Stable salt-free polyaluminum chlorosulfates

Abstract

Highly sulfated, high basicity polyaluminum chlorosulfate compositions that can be made by mixing dry aluminum hydroxychloride with a solution of aluminum sulfate or by diluting a dry mixture of aluminum hydroxychloride and aluminum sulfate with water.

Claims

1. Polyaluminum chlorosulfate (PACS) having a basicity of 55 to 75% and formula (I):
Al(OH).sub.xCl.sub.(3-x-2y)(SO.sub.4).sub.y(I) wherein 1.78<x<2.02, 0.03<y<0.45, and 1.8<x+y/2<2.1; Al:SO.sub.4=2 to 34; Al:Cl=0.9 to 3.0, Al:OH=0.5 to 0.6; and the average molecular weight of the PACS is greater than or equal to 95 and less than or equal to 111, and wherein salts present in the PACS comprise 0-1.0% sodium chloride by weight and 0-1.0% sodium sulfate by weight.

2. The PACS of claim 1, further comprising a sulfate content of 0.5-13% by weight in solution or 2.0-30% by weight in a dry state.

3. The PACS composition of claim 1, wherein: x=1.78 to 1.82; 3x2y=0.35 to 1.1; y=0.065 to 0.45; and x+y/2=1.83 to 2.02; or x=1.95 to 2.02; 3x2y=0.6 to 1.0; y=0.03 to 0.20; and x+y/2=1.95 to 2.1.

4. A process for producing the polyaluminum chlorosulfate (PACS) of claim 1, said process comprising: a) providing solid aluminum hydroxychloride and aqueous aluminum sulfate; b) mixing said aluminum hydroxychloride with said aqueous aluminum sulfate to form an aqueous milky suspension, wherein, on a dry weight basis, the ratio of said aluminum hydroxychloride to said aluminum sulfate is 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate; and c) maintaining the milky suspension of step b) for a period sufficient to allow said milky suspension to form a clear to slightly turbid solution.

5. The process of claim 4, wherein, in step b), 62-83% basic solid aluminum hydroxychloride is added to said aqueous aluminum sulfate solution to form said aqueous milky suspension.

6. The process of claim 4, wherein said process is carried out at a temperature of 5-50 degrees centigrade.

7. The process of claim 4, wherein said process is carried out at a temperature of 10-40 degrees centigrade.

8. The process of claim 4, wherein said clear solution is formed in step c) by mixing said milky suspension while gradually increasing its temperature until the clear solution is obtained.

9. A process according to claim 4, wherein said aluminum hydroxychloride has 1.5 or less moles of hydration.

10. A process according to claim 9, wherein said aluminum hydroxychloride has 1.0 or less moles of hydration.

11. A process for producing the polyaluminum chlorosulfate (PACS) of claim 1, said process comprising: a) providing a dry mixture of solid aluminum sulfate and solid aluminum hydroxychloride in an amount sufficient to provide a ratio on a dry weight basis, of said aluminum hydroxychloride to said aluminum sulfate of about 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate; b) dissolving said dry mixture in water to form a milky suspension; and c) maintaining the milky suspension of step b) for a period of time sufficient to allow said suspension to form a clear to slightly turbid solution.

12. The process of claim 11, wherein said process is carried out at a temperature of 5-50 degrees centigrade.

13. The process of claim 11, wherein said process is carried out at a temperature of 10-40 degrees centigrade.

14. The process of claim 11, wherein the clear solution is formed in step (c) by mixing said milky suspension while gradually increasing its temperature until the clear solution is obtained.

15. A process according to claim 11, wherein said aluminum hydroxychloride has 1.5 or less moles of hydration.

16. The process of claim 11, wherein said ratio of aluminum hydroxychloride to aluminum sulfate is 5-10 or 10-20 parts aluminum hydroxychloride to one part aluminum sulfate.

17. The process of claim 11, wherein said dry mixture provides a ratio of said aluminum hydroxychloride to said aluminum sulfate of about 5-10 parts aluminum hydroxychloride to 1 part aluminum sulfate.

18. The process of claim 11, wherein said dry mixture provides a ratio of said aluminum hydroxychloride to said aluminum sulfate of about 10-20 parts aluminum hydroxychloride to 1 part aluminum sulfate.

19. A PACS according to claim 1, wherein the polyaluminum chlorosulfate is dry.

20. A PACS according to claim 1, comprising 14-38% Al.sub.2O.sub.3 and a basicity of 55-70%.

21. A PACS according to claim 1, having a basicity of 55-70% and a ratio of Al to SO.sub.4 of 2-3.0.

22. A PACS according to claim 1, wherein said aluminum hydroxychloride has 1.0 or less moles of hydration.

23. A premixed package of polyaluminum chlorosulfate for the treatment of wastewater, said package comprising: a) a dry, pre-mixed amount of the PACS of claim 1, said PACS comprising 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate, said aluminum hydroxychloride having 1.5 mole of hydration or less; and b) instructions for using said dry, pre-mixed composition in the treatment of wastewater.

24. The PACS of claim 1 in solution, comprising 15-16 wt % Al.sub.2O.sub.3, 60-66% basicity; and 2-7% sulfate.

25. The PACS of claim 1, comprising 38 wt % Al.sub.2O.sub.3, 66-70% basicity; and 6% sulfate.

26. The PACS of claim 1, wherein said PACS composition has the following formula: Al(OH).sub.1.83Cl.sub.0.75(SO.sub.4).sub.0.21 or Al(OH).sub.2.01Cl.sub.0.93(SO.sub.4).sub.0.03.

27. A method for treating water to remove impurities, said method comprising: a. adding the PACS composition of claim 1 to said water to coagulate and flocculate impurities; and b. separating the coagulated and flocculated impurities from the treated water to produce a treated water reduced in impurities.

28. The method of claim 27, wherein said PACS composition comprises formula (I): Al(OH).sub.xCl.sub.(3-x-2y)(SO.sub.4).sub.y, wherein: a) 1.78x2.02, and 0.03y0.45, and 1.8x+y/22.1; b) Al:SO.sub.4=2 to 34; Al:Cl=0.9 to 1.3; Al:OH=0.5 to 0.6; c) % Basicity=55 to 70%; and d) the average molecular weight of said PACS is greater than or equal to 95 and less than or equal to 111.

29. The method of claim 28, wherein: x=1.78 to 1.82; 3x2y=0.35 to 1.1; y=0.065 to 0.45; and x+y/2=1.83 to 2.02; or x=1.95 to 2.02; 3x2y=0.6 to 1.0; y=0.03 to 0.20; and x+y/2=1.95 to 2.1.

30. Polyaluminum chlorosulfate (PACS), made by the process of: a) mixing solid aluminum hydroxychloride having 1.5 or less moles of hydration with an aqueous aluminum sulfate solution to form an aqueous milky suspension, wherein, on a dry weight basis, the ratio of aluminum hydroxychloride to aluminum sulfate is 0.75-20 parts aluminum hydroxychloride to 1 part aluminum sulfate; and b) maintaining the milky suspension of step a) for a period of time sufficient to allow said milky suspension to form a clear or slightly turbid solution; wherein said PACS comprises a sulfate content of 0.5-13% by weight of said composition in solution, or of 2.0 to 30% by weight of said composition in a dry state, and a basicity of 55 to 75%; and wherein salts present in the PACS comprise 0-1.0% sodium chloride by weight and 0-1.0% sodium sulfate by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Polyaluminum Chlorosulfates

(2) 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(OH).sub.xCl.sub.(3-x-2y)(SO.sub.4).sub.y, (formula I), where: 1.78x2.02; 0.03y<0.45; and 1.8x+y/22.1. Ratios are preferably: Al:SO.sub.4=2 to 34 Al:Cl=0.9 to 3.0; and Al:OH=0.5 to 0.6 Basicity should be 55 to 70% by weight (defined as x/3n) and the molecular weight is preferably at least 95 and less than or equal to 111. Specific PACSs of the invention include: Al(OH).sub.1.83Cl.sub.0.75(SO.sub.4).sub.0.21; and Al(OH).sub.2.01Cl.sub.0.93(SO.sub.4).sub.0.03.

(3) Processes of Making PACSs

(4) 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.

(5) 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. If the PACS is going to be used on site it can be made as dilute as practical, but if it is going to be shipped elsewhere the concentration of the solution should be maximized. Solutions of PACS can be made as high as 20% aluminum oxide or higher. According to a first embodiment, 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. According to a second embodiment, 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. According to a third embodiment, 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.

(6) 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:
2AlCl.sub.3-6H.sub.2O.fwdarw.Heat.fwdarw.Al.sub.2(OH).sub.nCl.sub.(6-n)(H.sub.2O)+H.sub.2O+nHCl

(7) 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.

(8) Mixing of the solid aluminum hydroxychloride should continue until it has been mostly dissolved and until the final solution has a clear to slightly turbid appearance. When performed at about room temperature, this will typically take from 3 to 8 hours. If desired, 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.

(9) As an alternative, 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.

(10) The procedures described above should result in the formation of 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%). Most typically, the PACS solution will be added to raw water or wastewater to coagulate and remove impurities. Typically, 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 supernate 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.

(11) Advantages

(12) 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 components that can be shipped dry and reacted after receipt by a purchaser. This should reduce shipping costs, minimize degradation due to heat and/or storage, and allow end users to maintain larger stocks. The PACS described herein should be stable for long periods, work efficiently in cold or turbid water and be effective in a broad pH range.

EXAMPLES

Example 1

(13) In a 600 ml beaker, 130 grams of commercially available liquid aluminum sulfate (8.3% Al.sub.2O.sub.3) is diluted with 202 grams of water. The beaker is stirred on a magnetic stirrer to which is added 146 grams of a solid aluminum hydroxychloride (42% Al.sub.2O.sub.3, 71% basic) powder. The solution is allowed to mix for 24 hours after which the milky solution becomes clear. The solution yields a PACS solution of 15% Al.sub.2O.sub.3, 60.5% basic and 6.3% sulfate.

Example 2

(14) In a pint jar, 350 grams of a solid aluminum hydroxychloride (41% Al.sub.2O.sub.3, 70% basic) powder is blended with 50 grams of dry alum (17% Al.sub.2O.sub.3). This produces a dry PACS of 38% Al.sub.2O.sub.3, 66% basic and 6% sulfate. Six months later the contents of the jar are added to a one liter beaker that contains 600 mls of water, while stirring on a magnetic stirrer. The solution is allowed to mix for 24 hours, after which the milky solution becomes clear. The solution yields a PACS solution of 15.2% Al.sub.2O.sub.3, 66.1% basic and 2.4% sulfate.

(15) All references cited herein are fully incorporated by reference. Having now fully described the invention, it will be understood by those of skill in the art that the invention may be practiced within a wide and equivalent range of conditions, parameters and the like, without affecting the spirit or scope of the invention or any embodiment thereof.