Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
  • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/41—Preparation of salts of carboxylic acids
  • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/08—Acetic acid
  • C07C53/10—Salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/0004—General aspects of dyeing
  • D06P1/0016—Dye baths containing a dyeing agent in a special form such as for instance in melted or solid form, as a floating film or gel, spray or aerosol, or atomised dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/653—Nitrogen-free carboxylic acids or their salts
  • D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
• • 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
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • 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
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • 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

Definitions

• the present invention relates to a cationic fibrous acetate salt of boehmite alumina, a method for its preparation, its use in dyeing fabrics e.g. cotton and for removing waste from waste streams e.g. waste streams containing dyes.
• dyeing is accomplished by placing a solution containing a dye in contact with fibers or fabric composed of many fibers whereby dye is entrapped within or attached to the lattices of the entwined fibers. The fibers or fabric are then washed to remove unfixed dye, i.e., dye which is not fully attached or trapped.
• the word dye as used herein includes dyestuff and formulations or combinations of dyes and carriers, fillers, and the like.
• the present invention relates to a salt of boehmite alumina suitable for use in dyeing and in purifying a waste stream or effluent.
• the present invention also relates to purification of municipal and dye waste streams by flocculation and/or precipitation. In the dyeing of fabrics, the ability of a material useful in the dyeing process to remove a substantial amount of dye from the dye waste stream serves to improve efficiency and reduce treatment costs.
• the salt of boehmite alumina is not only useful in the dyeing process but is also capable of precipitating, associating with and/or flocculating the dyes (e.g. anionic dyes) whether the dye is present as a contaminant in a municipal waste stream or as residual dye (which was untrapped by or unattached to fibers) in a dye bath waste stream.
• the removed dye may be recycled to the dyeing process.
• the present invention provides a cationic fibrous acetate salt of boehmite alumina obtainable by stirring a slurry of water and basic aluminium acetate to ensure substantially complete mixing thereof, reacting the slurry to produce a fibrous cationic acetate salt of boehmite alumina having a zeta potential of greater than about 25 and a weight ratio of aluminium to acetate of less than about 4.
• the surface area to volume ratio of the salt according to the invention can be about 50% or greater.
• the fibrous acetate has at least about 40% more active/reactive sites than commercially available colloidal alumina.
• the invention provides a method for preparing a cationic fibrous acetate salt of boehmite alumina according to the invention comprising: stirring a slurry of water and basic aluminum acetate to ensure substantially complete mixing thereof, reacting the slurry to produce a fibrous cationic acetate salt of boehmite alumina having a zeta potential of greater than about 25 and a weight ratio of aluminum to acetate of less than about 4.
• the slurry contains (on the basis of Al 2 0 3 ) from about 0.5 weight % to about 30 weight % Al 2 0 3 , preferably from about 0.5 weight % to about 15 weight % Al 2 0 3 .
• the slurry is stirred for from less than about 1 minute to about 60 minutes prior to initiating the reaction, preferably from about 5 minutes to about 30 minutes.
• the slurry is reacted at a temperature of from about 100 C C to about 180°C, preferably from about 140°C to about 160°C and is reacted for a time of from less than about 1 second to about 240 minutes.
• the slurry can be reacted for a time of from about 10 minutes to about 120 minutes.
• the slurry is reacted at a temperature of about 140°C for about 120 minutes for one type of final product .
• Another type of product is produced where the slurry is reacted at a temperature of about 153°C for less than about 5 seconds, wherein the slurry temperature increase is halted and cooling is started when the slurry temperature reaches 153°C.
• the slurry is stirred during the reaction at a rate of from about 50 to about 800 rpm. After completion of the reaction, the reacted slurry is advantageously cooled to a temperature of from about
• the present invention further provides a process for dyeing fibers with a dye selected from the group consisting of direct, reactive, sulfur and acid dyes comprising: passing undyed fibers through a bath containing dye which is associated with or attached to a cationic fibrous acetate salt of boehmite alumina according to the invention whereby the fibers remove the dye from the fibrous acetate salt of boehmite alumina upon contact therewith.
• the present invention provides a process for treating a dye waste stream comprising the steps of introducing into the stream at least one flocculating or precipitating agent comprising a cationic fibrous acetate salt of boehmite alumina according to the invention; forming a precipitate or flocculant of the dye and agent; and separating said precipitate or flocculant from the stream.
• the flocculating or precipitating agent itself forms a further aspect of the invention and may further comprise components selected from the group consisting of inorganic salts, coagulants, organic flocculants, polymeric flocculants and mixtures thereof.
• the agent advantageously has an ionic charge opposite to that of the dye contained in the dye waste stream whereby the dye is attached to the agent by ionic substitution.
• the agent has a positive ionic charge and the dye has a negative ionic charge.
• the process includes the step of adjusting the pH of the waste stream and fibrous acetate suspension to between about 2 and about 8.
• the precipitate or flocculant is conveniently removed by flotation separation and filtered and may include the step of separating the dye from the precipitate or flocculant and the step of regenerating the dye from the precipitate or flocculant. Such regeneration may be achieved by contacting the precipitant or flocculant with a negatively charged group such as for example OH " or C0 3 "2 .
• the separated or regenerated dye is reused in the dyeing process.
• a further aspect of the present invention is a process for removing contaminants from a municipal waste treatment stream which comprises: adding a cationic fibrous acetate salt of boehmite alumina according to the invention to the waste stream; forming a precipitate or flocculant of the contaminants and the salt; and separating the precipitate or flocculant from the waste stream.
• the dye waste stream was typically treated and discharged as effluent .
• the ionic charge of the fibrous acetate salt of boehmite alumina is opposite to that of the dye.
• the fibrous acetate has a positive charge and the dye has a negative charge. Since the dye is negatively charged, it is attracted to and attaches to the positively charged fibrous acetate. The differences in the charges result in a high degree of reactivity or attachment between the dye and the fibrous acetate.
• the pH of the waste stream is adjusted to between about 2 and about 8 by the addition of mineral acids or organic acids to aid in the precipitation or flocculation of alumina acetate monohydrate salt fibers and dye.
• the dye (excluding reactive dyes) may be regenerated or separated and recycled to the dyeing process. Particularly preferred results are obtained when the waste stream has a pH of between about 3 and about 5.
• a sufficient quantity of fibrous acetate can be added to the dye waste stream in any convenient manner.
• One method of separating the precipitate or flocculant is by the use of a flotation separator. Flotation of the particles may be achieved by supersaturation with air under pressure. The pressure is then released and the air in the suspension lifts the particles to the surface.
• the floating particles are then removed by a mechanical skimmer and the waste decolorized effluent discharged.
• the particles may then be recycled and used in the dyeing process by any convenient means.
• the concentration of the particles can also be increased by filtration through a filter. A large percentage of the alumina monohydrate fibers used in the precipitation or flocculation process can be easily recovered.
• flotation separation is a preferred method of separation
• the removed dye can be separated by other methods known to the skilled man such as high pressure filtration. However, high pressure filtration requires more energy than the flotation separation.
• the dye in certain instances can be regenerated, returned to the dyeing process and reused.
• solubility based on the differences in charge between the fibrous acetate and the dye is largely responsible for the unexpected results of the present invention.
• the dye may be regenerated by substituting a negatively charged group for the negatively charged dye, thereby releasing the dye from the fibrous acetate.
• a negatively charged group is an OH " , C0 3 "2 , or the like alkaline group.
• the precipitate or flocculant is filtered and a negatively charged group is used to contact the filter cake containing the alumina acetate monohydrate salt fibers and dye, thereby substituting the negatively charged group for the dye and releasing the dye to be reused.
• the process according to the invention for removing dye from waste streams containing dyes may be batch or may be operated on a continuous basis.
• the dyeing of fabric can be an environmental hazard.
• Commercial processes require heating of the dye bath up to 90°C and adding, up to 10% sodium salt, as either chloride, or sulfate for proper coloration.
• Application of the fibrous alumina acetate in accordance with the invention before dyeing the fabric (pre-treatment) can reduce or eliminate the need for heating the dye solution and the need for salt addition.
• the salt according to the invention may be prepared from basic aluminum acetate whith itself may be prepared from alumina trihydrate and acetic acid. With elevated temperature and pressure, basic aluminum acetate may be hydrolyzed to produce alumina monohydrate which polymerizes to form fibers.
• the overall process is:
• the equation shows the formation of boehmite; however, the product of this invention is actually a boehmite acetate salt.
• Basic aluminum acetate can also be formulated as Al 2 0(CH 3 C0 2 ) consult»H 2 0.
• the sol product is composed of alumina monohydrate fibers, acetic acid and water.
• the reaction conditions, temperature, solids concentration, pH and stirring rate determine the dimensional characteristics of the fibers. Fibers with a range of new and unexpected dimensional characteristics have been found to be generated e.g. short and very wide or flexible and hair-like. Solid concentrations and temperature are parameters that directly impact the size and dimensions of fibers and bundles. Bundles are large aggregations of individual fibers and are generated at specific reaction conditions.
• the highly cationic boehmite alumina acetate fibrous solution of the present invention is preferably generated in a pressure vessel (e.g. Parr reactor Model 4522M) , any type of equipment that permits rapid heating and cooling of a slurry may be used.
• a pressure vessel e.g. Parr reactor Model 4522M
• any type of equipment that permits rapid heating and cooling of a slurry may be used. The process advantageously may be summarized in four stages:
• the heating rate was varied from 4°C/minute initially to 5°C/minute approaching the desired temperature.
• the alumina monohydrate sol product was dried at 350°C.
• the high degree of cationic character of the boehmite alumina acetate salt is responsible for its reaction/adsorption with textile dye stuffs and waste water remediation.
• Characterization of the alumina acetate salt fibers was carried out by a variety of known analytical techniques e.g. scanning electron microscopy (SEM) , transmission electron microscopy (TEM) ; thermogravimetric methods and acid titration of acetic acid content in the sols; particle size analyses; and zeta potential.
• SEM scanning electron microscopy
• TEM transmission electron microscopy
• thermogravimetric methods and acid titration of acetic acid content in the sols particle size analyses
• particle size analyses and zeta potential.
• textile dye adsorption maxima, elemental analysis, thermogravimetric analyses (TGA) , X-ray diffraction and infrared spectroscopy have provided further insight into the nature of the alumina sols.
• sol A 3.0 weight percent as Al 2 0 3 sol was generated in the 2-liter Parr reactor at 140°C for 2 hours (sol A) . These reaction conditions produced sols comprised of short thin fibers. A second 3.0 weight percent as Al 2 0 3 sol was generated in the same reactor at 153°C with zero holding time at this temperature, e.g. the mixture was heated only to temperature (sol B) . This latter material contained only very small fibers ( ⁇ 145mn in length (TEM) ) . Samples of sols A and B were air dried at ambient temperature and elemental analysis was performed for aluminum, carbon and hydrogen. TGA was run on each air dried sample using a DuPont 9900 thermogravimetric cell.
• the sample was dried at 80°C for 15 minutes prior to ramping the temperature (20° per minute) to 650°C and in a second run ramping to 650°C without any drying period. Additional samples of the air dried sol were heated at 80°C for 17 hours and another at 350°C for 2 hours. Similarly, two air dried samples were examined by TGA experiments, one where the temperature was ramped at 20°C per minute and the other at 2°C per minute. X-ray diffraction was run on these dried sols. Infrared spectra of air dried sol were obtained.
• the elemental analysis for an air dried sample was C 8.79%, H 3.70% and Al 30.60% and for the elements (with total acetate 21.6%) was C 8.79%, H 1.10%, 0 11.72%.
• the dye adsorption of C.I. Direct Red 80 for freshly generated sol A was 2800 mg of dye per gram of Al 2 0 3 . However, values of nearly 5000 mg per gram of alumina are observed for an "aged" sol retain sample. If it is assumed that an adsorption site exists for every acetate molecule, the number of sites are calculated as 0.0033 moles per gram of alumina, Al 2 0 3 . Based on a molecular weight of 1417 gram/mole for Direct Red 80 and one dye molecule per site is adsorbed, the theoretical amount of dye which can be adsorbed is calculated to be 4700 mg per gram alumina. The empirical formula is thus consistent with the adsorption of dye .
• sol B the calculated adsorption (assuming one adsorption site per acetate ion) is 0.0062 moles of adsorbent per gram of alumina, A1 2 0 3 .
• the anticipated adsorption would be approximately 8800 mg per gram of alumina. Although this is not found in freshly generated sols, "aged" sols of this material have shown adsorptions of 8000 mg per gram of alumina.
• the thermal residual weight of sol A on heating to 650°C is calculated to be 65.66% for the compound resulting in alumina, Al 2 0 3 .
• the measured residual weight was found ( Figure 1) to be 69.50% without initial drying. It is suspected that some of the loosely bound acetate is lost as acetic acid at ambient conditions prior to the thermal analysis. For example, if it is assumed that only about half the moles of acetate are truly bonded to the alumina and the remainder is merely absorbed into the solids as acetic acid, the theoretical residual weight for heating Al 2 0 2 . 91 (CH 3 COO) 0 . 17 -1.92H 2 0 is 70.27%.
• the calculated residual weight based on this equation is 58.24%. As can be seen in Figs. 4 and 5, for the two temperature ramping speeds of 20 and 2 degrees per minute, the residual weights were found to be 61.59% and 61.99%, respectively.
• the X-ray diffraction of sol A air dried at 25°C showed broad lines consistent with boehmite alumina (Fig. 8) .
• the line broadening is due to the small particles of alumina present in the sample.
• the major difference observed is found in the first peak at 2- theta of about 14 degrees, e.g. at the d-spacing of 6.635 angstroms versus 6.110 for the literature value of boehmite. This, of course, would be expected if the acetic acid were clearly bonded to the alumina fiber, e.g. a salt complex.
• a slurry was made with water and basic aluminum acetate (BAA) .
• the amount of BAA used in the slurry varied from about 1% to about 5% (w/w) on the basis of Al 2 0 3 .
• the slurry was stirred via a magnetic stirrer for 10 minutes.
• This slurry was placed in a Parr Reactor Model 4522M two litre pressure reactor quickly to prevent any settling.
• the heating rate was set to high and within 30-45 minutes the reactor was at the desired temperature. A 2 to 5 gram sample was taken at this time and additional samples were taken every 30 minutes thereafter.
• the reactor was removed from the heat source and cooled to about 70-80°C by using a cooling pump.
• the reactor was opened, and the birefringent alumina sol was removed and samples taken for physical characterization. The pH, viscosity, and percent acetic acid were measured for each sample. An aliquot of the product sol was characterized for the fiber dimensions via transmission electron microscopy (TEM) .
• Table 1 contains the reaction parameters for the experiment generated by a three factor study.
• Bundles are agglomerated fibers that have specific properties. Sols containing bundles have a high sedimentation rate. With this separation ability, bundles can be used in applications where a high settling rate can be used to sediment environmentally unfavorable substances.
• the products of reactions at 180°C contain a higher percentage of bundles than those at the lower reaction temperatures.
• Bundles have varied sizes, with widths up to 3.8 microns and lengths to 18.2 microns.
• Table 4 contains physical characterization data of the final product samples obtained. These data, accompanied by the pressure, temperature, and stirring rate recorded by the computer during the reaction, are crucial to the comparison of each run. As shown, both the percent acetic acid, pH and viscosity are dependent on the percent solids concentration of Al 2 0 3 . In the 1% Al 2 0 3 sols, the percent acetic acid is approximately 2 percent, 3% sols contained about 6.5 percent and the 5% sols had 11 percent acetic acid in the final product. The percent acetic acid was determined by titration versus sodium hydroxide. The pH of each sol also varied with concentration. The viscosity varied with concentration and temperature. The 1% sols had a viscosity below the detection limit of the viscometer, and the 5% sols have viscosities up to 16,100 centipoise (cps) .
• cps centipoise
• EXAMPLE 2 A sol was diluted with deionized water to 0.75% w/w concentration alumina and thoroughly mixed. A fabric was weighed before and after treatment to obtain the percent weight pick up. The target pick up was 80 percent of the original pre-treatment weight. The fabric was dried in an oven at 50°C and then dyed in a solution containing 1 gram of dye per liter of solution at ambient temperature. After dyeing, the fabric was placed into the oven to dry and compared visibly to the commercial control (90°C, 10 wt.% NaCl) for intensity and even coloration.
• the commercial control 90°C, 10 wt.% NaCl
• the value for a simulated commercially dyed product (e.g., 10% salt at 90°C) was 5.346, therefore, the addition of the aluminum monohydrate sol improved the intensity of the dye on fabric.
• the reflectance testing procedure is a standard (ASTM) procedure used in the textile industry. By using this test and interpolating the data obtained, it can be determined whether a product or additive enhances the fabric significantly enough to be commercially marketable.
• the dye concentration of the supernatant can be determined by using the absorbance obtained and the standard plot .
• the amount of the dye adsorbed by the sol is the difference between the starting amount of the dye and the amount left in the supernatant . For example, if the diluted supernatant from centrifugation is found to have a concentration of 0.040 mg of dye per gram of the solution, then the ability of this sol to adsorb this dye can be calculated as follows:
• 0.040 mg/g is the dye concentration of the diluted supernatant obtained from the standard plot
• 60 is the dilution factor for the supernatant
• 200 g is the total weight of the mixture
• 600 mg is the starting amount of the dye
• 0.20 g is the amount of AlOOH solid used.
• the result of this example is that one gram of AlOOH solid is able to adsorb 600 mg of this dye.
• the general procedure for a dye adsorption experiment normally includes six steps:
• the total weight of the mixture as well as the amount of each component, including dye, sol, 0.1% Polyacrylamide (PAA) , and water, are determined before any experiment.
• the sequence of addition into the container is: dye, water, sol, and PAA.
• the dye has to be completely dissolved, however, before the sol can be added. In the cases of reactive dyes, hydrolysis of the dye is a necessary step before the addition of the sol.
• Table 5 summarizes the cloth dyeing experiments and indicates that short thin fibers give superior dye adsorption onto the cloth. Run number 6 shows the highest reflectance value; therefore, the best type of fibers to use are, for this purpose, the thin fibers.
• EXAMPLE 3 A screening test was done to evaluate the dye adsorption abilities of the 27 sol products obtained from Example 1. The experiments were designed to mix the same amount of the dye with the 27 sol solutions having the same solid concentration. The reduction of the concentration of the dye caused by adsorption of fibrous acetate is then judged by the changes of the absorbencies obtained from UV-Vis spectroscometer. In these tests, 10 ml of sol solution (0.75% Al 2 0 3 concentration) was mixed with 0.5 ml of dye (C.I. direct red 80) solution of 1 g/L concentratior . a 15 ml centrifuge tube. After 2 hours centrif ation, the supernatant was scanned, using a Perki: Imer Lamda 2 UV-Vis spectrophotometer. The absorbencies of screening tests are listed in Table 6.
• the alumina acetate monohydrate salt sol is stirred for ten minutes or more to ensure homogeneity. Typically, 5.67 g of this sol, which equals 0.20 g of alumina acetate monohydrate fiber was used. The following calculations were used:
• the excess dye concentration was calculated from the UV-Vis absorbance, based on a standard plot prepared earlier and the amount of adsorbed dye was determined by comparison with the reduction in dye concentration. The absorption capacity was reached when the amount of dye adsorbed became relatively unaffected by the starting dye concentration.
• Cone. #1 and #2 are the starting concentrations of 2.5 and 3 g/L, respectively.
• This experiment tested adsorption at a pH of 3 , 4, and 5 in order to determine which pH yielded the most adsorption of dye.
• Dye solutions were prepared at concentrations of 100 mg/L and the pH adjusted with concentrated HCl or with sodium carbonate (Na 2 C0 3 ) , the amount and type of adjustment was determined by earlier experimentation.
• Alumina acetate sol fiber diluted 60 times and 0.1% PAA were added and the samples centrifuged. Capacity was obtained as described in Example 2.
• the sols used in Examples 5, 6, 7, 8 and 9 were prepared using the same reaction parameters as run #6 of Example 1. Frequently, a dilution of this sol was made to enhance the dispersion of the alumina acetate fibers into the dye solution.
• alumina acetate monohydrate sol fibers to adsorb dye in different concentrations of sodium chloride (NaCl) was assessed.
• NaCl sodium chloride
• HCl concentrated hydrochloric acid
• Dye solutions were prepared for each of the six dyes tested, the final concentration of the dye being 100 mg/L. The pH of each was adjusted with HCl. Alumina acetate monohydrate sol fibers which had been diluted 60 times and 0.1% polyacrylamide (PAA) were added, the solution centrifuged and analyzed via visible spectroscopy to determine adsorption. (See Example 2) .
• PAA polyacrylamide
• alumina acetate monohydrate fibers to adsorb dye in different concentrations of sodium sulfate (Na 2 S0 4 ) was assessed. Previous experimentation revealed that adsorption occurs favorably at a more acidic pH, therefore the dye solutions were adjusted with concentrated HCl. Some of the dyes precipitate salt at higher concentrations of Na 2 S0 4 , therefore, these dyes were tested at lower concentrations.
• Dye solutions were prepared for each of the six dyes tested, the final concentration of the dye being 100 mg/L. The pH of each was adjusted with HCl. Alumina acetate monohydrate fibers which had been diluted 60 times and 0.1% PAA were added, the solution then centrifuged and analyzed via visible spectroscopy for a determination of adsorption (as described in Example 2) .
• EXAMPLE 7 This Example tests the ability of alumina acetate monohydrate sol fibers to adsorb dye at temperatures of typical jet dyeing effluents of commercial dye houses.
• Control dye solutions at concentrations of 3g/L, were prepared as normal at ambient temperature.
• Test dye solutions were prepared at 65°C and 85°C and at concentrations of 3g/L.
• Dye containers and the water used to dilute the dye were heated, and the alumina acetate monohydrate sol fibers were warmed to about 40°C.
• the solutions and sol were mixed while hot, poured into tubes, and centrifuged while hot. Capacity of the dye solutions were measured by UV - visible spectroscopy as described in Example 2.
• the standard acrylic latex white liquid coating material was mixed with increasing percentages of alumina acetate monohydrate salt sol .
• This sol was chosen because of the gloss and yellowing reduction effects observed from previous testing. This sol was very viscous, but easy to mix in the liquid latex coating using an electric laboratory turbine type stirrer.
• the liquid latex was coated on plate glass panels and allowed to dry for 48 hours. The percent gloss was measured, and the same panels were exposed to ultraviolet radiation for 48 hours. The following results were observed: 1. The percent gloss decreased significantly with the addition of sol. 2. Addition of colorless sol from 1-11 percent by weight reduced gloss and increased gloss after 11 percent. 3.
• the sol was an excellent additive to latex coatings for adjusting the percent gloss.
• the mechanism of this phenomenon is as follows: 1.
• the very hydrophilic and colorless sol was added to a water borne acrylic latex liquid coating which was easily dispersed due to the amount of water present. 2.
• the alumina acetate monohydrate particles formed nondispersed microparticles which roughen the surface slightly without an effect on color and disperse light when the gloss is measured.
• the addition of pigments of selective fineness of grind (particle size) is the standard method of adjusting gloss.
• This sol is colorless and non- interactive, and has an excellent application as a convenient coatings additive.
• Alumina acetate monohydrate salt fibers produced in accordance with Example 1 were compared with commercial polyelectrolytes to determine their utility in wastewater treatment.
• the bench scale tests comparing the alumina acetate monohydrate salt fibers to a variety of inorganic and organic cationic polyelectrolytes were run using the same basic procedure. The product presently in use was run first to establish its dosage and performance level. After the base line was established a series of tests were run using the fibers to establish the dosage range where it gave similar performance to the product presently in use. Once the dosage range for the fibers was established then a series of direct comaprison tests were run. Then a final test was run and specific performance characteristics (settling rate, floe size, effluent color and turbidity, etc.) were determined. Iron Ore Tailin ⁇ s Clarification
• the rejects leave the high rate classifiers and are clarified using Poly DADMAC in large diameter clarifiers.
• the solids in this tailings stream vary from 3% to 5%. These units produce a recycled water quality of 100 +/- 20 turbidity units.
• the feed rate of liquid Poly DADMAC (20% active) is 1.0 to 1.5 mg/1 depending on how many grinding circuits are in operation. At low operating rates the dosage is closer to 1.0 mg/1. This is because there is more time available for settling. At higher rates more material is needed to maintain good recycle water quality.
• graduate cylinder settling tests were run to determine the settling rates of Poly DADMAC and the alumina acetate monohydrate salt fibers. A 5 gallon sample of tailings was collected and the polymer was added to this sample.
• Poly DADMAC and the fibers were Poly DADMAC and the fibers.
• the dosage required for the fibers to produce results similar to Poly DADMAC was in the 400 to 500 mg/1 range.
• Fibers 150 180sec 220ml 300 385
• Fibers 600 180sec. 220 ml 300 399 The alumina acetate monohydrate salt fibers give comparable results to the polyamine at 600 mg/1.
• the sludge volume was slightly higher and the solids settle slightly slower than the polyamine.
• the fibers have a large floe like the polyamine whereas the PAC has a very fine floe.
• the fibers measurably outperform the PAC type products.
• Municipalities clarify river water using either Alum or Poly Aluminium Chloro Sulfate (PACS) and switch back and forth from alum to PACS depending on the water quality.
• the alum is 17% Al 2 0 3 and the PACS is a 50% basic product containing 10.5% Al 2 0 3 .
• PACS Poly Aluminium Chloro Sulfate
• Fibers 150 60sec. 6.0 4.0 7.0
• Wastewater Polyamine 50%) 100-150 mg/1 450-600 mg/1 Treatment 25-35 mg/1
• the alumina acetate monohydrate salt fibers worked in all three applications. It performed more like an organic polyelectrolyte (Poly DADMAC and polyamines) than inorganic products (alum, PAC and Poly Aluminium Chloro Sulfate) .
• the fibers have excellent floe forming characteristics, forming a good floe at lower dosages, but requires higher dosages to obtain color and turbidity removal.

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• 1997
  • 1997-04-29 AU AU26458/97A patent/AU2645897A/en not_active Abandoned
  • 1997-04-29 EP EP97918261A patent/EP0896569A1/en not_active Withdrawn
  • 1997-04-29 WO PCT/GB1997/001170 patent/WO1997041063A1/en not_active Application Discontinuation
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