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WO2019148179A1 - Chlorosulfates de polyaluminium stables sans sel - Google Patents

Chlorosulfates de polyaluminium stables sans sel Download PDF

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Publication number
WO2019148179A1
WO2019148179A1 PCT/US2019/015628 US2019015628W WO2019148179A1 WO 2019148179 A1 WO2019148179 A1 WO 2019148179A1 US 2019015628 W US2019015628 W US 2019015628W WO 2019148179 A1 WO2019148179 A1 WO 2019148179A1
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WO
WIPO (PCT)
Prior art keywords
aluminum
pacs
sulfate
solution
hydroxychloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2019/015628
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English (en)
Inventor
James M. Dulko
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Usalco LLC
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Usalco LLC
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Filing date
Publication date
Priority claimed from US15/882,748 external-priority patent/US10450209B2/en
Application filed by Usalco LLC filed Critical Usalco LLC
Publication of WO2019148179A1 publication Critical patent/WO2019148179A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/786—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements containing, besides aluminium, only anions, e.g. Al[OH]xCly[SO4]z

Definitions

  • the present invention is directed to polyaluminum chlorosulfates (PACSs) and methods of making and using them.
  • PESs polyaluminum chlorosulfates
  • Polyaluminum chlorides PACls
  • polyaluminum chlorosulfates PVSs
  • Low basicity PACls (0-45% basicity) are very stable in solution but can also be very corrosive. They tend to form small floes, depress pH and require a high concentration relative to other products used in water treatment.
  • High basicity PACls (45-75% basicity) are somewhat better as coagulants in water treatment, but can cost more to manufacture and have a limited shelf life.
  • Highly basic aluminum chlorohydrate (83% basicity) solves most issues of its lower basicity counterparts, but is not effective as a coagulant in cold water or highly turbid water.
  • PACSs are highly efficient coagulants and work well in either cold or highly turbid waters.
  • the main problem with these compounds is that they have a limited shelf life and degrade rapidly at elevated temperatures.
  • PACSs may be made by shearing sodium aluminate into a basic aluminum chlorosulfate solution. However, this produces as much as 5- 10% byproduct sodium chloride and sodium sulfate which becomes an impurity in water treatment. operations and results in an elevation of the chloride and sodium content of the treated waters.
  • the by-product salts also reduce the concentration of the PACSs and shorten the shelf life of these products.
  • PACS may be made by mixing lime with a mixture of aluminum chloride and aluminum sulfate solutions.
  • by-product calcium sulfate or gypsum are produced which need to be disposed of. It is also difficult to produce basicities of greater than 50% using this technology.
  • the present invention is directed to polyaluminum chlorosulfates (PACSs) that are high in basicity and that have a high percentage by weight of sulfate.
  • PACSs polyaluminum chlorosulfates
  • the PACSs are made by adding solid aluminum hydroxychloride to an aqueous solution of aluminum sulfate or by diluting a mixture of solid, dry aluminum sulfate and aluminum hydroxychloride with water.
  • the invention includes methods of using the PACS formed by these procedures in the treatment of water as well as packages containing dry aluminum hydroxychloride and aluminum sulfate as either separate components or as a mixture.
  • the present invention is based upon the development of methods for producing polyaluminum chlorosulfates (PACS) that have a high percentage by weight of sulfate, a high basicity and low levels of sodium chloride and sodium sulfate.
  • the methods involve the use of two components, aluminum sulfate and aluminum hydroxychloride, that can be maintained in a dry, solid state until immediately before they are used in making PACSs.
  • these components can be shipped dry (in either a mixed or unmixed form) without transporting water and are less susceptible to degradation by heat.
  • Water treatment compositions containing the PACS of the invention work efficiently in cold or turbid water and are effective in a broad pH range.
  • the PACSs of the invention have a high sulfate to mass ratio, they are less likely to contribute to high lead levels in drinking water than PACS with a low ratio.
  • the invention is directed compositions comprising PACSs having a sulfate content of 0.5% to 13% by weight or greater for the product in solution, or 2%-30% by weight for the dry product, and a basicity of 65%-70% for a first embodiment or a basicity of 58%-62% for a second embodiment.
  • These compositions are further characterized by having less than 1.0%, preferably less than 0.5% or less than 0.2%, and most preferably less than 0.1% of sodium chloride and less than 1.0%, preferably less than 0.5% or less than 0.2%, and most preferably less than 0.1% sodium sulfate by weight.
  • the PACS of the invention have the formula: Al(OH), ; Clo x 2y) (SO t ) y , (formula I), in which:
  • x is 1.78 to 2.02
  • y is 0.03 to 0.45
  • x+y/2 is 1.8 to 2.1;
  • the ratio of A1 to SO 4 is 2 to 34; the ratio of A1 to Cl is 0.9 to 3.0; and the ratio of A1 to
  • OH is 0.5 to 0.6
  • PACSs of formula I may be characterized as follows:
  • the invention is directed to a process for producing the compositions described above and comprising the steps of: a) adding 55-83% basic solid aluminum hydroxychloride to an aqueous aluminum sulfate solution to form a milky suspension; and b) maintaining the milky suspension for a period sufficient (generally from 2-16 hours, preferably 3 to 6 hours) to form a clear solution.
  • the process should be carried out at a temperature below 50 degrees centigrade (e.g., at 5-50 degrees centigrade), and preferably at 10- 40 degrees centigrade, and most preferably around 20-25 degrees centigrade.
  • the aqueous aluminum sulfate solution used in the process may also be made by dissolving solid aluminum sulfate in water after the addition of the basic solid aluminum hydroxychloride.
  • the ratio of aluminum hydroxychloride to aluminum sulfate should typically be 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate.
  • 0.75-20 parts of dry aluminum hydroxychloride may be added for each one part of dry aluminum sulfate.
  • Other ranges include 5.0-10.0 parts of dry aluminum hydroxychloride for each part of dry aluminum sulfate and 10.0-20 parts of dry aluminum hydroxychloride for each part of dry aluminum sulfate.
  • the clear solution produced is, optionally, formed by mixing the milky suspension while gradually increasing its temperature.
  • Compositions may also be made by: a) dissolving a mixture of solid aluminum sulfate and solid aluminum hydroxychloride in water to form a milky suspension; and then b) maintaining the milky suspension for a period sufficient to allow the suspension to form a clear solution.
  • the process should preferably be carried out at the temperatures indicated above and the solid aluminum sulfate may be dissolved in water before adding the solid aluminum hydroxy chloride.
  • the same ratios of aluminum hydroxychloride to aluminum sulfate discussed above may be used.
  • the invention is directed to a package , e.g., bags or drums, comprising two components, solid dry aluminum sulfate and solid dry aluminum hydroxychloride, that can be used to form a coagulant PACS for wastewater treatment.
  • the package may take the form of a single container having solid aluminum sulfate and solid aluminum hydroxychloride in the form of a dry mixture (e.g, solid aluminum hydroxychloride having less than 3 waters of hydration).
  • the ratio of solid aluminum sulfate to solid aluminum hydroxychloride in the mixture is such that, by adding water, a solution may be formed comprising PACS of formula
  • y is 0.03 to 0.45
  • x+y/2 is 1.8 to 2.1;
  • the ratio of A1 to S04 is 2 to 34; the ratio of A1 to Cl is 0.9 to 3.0; and the ratio of A1 to OH is 0.5 to 0.6;
  • the basicity is 55 to 70%
  • the average molecular weight is greater than or equal to 95 and less than or equal to
  • the solution comprises less than 0.1 % sodium chloride by weight and less than 0.1 % sodium sulfate by weight.
  • a ratio of 0.75-20 parts dry aluminum hydroxychloride to 1 part dry aluminum sulfate may be used. Examples of ranges include: 0.75-5.0 parts of dry aluminum hydroxychloride to one part of dry aluminum sulfate; 5.0-10.0 parts of dry aluminum hydroxychloride for each part of dry aluminum sulfate; and 10.0-20.0 parts of dry aluminum hydroxychloride for each part of dry aluminum sulfate.
  • solutions are formed containing PACS 1, or 2, in which the parameters of formula (I) are as follows:
  • the invention encompasses a method of treating water to remove impurities by adding a sufficient amount of a PACS described above to the water to coagulate and flocculate impurities and subsequently separating the water from the coagulated or flocculated material.
  • the amount of PACS required may be determined using procedures well known in the art and separation may be achieved by standard procedures such as allowing coagulated or flocculated materials to sediment and/or employing filtration methods.
  • the overall procedure involves forming an aqueous solution from solid aluminum sulfate and solid aluminum hydroxychloride (as discussed above) and then adding this to wastewater to coagulate impurities.
  • the process includes: a) dissolving solid aluminum sulfate in water to form a solution; b) mixing solid 62-83% basic aluminum hydroxychloride into the aluminum sulfate solution formed in step a) to form a milky suspension comprising PACS; c) maintaining the milky suspension for a period sufficient to allow the suspension to form a clear solution; and d) adding the clear solution of step c) to wastewater to coagulate or flocculate impurities.
  • the PACS used in the water treatment procedures should have the characteristics described above. Specifically, the PACS should have formula: Al(0H) x Cl (3-x-2y) (S0 4 ) y , (I), wherein: x is greater than or equal to 1.78 and less than or equal to 2.02; y is greater than or equal to 0.03 and less than or equal to 0.45; x+y/2 is greater than or equal to 1.83 and less than or equal to 2.02; and the basicity is from 55% to 70%.
  • Polyaluminum Chlorides or Basic Aluminum Chlorides Polyaluminum chlorides are products of aluminum chloride hydroxide, AlCl(OH) 2 , AlCl 2 (OH), and Al 2 Cl(OH) 5 .
  • the polymeric species formed upon dilution may be expressed as: A1 I3 0 4 (0H) 24 (H 2 0) I2 +5Cl+S0 4 .
  • percent basicity As typically used in the art, percent basicity is defined as (%OH)(52.91)/(% Al). On a molar level, this may be expressed as ((OH)/(Al))/3 multiplied by
  • Dry Aluminum Sulfate This is a solid compound of crystallized, hydrated aluminum sulfate. It can be manufactured from aluminum oxide trihydrate, clays or bauxite. Typically, dry aluminum sulfate contains 14.3 waters of hydration, but 6.5 and 18 waters of hydration are also commercially available. These products typically have a small amount of aluminum hydroxide, usually less than 1% iron content (expressed as Fc 2 Ch), and an amount of insolubles that varies depending on the manufacturer and grade. It is preferred to utilize aluminum sulfate manufactured from aluminum hydroxide to limit the impurities in a PACs product.
  • Aluminum Sulfate solutions are solutions of dry aluminum sulfate of approximately 48.5 wt% of the 14.3 hydrated aluminum sulfate. They are widely available commercially and can contain as much as 0.5% aluminum hydroxide and as much as 1% Fe 2 C>3.
  • the present invention is directed to highly sulfated, high basicity polyaluminum chlorosulfate (PACS) compositions that have essentially no (less than 0.5%, and preferably less than 0.1 % or 0.05%) by-product salts. These compositions are highly effective at removing impurities from water and wastewater.
  • the PACS have the chemical formula: Al(0H) x Cl (3-x-2y) (S0 4 ) y , (formula I), where: 1.78 ⁇ x ⁇ 2.02; 0.03 ⁇ y ⁇ 0.45; and 1.8 ⁇ x+y/2 ⁇ 2.1.
  • Specific PACSs of the invention include: Al(OH)i. 83 Clo.7 5 (S0 4 )o. 2i ;; and Al(OH)2.oiClo.93(S0 4 )o.o3 ⁇
  • the present invention includes a process for producing polyaluminumchlorosulfate by mixing dry, solid aluminum hydroxychloride into an aqueous solution of aluminum sulfate.
  • the aluminum sulfate can be purchased commercially or made using processes well known in the art.
  • Aluminum sulfate is manufactured by digesting an aluminum source (aluminum oxide trihydrate, bauxite, etc.) in a solution of approximately 50 wt% sulfuric acid. The mixture is reacted until there is a slight excess of aluminum hydroxide in solution.
  • Solutions of liquid aluminum sulfate appropriate for the making of PACSs may be prepared from a molten aluminum sulfate solution by diluting it to about 8.3% aluminum oxide content.
  • Dry aluminum sulfate appropriate for the making of PACSs may be prepared by cooling molten aluminum sulfate and then grinding to the appropriate grind specification at a concentration of 17% aluminum oxide. This should be diluted with water to a final concentration of a 1 to 70 wt% equivalent of liquid aluminum sulfate in water prior to the addition of the solid aluminum hydroxychloride. The amount of water is dependent on the basicity of the solid aluminum hydroxychloride and the desired concentration of the PACS.
  • the dry aluminum sulfate may be diluted to 70-100% equivalent of liquid aluminum sulfate in water prior to the addition of the solid aluminum hydroxychloride.
  • the dry aluminum sulfate may be diluted to 30 to 70% equivalent of liquid aluminum sulfate in water prior to the addition of the solid aluminum hydroxychloride.
  • the dry aluminum sulfate may be diluted to 4 to 30% equivalent of liquid aluminum sulfate in water prior to the addition of the solid aluminum hydroxychloride.
  • the solid aluminum hydroxychloride used in the making of PACSs can be produced by thermally decomposing aluminum chloride hexahydrate in a fluid bed dryer until the desired basicity is achieved. This process may be represented chemically as follows:
  • the final basicity of the aluminum hydroxychloride should preferably be 62-83% basic, and should have waters of hydration of 0 to 1.5, preferably 0.5 to 1.2, and most preferably 0.8 to 1.2. It should be added to the aluminum sulfate solution while the solution is mixed using any of devices known in the art for this purpose.
  • the solution may be mildly heated to speed clarification but the temperature should preferably not exceed 50 degrees centigrade. In general, 10-40 degrees centigrade is a good range for carrying out the reaction at atmospheric pressure.
  • the PACSs of the invention can be made from a dry, solid mixture of aluminum sulfate and aluminum hydroxychloride.
  • the aluminum hydroxychloride should have a basicity of 62-83% and may be present in the mixture, for example, at a ratio of between 40 grams per gram of aluminum sulfate and 2 grams per gram of aluminum sulfate.
  • the mixture should be diluted with water to a final concentration of 20% to 40% PACS and mixed until all of the aluminum sulfate and aluminum hydroxychloride has been dissolved. All of the other parameters and procedures are the same as those described above.
  • PACSs with a sulfate content of at least 0.5% by weight (e.g., 6-8%) and a basicity of 55% or greater (e.g., 58-75%).
  • the PACS solution will be added to raw water or wastewater to coagulate and remove impurities.
  • the PACSs are mixed into raw water at dosage of 10 to 100 mg/L. The water is generally rapidly mixed with the PACS and then is slowly mixed for several minutes. Mixing is then stopped and the impurities that have been attracted to the PACS and are allowed to settle to the bottom of the water. The supemate is then filtered and proceeds through the rest of the treatment process.
  • PACS can be used in wastewater treatment to remove phosphorous and/or impurities. When used for this, 50 to 300 mg of PACS is typically used per liter of wastewater.
  • the highly sulfated PACSs of the present invention are highly effective as flocculants in water treatment procedures and should be less prone to increase lead levels in water than PACls or PACS with a lower percentage of sulfates.
  • Typical high basicity PACSs are made by shearing sodium aluminate into a solution of basic aluminum chlorosulfates. Since these products degrade with temperature, the PACSs are partially decomposed by the heat from the shearing and the heat of neutralization between the alkaline aluminate and the acidic basic aluminum chlorosulfates. In contrast, the products of the present invention are manufactured at low temperatures thereby avoiding heat degradation.
  • the PACSs are preferably made from solid Attorney Docket No.
  • the PACS described herein hydrolyze at different rates dependent on the sulfate to aluminum ratios.
  • the sulfate to aluminum ratio is dependent on the basicity of the aluminum hydroxychloride (AHC) used to make the PACS.
  • AHC aluminum hydroxychloride
  • the process of decomposing aluminum chloride hexahydrate to produce AHC is described in more detail in U.S. Patent No. 9,878,918, which is incorporate by reference herein in its entirety.
  • aluminum chloride hexahydrate may be decomposed at elevated temperatures by removing chloride from the molecule as hydrochloric acid and water. The following reactions detail the decomposition:
  • Second step decomposition (33% basic) Al 2 (0H) 2 Cl 4 *7H 2 0 + HC1 +2H 2 0
  • Embodiments of the present invention include an additional premixing process that allows for the production of P ACS from a source of higher basicity AHC. In addition, this process allows a lower amount of aluminum sulfate to be utilized, producing a PACS with a lower sulfate to aluminum ratio, which may be desired in certain applications.
  • the premixing process includes adding a lower basicity aluminum hydroxychloride (AHC) material, either to the aluminum sulfate or to the higher basicity solid aluminum hydroxychloride material, in order to form a stable solution or a dry blended product that can then be used to form the PACS described herein.
  • a lower basicity aluminum hydroxychloride material may include 8 to 18% aluminum oxide and 0 to 50% basicity, e.g., about 38%-43% basic aluminum hydroxychloride solution, and preferably about 40% basic.
  • the lower basicity AHC may contain a stabilizer, such as sodium sulfate, sodium borate, phosphates and/or phosphoric acid.
  • An aluminum hydroxychloride (AHC) in the higher basicity range includes 65% to 84% basicity, preferably about 73% to 83% basicity or 75% to 81% basicity, and may be made by the decomposition of aluminum chloride hexahydrate, as described in U.S. Patent No. 9,878,918, which are powders of 40% to 60% aluminum oxide content.
  • an aluminum hydroxychloride solution having about 38-43% basicity, and preferably about 40% basicity may be added to an aluminum sulfate solution and then the solid aluminum hydroxychloride material with the higher basicity range may be dissolved in the Attorney Docket No. 4143/1014WO solution of the aluminum sulfate and the aluminum hydroxychloride with a lower basicity to form an aqueous milky suspension.
  • the ratio of the aluminum hydroxychloride to the aluminum sulfate, on a dry weight basis, is 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate.
  • the milky suspension should be maintained for a period sufficient to allow the milky suspension to form a clear to slightly turbid solution, which includes the PACS described herein.
  • a dry blended product may be formed by mixing an aluminum
  • hydroxychloride solution with a lower basicity range e.g., having about 38-43% basicity and preferably about 40% basicity
  • blending may be accomplished by spraying the higher basicity solid aluminum hydroxychloride material with the lower basicity aluminum hydroxylchloride solution, e.g., in an apparatus such as a drying kiln, and then the sprayed solid aluminum hydroxychloride material may be dried, if needed. The resulting blend may then be dry blended with a solid aluminum sulfate.
  • the blended powder of the sprayed solid aluminum hydroxychloride material and solid aluminum sulfate may be dissolved in water to form an aqueous milky suspension.
  • the ratio of the aluminum hydroxychloride to the aluminum sulfate, on a dry weight basis, is 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate.
  • the milky suspension should be maintained for a period sufficient to allow the milky suspension to form a clear to slightly turbid solution, which includes the PACS described herein.
  • Example 3 In a 600 milliter beaker, 104 grams of the less basic AHC produced in Example 3 was mixed with 129 grams of ambient temperature water. 30 grams of commercial liquid aluminum sulfate at 8.3% AI2O3 was added to this solution. 52 grams of higher basicity AHC powder (79.4% basic and 52.7% AI2O3) was then added to the solution and stirred for 6 hours. This produced a slightly hazy solution that after filtration yielded a clear solution of PACS of 15% AI2O3, 60% basic and 2.2% sulfate.
  • Example 3 In a 600 milliter beaker, 56 grams of the less basic AHC produced in Example 3 was mixed with 120 grams of ambient temperature water. 83 grams of commercial liquid aluminum sulfate at 8.3% AI2O3 was added to this solution. 60 grams of 79.4% basic and 52.7% AI2O3 Attorney Docket No. 4143/1014WO
  • liquid aluminum sulfate 30 grams was blended with 50.3 grams of water and 34.5 grams of liquid aluminum hydroxychloride (16.09% A1 2 0 3 and 40% basicity). 27 grams of powdered aluminum hydroxychloride (52.7% A1 2 0 3 and 79.35% basicity) was added to this solution. The solution was stirred until a slightly hazy solution resulted. After filtration, this yielded a PACS solution of 15.7% Al 2 0 3 , 60.9% basicity, 4.9% sulfate that was stable and clear for over 6 months.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

Un procédé de production d'un chlorosulfate de polyaluminium (PACS) comprenant l'ajout d'une solution d'hydroxychlorure d'aluminium (AHC) de basicité d'environ 38 à 43 % avec (1) du sulfate d'aluminium aqueux afin de former une solution et le mélange d'un AHC solide avec la solution pour former une suspension aqueuse laiteuse, ou (2) un AHC solide et du sulfate d'aluminium solide et l'ajout d'eau au mélange solide afin de former une suspension aqueuse laiteuse, et le maintien de la suspension laiteuse pendant une période suffisante pour permettre à la suspension laiteuse de former une solution de claire à légèrement trouble comprenant le PACS, le PACS ayant une basicité de 55 à 75 %, le poids moléculaire moyen du PACS est supérieur ou égal à 95 et inférieur ou égal à 111, et les sels présents dans le PACS comprennent de 0 à 1,0 % de chlorure de sodium en poids et de 0 à 1,0 % de sulfate de sodium en poids.
PCT/US2019/015628 2018-01-29 2019-01-29 Chlorosulfates de polyaluminium stables sans sel Ceased WO2019148179A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/882,748 US10450209B2 (en) 2013-07-17 2018-01-29 Stable salt-free polyaluminum chlorosulfates
US15/882,748 2018-01-29

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WO2019148179A1 true WO2019148179A1 (fr) 2019-08-01

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150021514A1 (en) * 2013-07-17 2015-01-22 Usalco, Llc Stable Salt-Free Polyaluminum Chlorosulfates
US20160074873A1 (en) * 2014-09-12 2016-03-17 Usalco Llc Method for production of aluminum chloride derivatives
US20160244345A1 (en) * 2015-02-20 2016-08-25 Usalco, Llc Stable Concentrated Polyaluminum Chlorosilicate Solutions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150021514A1 (en) * 2013-07-17 2015-01-22 Usalco, Llc Stable Salt-Free Polyaluminum Chlorosulfates
US20170203981A1 (en) * 2013-07-17 2017-07-20 Usalco, Llc Stable Salt-Free Polyaluminum Chlorosulfates
US20160074873A1 (en) * 2014-09-12 2016-03-17 Usalco Llc Method for production of aluminum chloride derivatives
US20160244345A1 (en) * 2015-02-20 2016-08-25 Usalco, Llc Stable Concentrated Polyaluminum Chlorosilicate Solutions

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