---|---|
CA2185139C (en) | 2001-02-20 |
CA2185139A1 (en) | 1996-07-18 |
GB2301584A (en) | 1996-12-11 |
JP2963770B2 (en) | 1999-10-18 |
FI963595A (en) | 1996-09-12 |
JPH09506589A (en) | 1997-06-30 |
GB9618233D0 (en) | 1996-10-09 |
DE19680103T1 (en) | 1997-05-07 |
US5534057A (en) | 1996-07-09 |
AU4924696A (en) | 1996-07-31 |
BR9603815A (en) | 1997-10-07 |
AU690016B2 (en) | 1998-04-09 |
FI963595A0 (en) | 1996-09-12 |
GB2301584B (en) | 1998-11-25 |
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