Method of Acid Manufacturing Using Acid cation resins for Recycling Salt and/or Salt Products from Wastes and/or Waste Waters

Abstract

A method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters utilizes a brine solution, an acid cation resin, an acid solution, and an ion exchanger. The acid cation resin is into hydrogen form with the acid solution within the ion exchanger. The acid cation resin is then washed using water with salinity to remove any excess acid from the exterior of the acid cation resin. A selected brine of salts is then prepared of the desired acid(s) to be produced. The desired acid is produced by contacting the acid cation resin containing cations in concentration with the selected brine. A second ion exchange reaction is executed to substitute hydrogen for cations in the selected brine.

Claims

1. A method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters comprises the steps of: regenerating an acid cation resin into hydrogen form with a first acid solution within the ion exchanger in an ion exchanger; washing the acid cation resin using water with salinity; preparing a recycled salt brine for the desired acid(s) to be produced from recycled salts; contacting the recycled salt brine with the acid cation resin containing cations in concentration to produce the desired recycled acid; and executing an ion exchange reaction to substitute hydrogen for cations in the recycled salt brine.

2. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the anions of the first acid solution and the cations of the acid cation resin are low enough in concentration to prevent precipitation in unacceptable amounts.

3. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the anions of the first acid solution and the cations of the recycled salt brine are low enough in concentration to prevent precipitation in unacceptable amounts.

4. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the acid cation ion exchange media is natural zeolites, manufactured zeolites, or resins.

5. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 4, wherein natural zeolites is chabazite.

6. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the acid solution is sulfuric acid.

7. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the desired recycled acid is hydrochloric acid (HCl).

8. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the concentration of the desired acid is at least 2% by weight HCl.

9. The method of acid manufacturing using acid cation resins for recycling salt and/or salt products from wastes and/or waste waters, as claimed in claim 1, wherein the recycled salt brine is prepared from a selected recycled salt.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG. 1 is a flow diagram for the steps of the present invention.

DETAIL DESCRIPTIONS OF THE INVENTION

[0024] The method of acid manufacturing with acid cation resins requires a plurality of different starting materials and equipment, which include a brine, an acid cation resin in hydrogen form, an acid solution, and an ion exchanger. More specifically, the brine, also known as a salt solution or brackish water, can be any ionic aqueous solution that comprises various cations, including but not limited to sodium, potassium, calcium, and magnesium, and various anions including but not limited to nitrates, chlorides, and sulfates. The acid cation resin in hydrogen form may be a strong or weak cation resin, which is initially charged or saturated with hydrogen ions, allows for the removal of cation from the solution. The sulfuric acid solution is used, as an example for the purpose of description, to regenerate the acid cation resin to allow a reuse of the acid cation resin, as well as increase its service life. The ion exchanger is a reactor which contains the ion exchange process without oxidation or reduction between the ions present in the solution. Moreover, the present invention has applications in deionization including production of ultrapure water, and for very frequent use in the energy production area like periodic use for reduction of salts in water for cooling towers which, along with the removal of collected solids by settling and/or filtration, etc. allows continuous use of the remaining water used in the cooling towers. and in production of natural gas and oil. Sulfuric acid produced from the sulfur from fuel, especially in sulfuric acid made from sulfur dioxide from oxidation of minerals and/or combustion of coal, is planned for use in construction of a government subsidized power plant dubbed as clean burning coal.

[0025] In addition, the present invention may also be applied in treating produced water the practice of production of oil and/or natural gas from wells, and is particularly useful in making and/or regeneration of fluids used for hydraulic fracking where typically hydrochloric acid (HCl) is used to degrade the structure of shale formations, allowing access to previously untapped oil sources. Acidic solutions of salts which include recycled salts are pumped into the natural pores and induced fractures to open channels for the petroleum to flow through. Oils are then extracted according to industry standards including for flooding with various liquids that assist the release and flow of oil, gases, and water solutions through the production wells. The waste stream is then treated through the present invention and/or additional acid cation resin to recycle the waste stream into an effective and useable acid stream for the oil production process and/or, for recycling salts so the wastewater is conditioned for use in growing biomass for sustainability of fiber and fuel.

[0026] In one embodiment of the present invention, sulfuric acid is typically used for locally making hydrochloric acid and/or nitric acid, though most acids can be made using appropriate salts. There are technical benefits for this process. As mentioned before, a local production reduces pollution from fuel used during transport of dangerous material from distant sources. local production can utilize salts, and preferably waste salts and/or brines of sodium and/or potassium and/or other cations that do not precipitate in unacceptable amounts when contacted with the regeneration acid solution used for regeneration. In this manner, a wide variety of acids may be manufactured using whatever acid is locally available. This can provide an increased local use of sulfuric acid made from local acid gas and/or sulfur removed from fuels. The present invention reduces of dangers and costs for handling and transporting acid from more distant sources. Finally, handling acid cation resin in hydrogen form is inherently safe as compared with handling acids themselves.

[0027] In accordance to FIG. 1, the present invention contains the steps as follows: regenerating an acid cation resin into hydrogen form with a first acid solution within the ion exchanger, strong or weak, depending on intended use of a desired recycled acid. The first acid solution is typically 1% to 3% or more acid content by weight, depending on molecular weight of the specific acid and intended use of the resin, and load an acid cation resin with hydrogen. The anions of the first acid solution and the cations of the acid cation resin are low enough in concentration to prevent precipitation in unacceptable amounts; washing the acid cation resin (now in a hydrogen form) using water with salinity, recommended by the resin manufacturer, to remove the regeneration brine; preparing a recycled salt brine for the desired acid(s) to be produced from recycled salts. Typically, but not necessarily, the recycled salts are waste salts and/or waste waters of the strength required are implemented for local use of acid to be manufactured as per directions from resin manufacturer, and/or working experience. The selected solutions are low enough in cations that form precipitates with the anions from the selected acid that precipitates, but not in an unacceptable amount; contacting the recycled salt brine with the acid cation resin containing cations in concentration to produce the desired recycled acid. The anions of the first acid solution and the cations of the recycled salt brine are low enough in concentration to prevent precipitation in unacceptable amounts; and subsequently executing an ion exchange reaction to substitute hydrogen for cations in the recycled salt brine typically with, but not necessarily, a waste water, until eventually, the recycled salt brine has been converted to a solution of HCl or nitric acid (HNO.sub.3).

[0028] The acid cation ion exchange media may be chabazite or other natural zeolites, manufactured zeolites, or resins. In accordance to the process described above, all the steps may be performed in the same ion exchanger or locally, with no need of transportation. In addition, the process described above is not only able to remove sodium, the world's largest inorganic water pollutant from chloride brine to form hydrochloric acid, but also able to remove metals and other elements sequentially according preference of the acid cation resin except for calcium and/or other elements that form sulfates that precipitate under conditions of regeneration. Moreover, the same process may also be used to generate nitric acid. In this process, sulfuric acid is firstly used to regenerate an ion exchange, and then a nitrate brine is loaded to the ion exchange to generate a nitric acid. At the same time, the present invention can also remove metals and other elements sequentially according a preference of the resin because elements soluble in water do not form insoluble nitrates.

[0029] The process provided in the present invention allows local production of a plurality of acids using widely distributed sulfuric acid and reduces the known hazards of handling and transport of other acids from more distant sources. When an acid cation resin is regenerated to the hydrogen form and has been well washed to remove all traces of the four elements previously removed, that acid cation resin is in a standard condition essentially irrespective of the anion in the acid used for regeneration. The present invention has provided a safer and economical method for regenerating acid cation resin for a plurality of uses, including where a reduction in pH value is beneficial for limiting scale formation and/or removal of scale.

[0030] Moreover, the method according the present invention may be employed in an electric power generation. Utilities and other large operations using cooling towers commonly use lime-soda softening. Production of lime produces huge amounts of carbon dioxide and when used in water softening produces a huge amount of waste solids for disposal. Moreover, lime-soda softening leaves a troublesome amount of hardness in the soft water that eventually concentrates and forms precipitates, which will foul the cooling towers or similar apparatus. Use the acid ion exchange is able to reduce the hardness to a very low level and the buildup in salts is primarily sodium and potassium which are highly soluble, and the cooling water can thus be used to much higher concentrations. Further, the regeneration brines from removal of salts can be concentrated to hydrates for use in storage of heat and/or cooling.

[0031] Exchange of a hydrogen cation for any other cation creates an acid of the anion previously associated with that cation. The present invention may be implemented through various embodiment. The present invention uses an acid cation resin in the hydrogen form for contacting a solution of salt strong enough to make another acid for regeneration of acid cation resin. Typically, at least 2% for HCl, and preferably at least 3% for hydrochloride acid when used in regeneration of acid cation resin. In addition, the higher the acid content, the more uses in addition to regeneration of acid cation resin.

[0032] In one example of the present invention, about 3% of HCl is generated with acid cation resin and sodium chloride brine. A change from sodium chloride (NaCl) at molecular weight of 58.453 to molecular weight of about for HCl is a 41% reduction in produced weight from starting material to the obtained product. Sulfuric acid will produce certain CaSO4 precipitate and/or some other multivalent cations are precipitated as small solids that are mixed with the acid cation resin, and therefore sulfuric acid is not used with those salt solutions. Sulfuric acid is used to make acids primarily to remove such cations which are predominately in low amounts as compared with sodium, and because removing the cations separately, provides products with beneficial use or uses. In particular, the calcium chlorides or nitrates and magnesium chlorides or nitrates are particularly valuable for use with agricultural soils and for use in storage of solar energy and other sources of heat energy.

[0033] In the present invention, an acid cation resin in hydrogen form is used to remove the calcium; and then the regeneration is performed using an acid that does not precipitates form precipitates with any multivalent calcium or any other multivalent cation that may present in the water. Example of safety benefit is the regeneration of the acid cation resin to acid form in a safe centralized operation. Regenerated acid cation resin is used in portable ion exchange unit that may be transported to the point of use. For example, use in pH control of calcium and magnesium that form precipitates with carbon dioxide and/or sulfate ions which deposit to form scale and restrict flow in pumps and pipelines. Rather than injection of dangerous hydrochloride solution, a portion of the fluid is withdrawn, contacted with acid cation resin in hydrogen form, in amount to replace enough calcium and the like with hydrogen to reduce the pH value of the solution enough to avoid precipitates, as well as produce a usable brine.

[0034] The present invention has increased ecological benefits. Sulfuric acid that is made using sulfur dioxide, the world's largest volume acid gas, is used to recycle sodium, the world's largest volume of inorganic water pollutant, to make sodium sulfate, the world's most versatile material for storage of solar energy at child safe and pet safe temperatures in narrowed between narrowed intervals selected between 80 degrees Fahrenheit and about 89 degrees Fahrenheit. In addition, it has increased the safety for handling the hazardous acid. Adding acid to a solution is a common practice for pH control and is much used to minimize or prevent scale in heat transfer equipment, storage vessels, pumps and pipelines.

[0035] Although the invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of recycling as previously described in US patents.

REFERENCES

[0036] 1. Salt Production and ProcessingMorton Salt www.mortonsalt.com/salt-production-and-processing/ [0037] Note: Solar salt production is, typically, the capturing of salt water in shallow ponds where the sun evaporates most of the water. The concentrated brine precipitates . . . . This method yields a very high purity salt, fine in texture, and principally used in those applications requiring the highest quality salt. [0038] 2. U.S. Pat. No. 5,300,123, 1994Method of reforming soluble salts to effect purification and increase crystal size thereof [0039] 3. U.S. Pat. No. 6,071,411, Method of treating soil for controlling dust and for effecting soil stabilization through the application of waste water, Jun. 6, 2000, Gerald J. Grott [0040] Note: Dust control and soil stabilization as in road beds, foundations, earthen dams, etc. Road bases in Northern Indiana and southern Michigan in 1960's have required minimal repair as compared with other road bases. Millions of tons of salts are required to optimize productivity of crop soils and increase permeability to gases and Water. Reduces Flood Water and retains it for use during summers. [0041] 4. U.S. Pat. No. 6,374,539, Methods of utilizing waste waters produced by water purification processing, Apr. 23, 2002, Gerald J. Grott [0042] Note: Use of sodium chloride and/or sodium sulfate to remediate excess calcium carbonate in soils. There are huge acreages of Carbonaceous soils in Arizona, California, New Mexico and on the east side of the continental divide. south of an East-West line through mid-Oklahoma, where summer soil temperatures can reach the 83 degrees Fahrenheit which is the temperature at which a Root eating Fungus will grow, but only if the carbon dioxide in the soil atmosphere reaches a minimum amount. High calcium and/or high sodium content result in soils with low permeability to gases as well as low permeability to water. Known as Texas Root Rot, by late 1800's the Texans funded an Agricultural Research Facility at College Station with specific goal of finding a remedy for Texas Root Rot. Eventually College Station became the base for Texas A&M Agricultural School but the cause for Texas Root Rot was discovered by Dr. Stuart D. Lyda while he was a Professor in Nevada. First, he found that only the roots of dicots were attacked. But that includes alfalfa, citrus, cotton and nuts which age large volume in Texas so College Station employed Dr. Lyda. Dr. Lyda found that adding one ton/acre of lowest grade of mined sodium chloride would cure Texas Root Rot. (about 95% sodium chloride or 1900 pounds per acre). Research and development in Montana found optimum treatment for all crops is about the same. We sold many truckloads of salt to Cotton Farmers who leased or purchased idle calcareous land, added a measured amount of salt and grew bumper crops. Cotton Incorporated gave massive support but environmentalists soon objected to adding chloride which would eventually reach the water table and Cotton Inc. quit advertising their support. But the sodium does the work, therefore, we patented use of both recycled sodium chloride and sodium sulfate. U.S. Pat. No. 6,651,383, Methods of utilizing waste waters produced by water purification processing, Nov. 25, 2003, Gerald J. Grott [0043] 5. U.S. Pat. No. 7,353,634, Methods of utilizing waste waters produced by water purification processing, Apr. 8, 2008, Gerald J. Grott [0044] 6. U.S. Pat. No. 7,622,044, Methods of sealing ponds and increasing water catchment with purified waste water, Nov. 24, 2009, Gerald J. Grott [0045] 7. U.S. Pat. No. 7,771,600, Methods of utilizing waste waters produced by water purification processing, Aug. 8, 2010, Gerald J. Grott [0046] 8. U.S. Pat. No. 7,717,173, Methods for Improving Oil and Gas Production with recycled, increased sodium water, May 18, 2010, Gerald J. Grott [0047] Note: Includes use of electrolysis because caustic soda and bleach were used in the successful department of energy (DOE) chemically enhanced oil recovery tests where we supplied the sodium chloride very low in calcium and magnesium used in improving oil recovery. Also covers some practices for recycling fracking water. [0048] 9. U.S. Pat. No. 7,823,641, Methods of formulating cements for drilled wells using processed waste water, Nov. 2, 2010, Gerald J. Grott [0049] Note: For sealing well casings. [0050] 10. U.S. Pat. No. 7,866,916, Recycled brines and salts for Ice Control. [0051] 11. U.S. Pat. No. 7,947,185, Water sanitation methods, May 24, 2011, Gerald J. Grott [0052] Note: A portion of the microbial contaminated water (as in drinking water, acid gas water, or sewage water) is electrolyzed to make bleach for use with the contaminated water [0053] 12. U.S. Pat. No. 8,062,532, Process for electrolytic production of chlorine products and byproducts, Nov. 22, 2011, Gerald J. Grott [0054] Note: Use Recycled sodium chloride as feed for electrolysis operations. [0055] 13. U.S. Pat. No. 8,091,653, Methods of formulating weighting agents using processed waste waters, Jan. 10, 2012, Gerald J. Grott [0056] Note: Use of Recycled Sodium chloride and calcium chloride as weighting agents in drilling fluid and fracking water. [0057] 14. U.S. Pat. No. 8,192,633, Methods of energy storage and transfer, Jun. 5, 2012, Gerald J. Grott [0058] Note: Use of low grade natural or recycled sodium sulfate in energy storage.