WO1996036372A1

WO1996036372A1 - Method for producing chlorine dioxide and removing chlorine dioxide using chemically impregnated zeolite

Info

Publication number: WO1996036372A1
Application number: PCT/US1996/006429
Authority: WO
Inventors: Fred Klatte; James Aamodt; David Biswell
Original assignee: Klatte Inc.
Priority date: 1995-05-19
Filing date: 1996-05-08
Publication date: 1996-11-21

Abstract

A method for producing chlorine dioxide by moving fluid (such as air) relative to a first bed of zeolite crystals impregnated with sodium chlorite and/or zeolite crystals impregnated with chlorine, and by moving the fluid relative to a second bed of zeolite crystals impregnated with one of the following: phosphoric acid, acetic acid and citric acid. The first and second beds may be physically mixed together. Another aspect of the invention is a method of removing chlorine dioxide from a fluid by moving the fluid relative to a bed of zeolite crystals impregnated with one of the following: potassium hydroxide, sodium sulfite, sodium bisulfate and ferrous sulfate. This method can be used to remove chlorine dioxide produced using the above-described method for producing chlorine dioxide. Other aspects of the invention are methods for impregnating zeolite crystals with sodium chlorite, acetic acid, citric acid, chlorine, sodium sulfite, or sodium bisulfite, and the resulting impregnated zeolite crystals.

Description

METHOD FOR PRODUCING CHLORINE DIOXIDE AND REMOVING CHLORINE DIOXIDE USING CHEMICALLY IMPREGNATED ZEOLITE

Field of the Invention

The invention relates to processes for producing chemically impregnated zeolite and coated, chemically impregnated zeolite, to the products of such processes, and to use of such products for absorbing a contaminant from a fluid. Preferred embodiments of the invention are processes for impregnating zeolite crystals with chemicals, and methods for using chemically impregnated zeolite crystals to produce chlorine dioxide and optionally also to absorb the produced chlorine dioxide.

Background of the Invention

Zeolites are hydrated metal aluminosilicate compounds with well-defined (tetrahedral) crystalline structures. Because zeolite crystals (both natural and synthetic) have a porous structure with connected channels extending through them, they have been employed as molecular sieves for selectively absorbing molecules on the basis of size, shape, and polarity. Volumes packed with zeolite crystals (for example, small zeolite crystals chosen to have size in the range from 0.2 mm to several millimeters) have been employed in water and air (or other gas) filtration systems to selectively absorb contaminants from a flowing stream of water or gas.

It has been proposed to treat zeolite crystals by impregnating them with quaternary ammonium cations (such as tetramethylammonium, tetraethylammonium, hexadecyltrimethylammonium, dibenzyldimethylammonium, benzyltriethylammonium, and cetyltrimethylammonium) , to enhance the zeolite's capacity to absorb heavy- metal, benzene, toluene, and xylene contaminants from water. See, for example, Cadena, et al., "Treatment of Waters Contaminated with BTX and Heavy Metals Using Tailored Zeolites," New Mexico Waste-management Education and Research Consortium Technical Completion Report for Project No. WERC-91-41 (February 1992) . If not impregnated with a quaternary ammonium cation (QAC) , zeolite does not function adequately as a molecular sieve for organic chemicals such as benzene, toluene, and xylene. It has also been proposed to impregnate an aqueous solution of permanganate (such as permanganate of potassium, sodium, magnesium, calcium, barium, or lithium) into pores of substrates such as silica gel, alumina, silica-alumina, activated bauxite, and activated clay. The resulting impregnated porous substrates have been employed for filtering and deodorizing air. See, for example, U.S. Patent 3,049,399, issued August 14, 1962, to Gamson, et al.

However, above-mentioned U.S. Patent 5,278,112 represents the first teaching of how to impregnate zeolite crystals (throughout their volume) with permanganate.

Further, because permanganates are strong oxidizing agents, those skilled in the art have avoided exposing quaternary ammonium cations or salts to permanganates (to avoid violent reactions of the type predicted in the literature) . For this reason, until U.S. Patent 5,278,112, it had not been proposed to treat a permanganate-impregnated substrate (such as permanganate-impregnated zeolite) with a quaternary ammonium cation or salt, nor to treat a substrate impregnated with a QAC (quaternary ammonium cation) to permanganate. One of the inventors has found that zeolite crystals can readily be impregnated with a usefully high concentration of potassium permanganate. However, this inventor has recognized that, under certain conditions, such permanganate-impregnated zeolite reacts too rapidly to be practically useful for some air filtration applications. For example, when air contaminated with 50 ppm of hydrogen sulfide is caused to flow (at a rate of 15 liters per minute) through a bed of the inventive permanganate- impregnated zeolite crystals (where the crystals have size about 0.25 inch x 0.125 inch (0.64 cm. x 0.32 cm.), and the bed has volume of 75 cubic centimeters, and dimensions 1" (Id) x 6"), the crystals typically become saturated with hydrogen sulfide within about 48 hours. Although the impregnated zeolite crystals usefully absorb hydrogen sulfide from air, the hydrogen sulfide absorption rate is significantly higher than can be achieved using conventional permanganate-impregnated alumina products, and is undesirably high for some applications.

For both air (and other gas) and water filtration applications, it would be desirable to reduce the rate at which permanganate-impregnated zeolite absorbs selected contaminants, and to control such absorption rate. Similarly, it would be desirable to reduce the rate at which QAC-impregnated zeolite absorbs selected contaminants, and to control such absorption rate. However, until the present invention, it was not known how to achieve either of these objectives.

Zeolite coated (but not impregnated) with manganese dioxide has been employed in water filtration systems to selectively absorb contaminants from a flowing stream of water, as described in U.S. Patent 4,581,219, issued April 8, 1986 to Imada, et al. However, until the present invention, it was not known how to impregnate zeolite with manganese dioxide, or to employ zeolite impregnated with manganese dioxide in water or gas filtration systems to selectively absorb contaminants from a flowing stream of water or gas .

Summary of the Invention

In one class of embodiments, the invention is a process for producing zeolite crystals impregnated with one or more of sodium chlorite, acetic acid, citric acid, chlorine, sodium sulfite, and sodium bisulfite. The product of each such process is another class of embodiments of the invention.

Throughout the specification, including in the claims, the term "permanganate" used alone is intended to refer to any permanganate, including permanganate of potassium, sodium, magnesium, calcium, barium, or lithium.

A further aspect of the present invention relates to production of chlorine dioxide by moving fluid (such as air) relative to a first bed of zeolite crystals impregnated with sodium chlorite and/or zeolite crystals impregnated with chlorine, and by moving the fluid relative to a second bed of zeolite crystals impregnated with one of the following: phosphoric acid, acetic acid and citric acid. The first and second beds can be physically mixed together, or the fluid can flow sequentially through distinct first and second beds. A further aspect of the present invention relates to removing chlorine dioxide from a fluid by moving the fluid relative to a bed of zeolite crystals impregnated with one of the following: potassium hydroxide, sodium sulfite, sodium bisulfate and ferrous sulfate. This method may be used to remove chlorine dioxide produced using the method for producing chlorine dioxide described above.

Brief Description of the Drawings

Figure 1 is a cross-sectional view of a zeolite crystal impregnated with permanganate.

Figure 2 is a cross-sectional view of the impregnated zeolite crystal of Fig. 1, after it has been coated with a QAC in accordance with the invention. Figure 3 is a cross-sectional view of a zeolite crystal impregnated with manganese dioxide.

Figure 4 is a cross-sectional view of the impregnated zeolite crystal of Fig. 3, after it has been coated with a QAC in accordance with the invention.

Figure 5 is a cross-sectional view of a zeolite crystal impregnated with phosphoric acid.

Figure 6 is a cross-sectional view of a zeolite crystal impregnated with one of the following impregnating agents: sodium chlorite, acetic acid, citric acid, and chlorine.

Figure 7 is a cross-sectional view of a zeolite crystal impregnated with one of the following impregnating agents: sodium sulfite, sodium bisulfite, and ferrous sulfate.

Detailed Description of the Preferred Embodiments

In one class of embodiments, the invention is a process for impregnating zeolite crystals (for example, crystals having size 0.125 inch x 0.10 inch (0.32 cm x 0.25 cm), 0.25 inch x 0.125 inch (0.64 cm x 0.32 cm), 0.125 inch x 0.50 inch (0.32 cm x 1.27 cm), or 0.50 inch x 0.75 inch (1.27 cm x 1.96 cm)) with manganese dioxide, and the product of such process. Preferred embodiments of such process employ, as input material, zeolite crystals uniformly impregnated with potassium permanganate, with a 4% potassium permanganate content and a 15% moisture content. Such input material is preferably produced by a method including the steps of initially dehydrating the zeolite crystals to have about 5% moisture content, then mixing the dehydrated zeolite crystals with potassium permanganate crystals (preferably with a weight ratio P/T substantially equal to 4%, where P is the potassium permanganate weight and T is the total weight of the final product of the process) , then immersing the crystal mixture in (or spraying the mixture with) water at about 190° F (87.8° C) , thoroughly mixing the resulting slurry, and then air drying the mixed slurry to produce potassium permanganate-impregnated zeolite crystals having about 15% moisture content. Typically, the process employs four pounds of potassium permanganate and fifteen pounds of water for every 86 pounds of dehydrated (5% moisture) zeolite crystals, and this mixture (105 pounds) is dried to produce 100 pounds of permanganate-impregnated zeolite crystals having about 15% moisture content. Fig. 1 represents one such impregnated crystal, having channels uniformly impregnated with potassium permanganate 2.

Variations on the method described above produce zeolite crystals uniformly impregnated with potassium permanganate, having a potassium permanganate content of XI, where X is greater than 4, and is preferably in the range from 8 to 10. In such variations, the dehydrated zeolite crystals are mixed with solid potassium permanganate with a weight ratio P/T substantially equal to X%, where P is the potassium permanganate weight and T is the total weight of the final product of the process. In variations on any of the above-described methods, permanganate other than potassium permanganate (such as permanganate of sodium, magnesium, calcium, barium, or lithium) is employed to impregnate the zeolite crystals.

In another variation on the described methods, zeolite crystals are immersed in (or sprayed with) aqueous potassium permanganate (having permanganate concentration in the range from about 10% to about 20%) , where the weight of aqueous potassium permanganate is about 10% of the weight of the final product of the process. The crystals (after they are dried) will be uniformly impregnated with about a 1% concentration of potassium permanganate. In yet another variation on the described methods, zeolite crystals are immersed in (or sprayed with) supersaturated aqueous potassium permanganate (having permanganate concentration of 20% or higher) at 190° F (87.8° C) , where the weight of aqueous potassium permanganate is about 10% of the weight of the final product of the process. The zeolite crystals (after they are dried) are uniformly impregnated with a concentration of potassium permanganate greater than 1%. For many applications (including air and water filtration applications) , the desired concentration of potassium permanganate impregnated in zeolite crystals is in the range from about 1% to about 4% (or from about 1% to about 8% or 10%) . However, as explained above, permanganate- impregnated zeolite may have an activity rate too high or too low for some useful applications (i.e., its rate of absorption of contaminants may be too high, or too low, for some air or water filtration applications) . One of the inventors has found that the rate at which permanganate-impregnated zeolite absorbs (or reacts with, or both absorbs and reacts with) selected contaminants can be controlled (and reduced or increased to a desired level) by applying a quaternary ammonium cation (QAC) coating to the permanganate-impregnated zeolite. This inventor has also found that the rate at which QAC-impregnated zeolite absorbs selected contaminants can be controlled (and reduced or increased to a desired level) by applying a permanganate coating to the QAC- impregnated zeolite.

Thus, in a first class of preferred embodiments, the inventive method uses zeolite which has first been impregnated with permanganate (preferably, potassium permanganate) and then coated with a QAC (preferably, cetyltrimethylammonium, although other QACs are suitable for certain applications) . Fig. 2 represents one such impregnated crystal, whose channels contain QAC 4 in the region near the crystal's surface, and whose channels are impregnated with potassium permanganate 2A throughout the volume of the crystal inside the region containing QAC 4.

In a second class of preferred embodiments, the invention uses zeolite which has been impregnated with a QAC (preferably, cetyltrimethylammonium) and then coated with permanganate (preferably, potassium permanganate) . Either type of coated, impregnated zeolite (or a mixture of both types of coated, impregnated zeolite, or a mixture of uncoated impregnated zeolite with coated, impregnated zeolite of either type) is useful for a variety of molecular sieving applications (such as filtration of contaminants from air or water) .

Development of the first class of preferred embodiments began with our unexpected observation that no obvious reaction resulted from immersion of potassium permanganate-impregnated zeolite in (or spraying of such impregnated zeolite with) liquid cetyltrimethylammonium chloride (with a weight ratio Q/T in the range from 0.1% to 5%, where Q is the cetyltrimethylammonium chloride weight and T is the total weight of the final product of the process) . As a result of such immersion (or spraying) , a QAC coating was applied to each permanganate-impregnated zeolite crystal in the sense that the QAC (cetyltrimethylammonium) entered the channels near each crystal's outer surface but the QAC did not penetrate farther into the interior of each crystal. From a practical point of view, one of the inventors has found that the weight ratio of liquid cetyltrimethylammonium chloride employed for coating permanganate-impregnated zeolite crystals should preferably (at least for most air filtration applications) satisfy the following relation: 0.1% < Q/T < 0.5%, where Q is the cetyltrimethylammonium chloride weight and T is the total weight of the final product of the process.

As a result of permanganate leaching studies on the inventive QAC-coated, potassium permanganate- impregnated zeolite crystals (in which the coated, permanganate-impregnated zeolite crystals were immersed in, or sprayed with, water and the permanganate concentration in the water measured over time) , one of the inventors determined that the QAC coating substantially slowed the permanganate leaching rate (and thus would substantially slow the expected activity rate, i.e., the rate at which the impregnated zeolite would absorb and/or react with contaminants such as organic chemicals) . This result was highly unexpected in view of the conventional belief that the presence of QAC would increase zeolite's absorption of organic chemicals (such as toluene) . One of the inventors found that the activity rate of QAC-coated, potassium permanganate- impregnated zeolite depends on the concentration of the QAC solution with which the permanganate- impregnated zeolite is coated. Increasing the QAC concentration will decrease the activity rate. This inventor found that the leaching rate of permanganate from within QAC-coated, impregnated zeolite (and hence the expected activity rate) is negligible if the weight ratio of the QAC coating is in the range from 1% to 2% (i.e., if the weight of liquid cetyltrimethylammonium chloride employed for coating permanganate-impregnated zeolite crystals satisfies the relation 1% < Q/T < 2%, where Q is the cetyltrimethylammonium chloride weight and T is the total weight of the final product of the process) . To produce QAC-coated, potassium permanganate- impregnated zeolite for most air filtration applications, the optimum QAC coating weight ratio is in the range from 0.1% to 0.5% (i.e., the weight of liquid cetyltrimethylammonium chloride employed for coating the permanganate-impregnated zeolite crystals satisfies the relation 0.1% < Q/T < 0.5%, where Q is the cetyltrimethylammonium chloride weight and T is the total weight of the final product of the process) . However, for permanganate-impregnated zeolite crystals with a permanganate concentration greater than 4%, it may be desirable to employ a greater amount of QAC for the coating (i.e., the weight of liquid cetyltrimethylammonium chloride employed for the coating should satisfy the relation 1% < Q/T < 2%, where Q is the cetyltrimethylammonium chloride weight and T is the total weight of the final product of the process) . An optimal permanganate-impregnated zeolite product for absorbing (and/or reacting with) any of a wide variety of contaminants (or contaminant groups) from a fluid (such as air or water) can be determined experimentally in the following manner. Uncoated, QAC-impregnated zeolite crystals (preferably produced in the manner described below) are mixed in various ratios with QAC-coated, permanganate-impregnated zeolite crystals, and the contaminant absorption and/or reaction characteristics of each mixture studied. The mixture producing the best absorption and/or reaction characteristics is identified as the optimal mixture.

Since the QAC known as cetyltrimethylammonium is commercially available in aqueous form, impregnation of zeolite with this aqueous QAC product can be accomplished more easily than can impregnation of zeolite with potassium permanganate. A preferred method for impregnating zeolite crystals with QAC to produce zeolite crystals uniformly impregnated with cetyltrimethylammonium cations includes the following steps: dehydrating the zeolite crystals to have about 5% moisture content, then immersing the dehydrated zeolite crystals in (or spraying the dehydrated crystals with) liquid cetyltrimethylammonium chloride (the cetyltrimethylammonium chloride weight is preferably in the range from 5% to 15% of the total weight of the final product of the process) and thoroughly mixing the resulting slurry, and finally air drying the mixed slurry to produce the cetyltrimethylammonium-impregnated zeolite crystals. Typically, fifteen pounds of liquid QAC and 90 pounds of dehydrated (5% moisture) zeolite crystals are employed to produce each 100 pounds of such cetyltrimethylammonium-impregnated zeolite crystals. Although the QAC in preferred embodiments of the invention is cetyltrimethylammonium, other QACs can be substituted for cetyltrimethylammonium in alternative embodiments.

One of the inventors has also unexpectedly observed that no obvious reaction resulted from immersion of cetyltrimethylammonium-impregnated zeolite in (or spraying of such impregnated zeolite with) aqueous potassium permanganate (where the weight of the potassium permanganate is in the range from 0.1% to 2% of the weight of the impregnated zeolite) . Where the weight of the potassium permanganate in the immersing (or spraying) solution is in the range from 0.1% to 1% of the weight of the impregnated zeolite, the immersion (or spraying) results in application of a permanganate coating to each QAC-impregnated zeolite crystal (in the sense that permanganate enters the channels near each crystal's outer surface but permanganate does not penetrate farther into the interior of each crystal) . Where the weight of the permanganate in the immersing (or spraying) solution is above 1% of the weight of the impregnated zeolite, this inventor has found that immersion of QAC-impregnated zeolite crystals in (or spraying of QAC-impregnated zeolite with) aqueous permanganate results in penetration of permanganate throughout the channels of each crystal (with permanganate displacing QAC from channels not only near each crystal's outer surface but also from channels deep within the interior of each crystal) . From a practical point of view, potassium permanganate solution for coating QAC-impregnated zeolite crystals, preferably (at least for many air filtration applications) includes a total weight of permanganate in the range from 0.1% to 0.5% of the weight of the final weight of the permanganate- coated, QAC-impregnated product of the process. As a result of permanganate leaching studies on potassium permanganate-coated, QAC-impregnated zeolite crystals (in which the coated, QAC- impregnated zeolite crystals were immersed in water and the QAC concentration in the water measured over time) , it has been determined that the permanganate coating substantially slowed the QAC leaching rate (and thus would substantially slow the expected activity rate, i.e., the rate at which the impregnated zeolite would absorb contaminants such as organic chemicals) .

The activity rate of permanganate-coated, QAC- impregnated zeolite depends on the concentration of the permanganate solution with which the QAC- impregnated zeolite is coated. Increasing the permanganate concentration of the coating solution will decrease the activity rate (until the concentration is reached at which the permanganate penetrates through the entire volume of each zeolite crystal, displacing QAC impregnated throughout such volume) . To produce potassium permanganate-coated, QAC-impregnated zeolite for most air filtration applications, the optimum weight of permanganate in the coating solution is in the range from 0.1% to 0.5% of the final weight of the permanganate-coated, QAC-impregnated product of the process.

An optimal QAC-impregnated zeolite product for absorbing any of a wide variety of contaminants (or contaminant groups) from a fluid (such as air or water) can be determined experimentally in the following manner. Uncoated, permanganate-impregnated zeolite crystals are mixed in various ratios with permanganate-coated, QAC-impregnated zeolite crystals, and the contaminant absorption characteristics of each mixture studied. The mixture producing the best absorption characteristics is identified as the optimal mixture.

It may also be useful to mix permanganate- coated, QAC-impregnated zeolite crystals with QAC- coated, permanganate-impregnated zeolite crystals.

The characteristics of a QAC (or permanganate) coating on a zeolite crystal impregnated with permanganate (or QAC) can be varied to control the reaction rate of the substance impregnated within the zeolite. Such characteristics can be varied by changing the concentration of the coating solution in which (or with which) the impregnated zeolite crystal is immersed (or sprayed) to form the coating.

Important aspects of the invention are methods for producing zeolite crystals impregnated with manganese dioxide, the product of such methods, and methods for using such manganese dioxide-impregnated zeolite crystals to absorb contaminants from fluid (especially liquids) . One preferred technique for producing the inventive manganese dioxide-impregnated crystals is to flow a gas comprising one or more of hydrogen, nitrogen, ethylene, and formaldehyde through a bed of permanganate-impregnated zeolite crystals (preferably, with the crystals enclosed in a vessel or other container having a gas inlet and a gas outlet) . Alternatively, the permanganate-impregnated zeolite crystals are caused to flow through a non- flowing volume of such gas. Also alternatively, the gas which flows through the permanganate-impregnated zeolite crystals comprises one or more of hydrogen, nitrogen, ethylene, formaldehyde, and other gases similar' to these gases (but not H₂S gas) .

In another preferred embodiment, the invention produces manganese dioxide-impregnated zeolite crystals from zeolite crystals impregnated with permanganate (with or without a QAC coating) in the following manner. The permanganate-impregnated zeolite crystals (e.g., crystals having a potassium permanganate content of about 4% and a moisture content of about 15%) are employed to filter fluid

(such as air or liquid water) containing a gas (e.g., a contaminant gas) comprising one or more of hydrogen, nitrogen, ethylene, and formaldehyde. The filtration can be performed either by flowing the fluid through the crystals or by flowing the crystals through the fluid. During the filtration step, the crystals eventually become "spent" due to chemical reaction with the fluid (including one or more of the listed gases in the fluid) . One of the inventors has recognized that each of the "spent" zeolite crystals is substantially uniformly impregnated with manganese dioxide throughout its volume.

One mechanism by which permanganate-impregnated zeolite becomes impregnated with manganese dioxide (as it becomes "spent" when employed to filter air) is believed to be as follows. This example assumes that the zeolite is initially impregnated with potassium permanganate (KMn0₄) , and that the potassium permanganate-zeolite is employed to filter air contaminated with ethylene (C₂H₄) . The following reaction is believed to explain the result that manganese dioxide forms in the pores throughout the volume of each zeolite crystal as it becomes "spent" (activated to Mn0₂) : KMn0₄ +C₂H₄ --> KMn0₂ +C0₂ +H₂0.

In a variation on the previous example, the air is contaminated with another oxidizable gas similar to ethylene, such as formaldehyde (HCHO) . In the latter case, the following reaction is believed to explain the result that manganese dioxide forms in the pores throughout the volume of each zeolite crystal as it becomes "spent" (activated to Mn0₂) : KMn0₄ +HCHO + H₂0 --> KOH + C0₂ + Mn0₂ +H₂0.

Fig. 3 represents a "spent" zeolite crystal produced according to the invention, having channels substantially uniformly impregnated with manganese dioxide 6 throughout the crystal's volume.

The manganese dioxide-impregnated zeolite crystals of the invention can be coated with a QAC (or with a permanganate), e.g., as a result of any of the above-described coating operations. Fig. 4 represents one such coated, impregnated crystal, whose channels contain QAC 8 in the region near the crystal's surface, and whose channels are impregnated with manganese dioxide 6A throughout the volume of the crystal inside the region containing QAC 8. The presence of such a QAC coating allows regulated time release control of the impregnating manganese dioxide 6A (which is an oxidizing filtering agent) , and thus permits a controlled diffusion (or absorption) rate in applications in which QAC-coated, manganese dioxide-impregnated zeolite crystals are employed to absorb contaminants from a fluid (especially a liquid such as water) . The characteristics of the QAC coating can be varied to control the reaction rate of the impregnating substance (manganese dioxide) within the zeolite crystals. Such characteristics can be varied by changing the concentration of the coating solution employed to coat the impregnated zeolite crystals.

The manganese dioxide-impregnated zeolite crystals, or QAC-coated, manganese dioxide- impregnated zeolite crystals of the invention, can be used for a variety of molecular sieving applications, such as filtration of contaminants from fluid (especially liquid) . Various combinations of such coated and uncoated crystals can be employed to match specific environmental circumstances which can be calculated by analysis of the fluid to be treated. To perform fluid filtration, the fluid is caused to flow through a bed of the inventive manganese dioxide-impregnated zeolite crystals (coated or uncoated) , or the crystals are caused to flow through the fluid. Other embodiments of the invention are a process for producing zeolite crystals impregnated with phosphoric acid, phosphoric acid-impregnated zeolite crystals produced by such process, and methods for using phosphoric acid-impregnated crystals to absorb contaminants from fluid.

Zeolite crystals have some capacity to absorb NH₃ due to their cation exchange capacity. By impregnating zeolite crystals uniformly throughout their volume with phosphoric acid (to cause the impregnated zeolite crystals to include from 1% to 10% phosphoric acid by weight) , the NH₃ absorption capacity is increased greatly (up to five times the NH₃ absorption capacity of non-impregnated zeolite crystals) . Preferably, the impregnation step is performed by immersing the zeolite in (or spraying the zeolite with) aqueous phosphoric acid. The inventive method preferably includes the steps of: dehydrating the zeolite crystals until they have moisture content substantially below their initial moisture content (preferably until their moisture content is about 5%) , then immersing the dehydrated zeolite crystals in (or 'spraying the dehydrated crystals with) an aqueous solution of phosphoric acid at high temperature and thoroughly mixing the resulting slurry, and finally air drying the mixed slurry to produce impregnated zeolite crystals. Fig. 5 represents one such impregnated crystal, having channels uniformly impregnated with phosphoric acid 10. Phosphoric acid-impregnated zeolite crystals can be- used to control NH₃ odor in fluids such as air (or liquid manure) . The reaction for neutralizing NH₃ gas in such fluids is believed to be 2NH₃ + H₃P0₄ --> (NH₄)₂HP0₄ , where (NH₄)₂HP0₄ has no odor.

We contemplate that beds of phosphoric acid- impregnated zeolite crystals can be used in animal confinement facilities to receive liquid animal wastes. Similarly, phosphoric acid-impregnated zeolite crystals can be used for such applications as in cat litter boxes and in stable "freshener" products for filtering air (or liquids) .

Other embodiments of the invention are a process for producing zeolite crystals impregnated with one of the following: (1) sodium chlorite, (2) acetic acid, (3) citric acid, and (4) chlorine solution. Other embodiments of the invention are directed to zeolite crystals impregnated with one of the following: (1) sodium chlorite, (2) acetic acid, (3) citric acid, and (4) chlorine solution. Other embodiments of the invention are directed to using zeolite crystals impregnated with one of the chemicals listed directly above (i.e., (1) sodium chlorite, (2) acetic acid, (3) citric acid, and (4) chlorine solution) to absorb contaminants from fluid.

The impregnation step is performed by immersing the zeolite in (or spraying the zeolite with) an aqueous solution of one or more of the following: (1) sodium chlorite, (2) acetic acid, (3) citric acid, and (4) chlorine. The inventive method preferably includes the steps of: dehydrating the zeolite crystals until they have moisture content substantially below their initial moisture content (preferably until their moisture content is about 5%) , then immersing the dehydrated zeolite crystals in (or spraying the dehydrated crystals with) one or more of the aqueous solutions listed above (i.e., (1) sodium chlorite, (2) acetic acid, (3) citric acid, and (4) chlorine) at high temperature and thoroughly mixing the resulting slurry, and finally air drying the mixed slurry to produce impregnated zeolite crystals. Fig. 6 represents one such impregnated crystal, having channels uniformly impregnated with a chemical 12 chosen from the following group: (1) sodium chlorite, (2) acetic acid, (3) citric acid, and (4) chlorine solution. Chemical 12 is alternatively a mixture of two or more of these substances.

Other embodiments of the invention are a process for producing zeolite crystals impregnated with one of the following: (1) sodium sulfite, (2) sodium bisulfite (also called sodium metabisulfite) , and (3) ferrous sulfate. Other embodiments of the invention are directed to zeolite crystals impregnated with one of the following: (1) sodium sulfite, (2) sodium bisulfite, and (3) ferrous sulfate. Other embodiments of the invention are directed to using zeolite crystals impregnated with one of the chemicals listed directly above (i.e., (1) sodium sulfite, (2) sodium bisulfite, and (3) ferrous sulfate) to absorb contaminants from fluid.

The impregnation step is performed by immersing the zeolite in (or spraying the zeolite with) an aqueous solution of one or more of the following: (1) sodium sulfite, (2) sodium bisulfite, and (3) ferrous sulfate. The inventive method preferably includes the steps of: dehydrating the zeolite crystals until they have moisture content substantially below their initial moisture content (preferably until their moisture content is about 5%) , then immersing the dehydrated zeolite crystals in (or spraying the dehydrated crystals with) one or more of the aqueous solutions listed above (i.e., (1) sodium sulfite, (2) sodium bisulfite, and (3) ferrous sulfate) at high temperature and thoroughly mixing the resulting slurry, and finally air drying the mixed slurry to produce impregnated zeolite crystals. Fig. 7 represents one such impregnated crystal, having channels uniformly impregnated with a chemical 14 chosen from the following group: (1) sodium sulfite, (2) sodium bisulfite, and (3) ferrous sulfate. Chemical 14 is alternatively a mixture of two or more of these substances.

Some of the impregnated zeolite crystals described above can be used in a process to produce Chlorine dioxide (C10₂) . Chlorine dioxide is useful for killing biological contaminants such as microorganisms, mold, fungi, yeast and bacteria.

First, a fluid containing oxygen (typically, but not necessarily air) is caused to move relative to a first bed of: (1) zeolite crystals which are impregnated with sodium chlorite (NaCl0₂) or (2) a mixture of zeolite crystals impregnated with sodium chlorite and zeolite crystals impregnated with chlorine. The inclusion of zeolite crystals impregnated with chlorine is thought to enhance sodium dioxide production. Then, the fluid is caused to move relative to a second bed of zeolite crystals impregnated with: (1) phosphoric acid (H₃P0₄) , (2) acetic acid (CH₃COOH) , or (3) citric acid. Upon moving the fluid (containing oxygen) relative to the second bed, chlorine dioxide is released by one or more of the following equations. For a phosphoric acid impregnated second bed: 0₂ + H₃P0₄ + NaCl0₂ --> C10₂f + NaHP0₄ + H₂0

For an acetic acid impregnated second bed: 0₂ + CH₃COOH + NaC10₂ --> C10₂t + CH₃COONa (sodium acetate) + H₂0

For a citric acid impregnated second bed: 0₂ + citric acid + 3NaCl0₂ -->

CH₂COONa

I I Cl0₂t + HOC-COONa + H₂0

I I

CH₂COONa

While the foregoing process for producing C10₂ has been described with reference two distinct (first and second) beds of impregnated zeolite crystals, a single bed containing a mixture of crystals can be used as long as the mixed bed contains both impregnated zeolite crystals from the first bed described above and zeolite crystals from the second bed described above. As an illustrative example, a mixture bed of zeolite crystals impregnated with sodium chlorite, mixed with zeolite crystals impregnated with phosphoric acid can be used to produce chlorine dioxide (by flowing a fluid containing oxygen through it) .

While chlorine dioxide can kill microorganisms as described above, chlorine dioxide itself is a contaminant. Therefore, it is sometimes desirable to remove chlorine dioxide from the fluid stream after the chlorine dioxide has performed biological purification of the fluid stream. Another aspect of the present invention relates to a multi-step filtration process in which chlorine dioxide is first produced in a fluid stream and, subsequently, removed from the fluid stream.

First, a fluid is cased to be moved relative to primary bed(s) of zeolite crystals which will cause chlorine dioxide to be released, as described above. These primary bed(s) of zeolite crystals may include a first and second bed, or a mixture bed, as described above. Upon moving relative to the primary bed(s) , chlorine dioxide is released (generally as a gas) and biological contaminants are killed in the fluid.

Then, the fluid is moved relative to a secondary bed (filter) of zeolite crystals impregnated with one of the following: (1) potassium hydroxide (KOH) , (2) sodium sulfite, (3) sodium bisulfite, and (4) ferrous sulfate. The zeolite crystals of the secondary bed react with the chlorine dioxide to remove the chlorine dioxide from the fluid. Some chemical equations describing possible reactions in the secondary bed follow.

For a secondary bed of potassium hydroxide: 2KOH + 2C10₂ --> KC10₂ + KCL0₄ + H₂0

For a secondary bed of sodium sulfite: C10₂ + Na₂S0₃ --> H₂0 + S₂0₅ + H⁺ ₃C10₃ Note that H⁺⁺ from the acids involved in the previous reactions cancel this reaction.

For a secondary bed of sodium bisulfite: C10₂ + Na₂S0₅ --> H₂0 + S₂0₅ + H⁺ ₃C10₃

Note that H** from the acids involved in the previous reactions cancel this reaction. 23

The preferred composition of the secondary bed is ferrous sulfate. For a secondary bed of ferrous sulfate:

C10₂ + Fe⁺⁺S0₄ --> Fe⁺⁺⁺ + Cl^" + C10₂ ^" -->

FeCl₃ (primarily) . When using a secondary bed of ferrous sulfate a color change, from white to brown, takes place. This is an indicator of neutralization. Various modifications and variations of the described method of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments.

Claims

WHAT IS CLAIMED IS:

1. A method for filtering a fluid, including the steps of:

(a) moving the fluid through a first bed of impregnated zeolite crystals, which include zeolite crystals impregnated with sodium chlorite;

(b) moving the fluid through a second bed of impregnated zeolite crystals, which are impregnated with at least one of the following impregnating agents: phosphoric acid, acetic acid, and citric acid, thereby producing chlorine dioxide gas; and

(c) moving the fluid through a third bed of impregnated zeolite crystals, which are impregnated with one of the following impregnating agents: potassium hydroxide, sodium sulfite, sodium bisulfite, and ferrous sulfate, thereby removing at least some of the chlorine dioxide gas by chemical reaction with the third bed.

2. The method of claim 1, wherein the fluid is moved first through the first bed, then through the second bed, and then through the third bed.

3. The method of claim 1 wherein the third bed consists essentially of zeolite crystals impregnated with ferrous sulfate.

4. The method of claim 1, wherein the fluid is contaminated air.

5. The method of claim 1, wherein the fluid includes microorganisms, and further including the steps of:

(d) after step (b) and before step (c) , exposing the microorganisms to the chlorine dioxide gas thereby killing at least some of said microorganisms.

6. A method for reacting a fluid with chemically impregnated zeolite crystals, including the steps of: (a) moving the fluid through a primary bed comprising a mixture of a first type of impregnated zeolite crystals and a second type of impregnated zeolite crystals, thereby producing chlorine dioxide gas, with the first type of impregnated zeolite crystals comprising zeolite crystals impregnated with sodium chlorite, and with the second type of impregnated zeolite crystals comprising zeolite crystals impregnated with one of the following impregnating agents: phosphoric acid, acetic acid, and citric acid; and

(b) moving the fluid through a secondary bed of impregnated zeolite crystals, which are impregnated with one of the following impregnating agents: potassium hydroxide, sodium sulfite, sodium bisulfite, and ferrous sulfate, thereby removing at least some of the chlorine dioxide gas by chemical reaction with the secondary bed.

7. The method of claim 6, wherein the fluid is moved first through the primary bed and then through the secondary bed.

8. The method of claim 6 wherein the secondary bed consists essentially of zeolite crystals impregnated with ferrous sulfate.

9. The method of claim 6, wherein the fluid is contaminated air.

10. The method of claim 6, wherein the fluid includes microorganisms, and further including the steps of:

11. A method of removing chlorine dioxide from a fluid containing said chlorine dioxide, including the step of: moving the fluid through a bed of impregnated zeolite crystals, which are impregnated with one of the following impregnating agents: sodium sulfite and sodium bisulfite, thereby removing at least some of the chlorine dioxide by chemical reaction with the bed.

12. A method for producing chlorine dioxide, including the steps of:

(a) moving a fluid containing oxygen through a first bed of impregnated zeolite crystals, which are impregnated with at least sodium chlorite; and

(b) moving the fluid through a second bed of impregnated zeolite crystals, which are impregnated with at least one of the following impregnating agents: phosphoric acid, acetic acid, and citric acid, thereby producing the chlorine dioxide as a result of chemical reaction of the fluid and said sodium chlorite and said at least one of the impregnating agents.

13. The method of claim 12 wherein the fluid is moved first through the first bed and then through the second bed.

14. The method of claim 12 wherein the first bed consists essentially of zeolite crystals impregnated with sodium chlorite.

15. The method of claim 12 wherein the first bed consists essentially of a mixture of zeolite crystals impregnated with sodium chlorite and zeolite crystals impregnated with chlorine.

16. The method of claim 12, wherein the chlorine dioxide is produced as a gas.

17. The method of claim 12, wherein the fluid is air.

18. The method of claim 12, wherein the fluid includes microorganisms, and further including the step of: (c) exposing the microorganisms to the chlorine dioxide, thereby killing at least some of said microorganisms.

19. A method for producing chlorine dioxide, including the step of: moving a fluid containing oxygen through a mixture bed comprising a mixture of a first type of impregnated zeolite crystals and a second type of impregnated zeolite crystals, thereby producing the chlorine dioxide, with the first type of impregnated zeolite crystals comprising zeolite crystals impregnated with at least sodium chlorite, and with the second type of impregnated zeolite crystals comprising zeolite crystals impregnated with one of the following impregnating agents: phosphoric acid, acetic acid, and citric acid, whereby the chlorine dioxide is produced as a result of chemical reaction of the fluid and said sodium chlorite and said at least one of the impregnating agents.

20. The method of claim 19, wherein the first type of impregnated zeolite crystals comprise zeolite crystals impregnated with sodium chlorite and zeolite crystals impregnated with chlorine.

21. The method of claim 19, wherein the chlorine dioxide is produced as a gas.

22. The method of claim 19, wherein the fluid is air.

23. The method of claim 19, wherein the fluid includes microorganisms, and further including the step of:

(c) exposing the microorganisms to the chlorine dioxide, thereby killing at least some of said microorganisms.

24. A zeolite crystal having channels uniformly impregnated with at least one impregnating agent selected from the group consisting of: sodium chlorite, acetic acid, citric acid, chlorine, sodium sulfite, and sodium bisulfite.

25. A crystal according to claim 24 having a size sufficient for filtration of a fluid.

26. A crystal according to claim 24 having a size of about 0.32 cm x 0.25 cm.

27. A crystal according to claim 24 having a size of about 0.64 cm x 0.32 cm.

28. A crystal according to claim 24 having a size of about 1.27 cm x 1.96 cm.

29. A crystal according to claim 24 wherein the impregnating agent is sodium chlorite.

30. A crystal according to claim 24 wherein the impregnating agent is acetic acid.

31. A crystal according to claim 24 wherein the impregnating agent is citric acid.

32. A crystal according to claim 24 wherein the impregnating agent is chlorine.

33. A crystal according to claim 24 wherein the impregnating agent is sodium sulfite.

34. A crystal according to claim 24 wherein the impregnating agent is sodium bisulfite.

35. A method for chemically impregnating zeolite crystals, including the steps of:

(a) dehydrating the zeolite crystals to substantially decrease their moisture content below their initial moisture content; (b) after step (a) , adding to the dehydrated zeolite crystals an aqueous solution of at least one impregnating agent selected from the group consisting of sodium chlorite, acetic acid, citric acid, chlorine, sodium sulfite, and sodium bisulfite; (c) after step (b) , drying the zeolite crystals to produce impregnated zeolite crystals having channels uniformly impregnated with the impregnating agent.

36. A method according to claim 35, wherein the aqueous solution is added at a temperature of at least 87.8° C.

37. A zeolite crystal impregnated with sodium chlorite, produced as a result of the method of claim 35.

38. A zeolite crystal impregnated with acetic acid, produced as a result of the method of claim 35.

39. A zeolite crystal impregnated with citric acid, produced as a result of the method of claim 35.

40. A zeolite crystal impregnated with chlorine, produced as a result of the method of claim 35.

41. A zeolite crystal impregnated with sodium sulfite, produced as a result of the method of claim 35.

42. A zeolite crystal impregnated with sodium bisulfate, produced as a result of the method of claim 35.