Catalytic oxidation of NO.SUB.x./SO.SUB.x .in flue gases with atmospheric oxygen as the oxidation reagent

Abstract

The present invention solves the existing problem of using very expensive oxidation reagents, such as H.sub.2O.sub.2 and ozone, in removal of NO.sub.x and SO.sub.x from flue gases, by performing simultaneous oxidation of NO.sub.x and SO.sub.x with atmospheric oxygen in a combined system for catalytic oxidation and wet-scrubbing of both NO.sub.x and SO.sub.x from a flue gas and manufacturing fertilisers. Two major configurations of the oxidation system are disclosed in the present invention. The first configuration operates on oxygen-enriched air to increase efficiency of the oxidation reaction and requires an additional oxygen concentrator unit. The second configuration operates on atmospheric air at ambient conditions and requires an additional catalyst activation unit. In the second configuration, the efficient oxidation process is carried out at low temperatures of about 30-90 C. in the presence of recovered and re-activated catalyst. This temperature is a result of the exothermic character of the reaction, and therefore, no heating is required in the process.

Claims

1. A combined system for catalytic oxidation and wet-scrubbing of simultaneously both nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) from a flue gas, and for manufacturing fertilisers comprising: a) An oxidation reactor (1) filled with an oxidation catalyst or with an adsorbing dispersion containing said oxidation catalyst and designed: to receive either (i) a mixture of oxygen-enriched air streamed from an oxygen concentrator and a flue gas containing NO.sub.x and SO.sub.x, or (ii) a mixture of ambient air and the flue gas containing NO.sub.x and SO.sub.x; to adsorb said gases on the particles of the oxidation catalyst; to carry out catalytic oxidation of said NO.sub.x and SO.sub.x to yield oxidised NO.sub.x and SO.sub.x, and to perform wet-scrubbing of said oxidised NO.sub.x and SO.sub.x, thereby yielding nitric and sulphuric acids; b) A vessel containing gas or liquid ammonia, connected to the oxidation reactor (1) or to a separating and reactor-controlling unit (2), said vessel having an inlet configured to stream said ammonia into the oxidation reactor (1) or into the separating and reactor-controlling unit (2) for reacting with the obtained nitric and sulphuric acids and to yield ammonium nitrate and ammonium sulphate fertilisers, thereby wet-scrubbing NO.sub.x and SO.sub.x from the flue gas and producing said fertilisers; and c) The separating and reactor-controlling unit (2) connected to said oxidation reactor (1) and designed to separate the obtained products (fertilisers) and liquids, and to control said catalytic oxidation reaction and wet-scrubbing of the gases in the reactor (1), wherein if the oxidation reactor (1) is configured to receive the mixture of ambient air and the flue gas containing NO.sub.x and SO.sub.x, said system further comprises an activation chamber (8) for activating the oxidation catalyst, said activation chamber (8) contains an activation reagent and is in fluid communication with the separating and reactor-controlling unit (2), from which it receives the deactivated oxidation catalyst, and with the oxidation reactor (1), to which it feeds the oxidation catalyst after its activation.

2. The system of claim 1, comprising: a) An oxidation reactor (1) filled with an oxidation catalyst or with an adsorbing dispersion containing said oxidation catalyst and configured: to receive a mixture of oxygen-enriched air streamed from an oxygen concentrator and a flue gas containing NO.sub.x and SO.sub.x; to adsorb said gases on the particles of the oxidation catalyst; to carry out catalytic oxidation of said NO.sub.x and SO.sub.x to yield oxidised NO.sub.x and SO.sub.x, and to perform wet-scrubbing of said oxidised NO.sub.x and SO.sub.x, thereby yielding nitric and sulphuric acids; b) A vessel containing gas or liquid ammonia, connected to the oxidation reactor (1) or to a separating and reactor-controlling unit (2), said vessel having an inlet configured to stream said ammonia into the oxidation reactor (1) or into the separating and reactor-controlling unit (2) for reacting with the obtained nitric and sulphuric acids and to yield ammonium nitrate and ammonium sulphate fertilisers, thereby wet-scrubbing NO.sub.x and SO.sub.x from the flue gas and producing said fertilisers; and c) The separating and reactor-controlling unit (2) connected to the oxidation reactor (1) and designed to separate the obtained products (fertilisers) and liquids, and to control said catalytic oxidation reaction and wet-scrubbing of the gases in the reactor (1).

3. The system of claim 2, further comprising a separate oxidation chamber (4) connected to the oxygen concentrator and configured to receive the oxygen-enriched air stream from the oxygen concentrator and a stream of the flue gas containing NO.sub.x and SO.sub.x, said oxidation chamber (4) is filled with the oxidation catalyst capable of catalysing oxidation of NO.sub.x and SO.sub.x in the flue gas by said oxygen, said oxidation chamber (4) is either dry and packed with inert solids promoting a better contact between said oxygen stream and said flue gas stream, or wet and containing a liquid circulating inside.

4. The system of claim 1, comprising: a) An oxidation reactor (1) filled with an oxidation catalyst or with an adsorbing dispersion containing said oxidation catalyst and configured: to receive a mixture of ambient air and the flue gas containing NO.sub.x and SO.sub.x; to adsorb said gases on the particles of the oxidation catalyst; to carry out catalytic oxidation of said NO.sub.x and SO.sub.x to yield oxidised NO.sub.x and SO.sub.x, and to perform wet-scrubbing of said oxidised NO.sub.x and SO.sub.x, thereby yielding nitric and sulphuric acids; b) A vessel containing gas or liquid ammonia, connected to the oxidation reactor (1) or to a separating and reactor-controlling unit (2), said vessel having an inlet configured to stream said ammonia into the oxidation reactor (1) or into the separating and reactor-controlling unit (2) for reacting with the obtained nitric and sulphuric acids and to yield ammonium nitrate and ammonium sulphate fertilisers, thereby wet-scrubbing NO.sub.x and SO.sub.x from the flue gas and producing said fertilisers; c) The separating and reactor-controlling unit (2) connected to said oxidation reactor (1) and designed to separate the obtained products (fertilisers) and liquids, and to control said catalytic oxidation reaction and wet-scrubbing of the gases in the reactor (1), and d) An activation chamber (8) for activating the oxidation catalyst, said activation chamber (8) contains an activation reagent and is in fluid communication with the separating and reactor-controlling unit (2), from which it receives the deactivated oxidation catalyst, and with the oxidation reactor (1), to which it feeds the oxidation catalyst after its activation.

5. The system of claim 4, further comprising a separate oxidation chamber (4) configured to receive the flue gas containing NO.sub.x and SO.sub.x together with ambient air, said oxidation chamber (4) is filled with the oxidation catalyst capable of catalysing oxidation of NO.sub.x and SO.sub.x in the flue gas, and said oxidation chamber (4) is either dry and packed with inert solids promoting a better contact between said oxygen stream and said flue gas stream, or wet and containing a liquid circulating inside.

6. The system of claim 1, wherein said oxidation reactor (1) is either dry and packed with inert solids promoting a better contact between said oxygen stream and said flue gas stream, or wet and containing a liquid circulating inside.

7. The system of claim 1, wherein said oxidation reactor (1) is selected from a bubble column, packed bed and spray tower.

8. The system of claim 1, wherein said oxidation reactor (1) is a spray tower equipped with spray means capable of spraying into said spray tower either (i) water or mother liquor onto the dry oxidation catalyst particles, thereby forming floating drops of the adsorbing dispersion directly inside the spray tower, or (ii) the adsorbing dispersion prepared in advance and comprising the oxidation catalyst particles.

9. The system of claim 1, wherein said adsorbing dispersion is an aqueous suspension of the oxidation catalyst particles.

10. The system of claim 9, wherein said oxidation catalyst comprises the mixture of an aqueous solution of a metal salt precursor with silica gel particles and used for catalysing the oxidation reaction of NO.sub.x and SO.sub.x in the flue gas.

11. The system of claim 10, wherein the metal salt precursor is a water-soluble inorganic salt of a transition metal selected from cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu) and chromium (Cr).

12. The system of claim 10, wherein the oxidation catalyst comprises an aqueous suspension of cobalt oxide/hydroxide particles supported on silica gel particles.

13. The system of claim 1, wherein said separating and reactor-controlling unit (2) comprises at least one of the following processing units: a phase separator, crossflow separator, mixer-settler, decanter, tricanter or filter.

14. The system of claim 13, further comprising a crystallisation vessel connected to the processing unit and configured to receive from said processing unit an aqueous solution containing the dissolved ammonium nitrate and ammonium sulphate products, said crystallisation vessel is capable of crystallising and precipitating the ammonium nitrate and ammonium sulphate from the aqueous solution.

15. The system of claim 1, wherein said adsorbing dispersion is an oil-water emulsion, and said separating and reactor-controlling unit (2) comprises an oil-water phase separator configured to receive said oil-water emulsion from the oxidation reactor (1) and to separate gross amounts of oil (organic phase) from water (aqueous phase).

16. The system of claim 15, wherein the oil-water emulsion comprises a filtered aqueous solution and an organic phase, said organic phase comprises elemental sulphur in saturated heavy mineral oil, said sulphur is capable of catalysing the oxidation reaction of NO.sub.x and SO.sub.x in the flue gas.

17. The system of claim 16, wherein said organic phase further comprises activators added to the sulphur oil solution to increase solubility of the elemental sulphur.

18. A method for catalytic oxidation and simultaneous removal of nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) from a flue gas containing said oxides, comprising: I. Catalytic oxidation of the NO.sub.x and SO.sub.x contained in the flue gas with oxygen, wherein said catalytic oxidation yields the oxidised NO.sub.x and SO.sub.x, said catalytic oxidation is carried out in the oxidation reactor (1) of the system of claim 1; and II. Wet-scrubbing of the oxidised NO.sub.x and SO.sub.x with an adsorbing dispersion comprising a solid oxidation catalyst suspended in water, an oxidation catalyst soluble in organic solvent and emulsified in water, or combination thereof, thereby removing the NO.sub.x and SO.sub.x from the flue gas and yielding nitric and sulphuric acids dissolved in water.

19. The method of claim 18, further comprising at least one of the steps selected from: III. Simultaneously removing the nitric and sulfuric acids from water by contacting the adsorbing dispersion with ammonia to produce ammonium nitrate and ammonium sulphate; IV. Separation, crystallisation and collection of the ammonium nitrate and ammonium sulphate fertiliser products; and V. Recycling water from mother liquor, said mother liquor is left after precipitation of said ammonium nitrate and ammonium sulphate.

20. The method of claim 18, wherein said method is carried out at the temperature of about 30-90 C. and pH 4-7.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present invention will be understood and appreciated more fully from the following detailed description taken in conjunction with the appended figures. Various exemplary embodiments are well illustrated in the accompanying figures with the intent that these examples not be restrictive. Of the accompanying figures:

(2) FIG. 1a shows the operational diagram of the system of the present invention for combined catalytic oxidation and wet-scrubbing of nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) from flue gases, where the system operates on oxygen-enriched air streamed from an oxygen concentrator.

(3) FIG. 1b shows the operational diagram of the system of the present invention for combined catalytic oxidation and wet-scrubbing of nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) from flue gases, where the system operates on ambient (atmospheric) air.

(4) FIG. 2a schematically shows the one-stage system of the present embodiment, wherein the adsorption and oxidation reactor (1) is a spray tower, where the system operates on oxygen-enriched air streamed from an oxygen concentrator.

(5) FIG. 2b schematically shows the one-stage system of the present embodiment, wherein the adsorption and oxidation reactor (1) is a spray tower, where the system operates on ambient (atmospheric) air.

(6) FIGS. 3a-3h show the scanning electron microscope (SEM) images of the obtained silica particles coated with cobalt hydrous oxide. According to the EDS analysis of cobalt, the weight of cobalt is 17.6% (=0.8) and the weight of oxygen is 82.4% (=0.8) in the catalyst.

(7) FIG. 4a schematically shows the separator and reactor control unit (2) for the system shown in FIGS. 1a and 2a of the present invention, where the system operates on oxygen-enriched air streamed from an oxygen concentrator.

(8) FIG. 4b schematically shows the separator and reactor control unit (2) for the system where the adsorbing dispersion contains the oil-water emulsion of the catalyst, and where the system operates on oxygen-enriched air streamed from an oxygen concentrator.

(9) FIG. 4c schematically shows the separator and reactor control unit (2) for the system shown in FIGS. 1b and 2b of the present invention, where the system operates on ambient (atmospheric) air.

(10) FIG. 4d schematically shows the separator and reactor control unit (2) for the system where the adsorbing dispersion contains the oil-water emulsion of the catalyst, and where the system operates on ambient (atmospheric) air.

(11) FIG. 5a shows the operational diagram of the industrial two-stage system of the present invention with the separate oxidation chamber (4) containing the oxidation catalyst, and where the system operates on oxygen-enriched air streamed from an oxygen concentrator.

(12) FIG. 5b shows the operational diagram of the industrial two-stage system of the present invention with the separate oxidation chamber (4) containing the oxidation catalyst, and where the system operates on ambient (atmospheric) air.

(13) FIG. 6a schematically shows the two-stage system of the present invention, wherein the wet scrubber (1) is a spray tower that is capable of spraying the adsorbing dispersion, and where the system operates on oxygen-enriched air streamed from an oxygen concentrator.

(14) FIG. 6b schematically shows the two-stage system of the present invention, wherein the wet scrubber (1) is a spray tower that is capable of spraying the adsorbing dispersion, and where the system operates on ambient (atmospheric) air.

(15) FIGS. 7 and 8 schematically show the corresponding one- and two-stage laboratory systems of the present invention shown in FIGS. 2a and 6a, respectively.

(16) FIG. 9 schematically shows the operational diagram of the one-stage laboratory system of the present invention fed with synthetic gases.

(17) FIG. 10 schematically shows the operational diagram of the one-stage laboratory system of the present invention fed with the fuel gases from a diesel engine.

DETAILED DESCRIPTION

(18) In the following description, various aspects of the invention will be described. For purposes of explanation, specific aspects and details are set forth in order to provide a thorough understanding of the invention. However, it will also be apparent to one skilled in the art that the invention may be practiced without the specific details presented herein. Furthermore, well-known features may be omitted or simplified in order not to obscure the invention.

(19) The terminology used herein is for describing particular embodiments only and is not intended to be limiting of the invention. The terms comprising and comprises, used in the claims, should not be interpreted as being restricted to the means listed thereafter; they do not exclude other elements or steps. They need to be interpreted as specifying the presence of the stated features, integers, steps and/or components as referred to, but does not preclude the presence and/or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression a device comprising x and z should not be limited to devices consisting only of components x and z. Also, the scope of the expression a method comprising the steps x and z should not be limited to methods consisting only of these steps.

(20) Unless specifically stated, as used herein, the term about is understood as within a range of normal tolerance in the art, for example within two standard deviations of the mean. In one embodiment, the term about means within 10% of the reported numerical value of the number with which it is being used, preferably within 5% of the reported numerical value. For example, the term about can be immediately understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. In other embodiments, the term about can mean a higher tolerance of variation depending on for instance the experimental technique used. Said variations of a specified value are understood by the skilled person and are within the context of the present invention. As an illustration, a numerical range of about 1 to about 5 should be interpreted to include not only the explicitly recited values of about 1 to about 5, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3, and 4 and sub-ranges, for example from 1-3, from 2-4, and from 3-5, as well as 1, 2, 3, 4, 5, or 6, individually. This same principle applies to ranges reciting only one numerical value as a minimum or a maximum. Unless otherwise clear from context, all numerical values provided herein are modified by the term about. Other similar terms, such as substantially, generally, up to and the like are to be construed as modifying a term or value such that it is not an absolute. Such terms will be defined by the circumstances and the terms that they modify as those terms are understood by those of skilled in the art. This includes, at very least, the degree of expected experimental error, technical error and instrumental error for a given experiment, technique or an instrument used to measure a value.

(21) As used herein, the term and/or includes any and all combinations of one or more of the associated listed items. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Well-known functions or constructions may not be described in detail for brevity and/or clarity.

(22) It will be understood that when an element is referred to as being on, attached to, connected to, coupled with, contacting, etc., another element, it can be directly on, attached to, connected to, coupled with or contacting the other element or intervening elements may also be present. In contrast, when an element is referred to as being, for example, directly on, directly attached to, directly connected to, directly coupled with or directly contacting another element, there are no intervening elements present. It will also be appreciated by those of skill in the art that references to a structure or feature that is disposed adjacent another feature may have portions that overlap or underlie the adjacent feature.

(23) Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealised or overly formal sense unless expressly so defined herein. Well-known functions or constructions may not be described in detail for brevity and/or clarity.

(24) The deficiencies of the prior art as discussed above are alleviated by the systems and processes described in the present application, wherein nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) of the emitted flue gases are simultaneously oxidised by atmospheric oxygen in the presence of a catalyst followed by wet scrubbing in the presence of ammonia to yield the corresponding ammonium salts used as fertilisers for agriculture.

(25) As mentioned above, the main problem associated with the existing methods for removal of NO.sub.x and SO.sub.x is the very low solubility of the nitric oxide gas in water. The oxidation of nitrogen to its higher valence states yields NO.sub.x soluble in water. Therefore, the removal of NO.sub.x in wet scrubbers may be greatly enhanced by gas-phase oxidation of water-insoluble NO gas to water-soluble NO.sub.2, HNO.sub.2, and HNO.sub.3 (the acid gases are much more soluble in water than nitric oxide). The gas-phase oxidation may be accomplished by injecting liquid hydrogen peroxide (H.sub.2O.sub.2) into the flue gas, so that hydrogen peroxide vaporises and dissociates into hydroxyl radicals. Ozone (O.sub.3) can also be used for the oxidation purposes. The oxidised NO.sub.x species may then be easily removed by caustic water scrubbing.

(26) However, the use of either O.sub.3 or H.sub.2O.sub.2 as oxidising reagents for NO.sub.x and SO.sub.x creates a series of safety and maintenance problems, because these oxidising reagents are relatively expensive, very reactive and corrosive. As a result, their use in wet scrubbing of NO.sub.x and SO.sub.x significantly increases the operational and maintaining costs of the process and system.

(27) Instead of using O.sub.3 or H.sub.2O.sub.2 for oxidation, the present inventors suggested using atmospheric oxygen (O.sub.2), which is abundance in the air, considerably reduces both the operational and maintenance cost of the wet scrubber and produces safer and less hazardous working environment. The use of the atmospheric O.sub.2 obviates the need for using the cumbersome and expensive H.sub.2O.sub.2/O.sub.3 oxidation systems and allows combining the catalytic oxidation and wet-scrubbing of the flue gas in one-step process.

(28) The present invention describes a combined system for catalytic oxidation and wet-scrubbing of simultaneously both nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) from a flue gas, and for manufacturing fertilisers comprising:

(29) a) An oxidation reactor (1) filled with an oxidation catalyst or with an adsorbing dispersion containing said oxidation catalyst and designed:

(30) to receive either (i) a mixture of oxygen-enriched air streamed from an oxygen concentrator and a flue gas containing NO.sub.x and SO.sub.x, or (ii) a mixture of ambient air and the flue gas containing NO.sub.x and SO.sub.x; to adsorb said gases on the particles of the oxidation catalyst; to carry out catalytic oxidation of said NO.sub.x and SO.sub.x to yield oxidised NO.sub.x and SO.sub.x, and to perform wet-scrubbing of said oxidised NO.sub.x and SO.sub.x, thereby yielding nitric and sulphuric acids;
b) A vessel containing gas or liquid ammonia, connected to the oxidation reactor (1) or to a separating and reactor-controlling unit (2), said vessel having an inlet configured to stream said ammonia into the oxidation reactor (1) or into the separating and reactor-controlling unit (2) for reacting with the obtained nitric and sulphuric acids and to yield ammonium nitrate and ammonium sulphate fertilisers, thereby wet-scrubbing NO.sub.x and SO.sub.x from the flue gas and producing said fertilisers; and
c) The separating and reactor-controlling unit (2) connected to said oxidation reactor (1) and designed to separate the obtained products (fertilisers) and liquids, and to control said catalytic oxidation reaction and wet-scrubbing of the gases in the reactor (1),

(31) wherein if the oxidation reactor (1) is configured to receive the mixture of ambient air and the flue gas containing NO.sub.x and SO.sub.x, said system further comprises an activation chamber (8) for activating the oxidation catalyst, said activation chamber (8) contains an activation reagent and is in fluid communication with the separating and reactor-controlling unit (2), from which it receives the deactivated oxidation catalyst, and with the oxidation reactor (1), to which it feeds the oxidation catalyst after its activation.

(32) The present invention discloses two configurations of the oxidation system. The first configuration operates on oxygen-enriched air to increase efficiency of the oxidation reaction and requires an additional oxygen concentrator unit. The second configuration operates on atmospheric air at ambient conditions and requires an additional catalyst activation unit. In the second configuration, the efficient oxidation process is carried out at low temperatures of about 30-90 C. in the presence of recovered and re-activated catalyst. This temperature is a result of the exothermic character of the reaction, and therefore, no heating is required in the process.

(33) Thus, in some embodiments, when the oxidation reactor (1) is configured to receive a mixture of oxygen-enriched air and a flue gas (i.e. the system operates on the oxygen-enriched air), the system further comprises the oxygen concentrator designed to concentrate oxygen from ambient air and generate an air stream enriched with oxygen. The oxygen concentrator (not shown in the figures) is in fluid communication with the oxidation reactor (1). The mixture of the oxygen-enriched air and flue gas streamed into the oxidation reactor (1) consists of about 50-80% of the oxygen-enriched air and 20-50% of the flue gas.

(34) Reference is now made to FIG. 1a showing the operational diagram of the system of the present invention for combined catalytic oxidation and wet-scrubbing of nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) from flue gases and manufacturing fertilisers from them, where the system operates on oxygen-enriched air streamed from an oxygen concentrator. This is essentially a one-stage system comprising the following components:

(35) a) An oxidation reactor (1) filled with an oxidation catalyst or with an adsorbing dispersion containing said oxidation catalyst and configured: to receive a mixture of oxygen-enriched air streamed from an oxygen concentrator and a flue gas containing NO.sub.x and SO.sub.x; to adsorb said gases on the particles of the oxidation catalyst; to carry out catalytic oxidation of said NO.sub.x and SO.sub.x to yield oxidised NO.sub.x and SO.sub.x, and to perform wet-scrubbing of said oxidised NO.sub.x and SO.sub.x, thereby yielding nitric and sulphuric acids;

(36) b) A vessel containing gas or liquid ammonia, connected to the oxidation reactor (1) or to a separating and reactor-controlling unit (2), said vessel having an inlet configured to stream said ammonia into the oxidation reactor (1) or into the separating and reactor-controlling unit (2) for reacting with the obtained nitric and sulphuric acids and to yield ammonium nitrate and ammonium sulphate fertilisers, thereby wet-scrubbing NO.sub.x and SO.sub.x from the flue gas and producing said fertilisers; and

(37) c) The separating and reactor-controlling unit (2) connected to the oxidation reactor (1) and designed to separate the obtained products (fertilisers) and liquids, and to control said catalytic oxidation reaction and wet-scrubbing of the gases in the reactor (1).

(38) The oxygen concentrator, which is not shown in this figure, is capable of concentrating oxygen from ambient air by selectively removing nitrogen from the air, thereby producing the air stream enriched with the atmospheric oxygen for oxidation of the NO.sub.x and SO.sub.x gases. In general, any air containing more than 21% is considered an oxygen-enriched air. Concentration of oxygen in the oxygen-enriched air strongly varies with the choice of equipment used for enriching air with oxygen. This equipment is not a part of the present invention, it is commercially available and is not essential for the problem to be solved. Dependent on the brand/model of the external air generator used for preparing the oxygen-enriched air, the level of oxygen in air supplied to the system of the present invention can strongly vary. Moreover, this parameter is not related to the process of the present invention and is not controlled in the process.

(39) As noted above, practically any commercially available oxygen concentrator can be used in the system of the embodiment. Most of them are based on fractional distillation. However, cryogenic oxygen distillators or oxygen concentrators based on membrane separation of oxygen, pressure swing adsorption and vacuum pressure swing adsorption can also be used to produce the air stream of enriched atmospheric oxygen from ambient air.

(40) In the second configuration shown in FIG. 1b, the system for combined catalytic oxidation and removal of NO.sub.x and SO.sub.x from a flue gas comprises:

(41) a) An oxidation reactor (1) filled with an oxidation catalyst or with an adsorbing dispersion containing said oxidation catalyst and configured: to receive a mixture of ambient air and the flue gas containing NO.sub.x and SO.sub.x; to adsorb said gases on the particles of the oxidation catalyst; to carry out catalytic oxidation of said NO.sub.x and SO.sub.x to yield oxidised NO.sub.x and SO.sub.x, and to perform wet-scrubbing of said oxidised NO.sub.x and SO.sub.x, thereby yielding nitric and sulphuric acids;

(42) b) A vessel containing gas or liquid ammonia, connected to the oxidation reactor (1) or to a separating and reactor-controlling unit (2), said vessel having an inlet configured to stream said ammonia into the oxidation reactor (1) or into the separating and reactor-controlling unit (2) for reacting with the obtained nitric and sulphuric acids and to yield ammonium nitrate and ammonium sulphate fertilisers, thereby wet-scrubbing NO.sub.x and SO.sub.x from the flue gas and producing said fertilisers;

(43) c) The separating and reactor-controlling unit (2) connected to said oxidation reactor (1) and designed to separate the obtained products (fertilisers) and liquids, and to control said catalytic oxidation reaction and wet-scrubbing of the gases in the reactor (1), and

(44) d) An activation chamber (8) for activating the oxidation catalyst, said activation chamber (8) contains an activation reagent and is in fluid communication with the separating and reactor-controlling unit (2), from which it receives the deactivated oxidation catalyst, and with the oxidation reactor (1), to which it feeds the oxidation catalyst after its activation.

(45) The activation reagent in the activation chamber (8), capable of activating the deactivated oxidation catalyst at low temperatures about 30-90 C., is selected from any suitable strong oxidising reagent, non-limiting examples of which are hydrogen peroxide (H.sub.2O.sub.2), hydroperoxides, such as tert-butyl hydroperoxide, benzoyl peroxide and the like.

(46) The system of the present invention may contain two types of the oxidation catalyst for facilitating the oxidation reaction of NO.sub.x and SO.sub.x. The first catalyst is used in the form of solid catalyst particles suspended in water, while the second catalyst is soluble in organic solvent and used in the oil-water emulsion. The term adsorbing dispersion used herein below thus defines both the aqueous suspension of the oxidation catalyst particles (suspended in water) and the oil-water emulsion of the oxidation catalyst (soluble in organic solvent). Depending on the type of the oxidation catalyst used or their combination, there are several possible system configurations, which are described in the present application:

(47) (A) One-stage configuration based on the oxidation catalyst particles suspended in water;

(48) (B) Two-stage configuration based on the oxidation catalyst particles suspended in water;

(49) (C) One-stage configuration based on the combination of two catalysts: the first oxidation catalyst suspended in water and the oil-water emulsion of the second oxidation catalyst (soluble in organic solvent); and

(50) (D) Two-stage configuration based on the combination of two catalysts: the first oxidation catalyst suspended in water and the oil-water emulsion of the second oxidation catalyst (soluble in organic solvent).

(51) The configurations (C) and (D) differ from the configurations (A) and (B), respectively, in the design of their separating and reactor-controlling unit (2), which should be modified for separating organic and aqueous phases.

(52) The above configurations may also contain different types of the oxidation reactor (1), which are selected from a bubble column, packed bed and spray tower. FIGS. 2a-2b show the one-stage system of the present invention operating either on oxygen-enriched air streamed from an oxygen concentrator (as in FIG. 2a) or on atmospheric (ambient) air streamed together with flue gas (as in FIG. 2b), wherein the oxidation reactor (1) constitutes a spray tower. The spray tower can spray the adsorbing dispersion containing the oxidation catalyst. The oxidation catalyst, in this case, may be either the solid catalyst suspended in water, the catalyst soluble in organic solvent and emulsified in water, or combination thereof. The spray tower is a type of a wet scrubber used to achieve mass and heat transfer between a continuous gas phase and a dispersed liquid phase. The spray tower may consist essentially of an empty cylindrical vessel made of steel or plastic and nozzles that spray the liquid into this vessel. The spray means may include one or more spray nozzles arrayed within the spray tower along the flue gas flow path. The spray nozzles may be equipped with a demister (3) for mist removal. In addition, a bottom tray (5) is used for forming a uniform gas flow in the tower cross section.

(53) The obtained oxidation catalyst particles may be stabilised by the negative charges of about 260 SiO surface groups per particle with sodium ions Na.sup.+ as the counter ions. The pH of the obtained suspension may be adjusted with a basic solution, for example, sodium hydroxide solution, to pH 8 or higher in order to hydrolyse cobalt on the silica particles (so called, pH-jump). The hydrolysis is carried out under vigorous stirring at room temperature. A Y-mixer with 20 mL/s flow rate may be employed to provide uniform conditions for cobalt hydrolysis and adsorption on silica. The resultant suspension has a blue colour.

(54) The size of the silica particles selected for the preparation of the catalyst of the present invention is dependent on the size of soot particles produced when the flue gases are emitted. Since the soot size ranges between 5 to 600 nm, the smaller or larger silica particles are needed. Based on extensive experimentation, the present inventors found that the large silica particles (more than 600 nm) constituting the oxidation catalyst of the present invention provide relatively low catalytic activity. The strongest catalytic activity was achieved using Cab-O-Sil M5 silica powder having 200-300 nm long chains of 10 nm spheres (supplier: http://www.cabotcorp.com/solutions/products-plus/fumed-metal-oxides/hydrophilic). The oxidation catalyst based on these silica particles allowed to remove 88% NO.sub.x from synthetic air-NO.sub.x mixture.

(55) Another silica used in the experiments performed by the present inventors comprised 10-nm silica spheres, which is commercially available as 30% silica in water from Alfa Aesar (supplied by: https://www.alfa.com/en/catalog/043111/), in a form of a colloidal dispersion. This silica is on the lower edge of the soot's size and hence, active too.

(56) As noted above, the catalyst using these types of silica was prepared by mixing cobalt sulphate (CoSO.sub.4) with the silica followed by addition of sodium hydroxide until the obtained suspension reaches pH 10 and maintains this pH at a constant value. At such high pH, the formed cobalt hydroxide is not dissolved in water, which prevents leaching of the metal catalyst from the silica particles into water, thereby preserving its catalytic activity.

(57) FIGS. 3a-3h show the SEM images of the obtained silica particles coated with cobalt hydrous oxide. The obtained Co(OH).sub.2/SiO.sub.2 catalyst is a very high surface-area, heterogeneous, yet suspendable in water catalyst that demonstrates both high selectivity and catalytic activity in the oxidation of the NO.sub.x and SO.sub.x gases by oxygen. The catalyst also shows high stability as no deactivation or precipitation of cobalt is observed upon multiple cycling of cobalt ions through their higher oxidation state that must be involved in the oxidation process. According to the EDS analysis of cobalt atoms, the relative weight of cobalt is 17.6% (=0.8) and the weight of oxygen is 82.4% (=0.8) in the catalyst. As seen from these SEM images, the particles are composed of essentially spheres, cobalt coats the particles and is not floating in solution, since there are no visible areas which contain only cobalt, and in the areas without silica, there is no visible cobalt.

(58) Thus, the oxidation catalyst provides a system which does not necessitate the utilisation of the expensive O.sub.3 and H.sub.2O.sub.2 that are usually used. The Co(II) oxidation state changes to Co(III) after its oxidation with oxygen. This oxidised cobalt is capable of oxidising NO and SO.sub.2 in the flue gas, thereby being reduced back to Co(II). The oxidation column is therefore filled with an aqueous suspension of cobalt oxide/hydroxide particles supported on silica gel particles, thereby catalysing the oxidation of NO.sub.x and SO.sub.x. When NO or SO.sub.2, which is contained in the flue gas, is being absorbed on these catalyst particles, the irreversible oxidation reaction occurs at a finite but high speed according to the following equations:

(59) ##STR00001##
The above oxidation reactions are considered to be globally of second order with respect to the reactants. Quite obviously an increase in the oxygen concentration (enrichment of the air stream with oxygen) enhances the rate of these oxidation reactions.

(60) As shown in FIGS. 2a-2b, either the oxygen-enriched air stream and the flue gas, or the flue gas with ambient air enter the spray tower from the bottom and flow counter current to the adsorbing dispersion, which is introduced at the top of the spray tower, sprayed downward the tower and adsorbs the oxidised NO.sub.x and SO.sub.x gases. The spray tower is often packed with some inert solids, such as ceramic beads, in order to promote better contact between the two streams (oxygen and flue gas).

(61) Separation of the oxidised NO.sub.x and SO.sub.x, for instance, NO.sub.2 and SO.sub.3, from the reactant NO and SO.sub.2 contained in the flue gas is achieved simply because of the solubility of the former in water. The pH of the resulted suspension decreases due to the formation of nitric and sulfuric acids via the following reactions:
2NO.sub.2+H.sub.2O.fwdarw.HNO.sub.3+HNO.sub.2
SO.sub.3+H.sub.2O.fwdarw.H.sub.2SO.sub.4

(62) As mentioned in the background, NO.sub.2 exists in equilibrium with the colourless gas dinitrogen tetroxide (N.sub.2O.sub.4):2NO.sub.2N.sub.2O.sub.4. Also, the relatively unstable dinitrogen trioxide (N.sub.2O.sub.3) may be formed according to the equilibrium: NO+NO.sub.2N.sub.2O.sub.3. In the presence of water, NO and NO.sub.2 may also exist in the equilibrium with nitrous acid: NO+NO.sub.2+H.sub.2O2HNO.sub.2. The concentrations of the various nitrogen oxides species present during the entire adsorption-oxidation process (NO, NO.sub.2, N.sub.2O.sub.3, N.sub.2O.sub.4) are not independent though, which complicates the whole process. When absorbed into water NO.sub.2, N.sub.2O.sub.3 and N.sub.2O.sub.4 undergo relatively fast hydrolysis, thereby producing nitric acid (HNO.sub.3) and nitrous acid (HNO.sub.2), the latter being decomposed in nitrous oxide NO, which desorbs to the gas phase according to the reaction: 3HNO.sub.2HNO.sub.3+H.sub.2O+2NO. The pH during the entire process must be maintained in the range of 4-7 with ammonium hydroxide injection in order to keep the reaction going and not to create the alkaline solution, from which ammonia gas (NH.sub.3) may evolve. The suspension colour may change from pink (acidic) to blue (alkaline) depending on the pH of the solution. The operating temperature is 60-70 C. due to the hot flue gas coming from the furnace.

(63) The term mother liquor used herein below defines the liquid portion of the circulating adsorbing dispersion that contains almost no suspended or dissolved oxidation catalyst or crystallisation product. It is either recycled into the spray tower together with the oxidation catalyst particles in a form of the aqueous suspension, or sprayed from the nozzles on the dry oxidation catalyst particles floating in the spray tower, thereby forming the aqueous suspension directly inside the reactor. The mother liquor is also the liquid left over after crystallisation of the fertiliser products and collected by filtering off the crystals.

(64) As schematically shown in FIGS. 2a and 2b, the adsorbing dispersion is filtered and recycled continuously in the system. The spray tower is connected to a vessel (not shown in the figure) containing either gas or liquid ammonia, which is streamed into a phase separator inside the separating and reactor-controlling unit (2) in order to react with the oxidised NO.sub.x and SO.sub.x species, thereby producing fertilisers (ammonium nitrate and ammonium sulphate) according to the following equation: HNO.sub.3 (aq)+H.sub.2SO.sub.4 (aq)+3NH.sub.4OH.fwdarw.NH.sub.4NO.sub.3 (s)+(NH.sub.4).sub.2SO.sub.4 (s)+3H.sub.2O.

(65) When the ammonia-containing vessel contains ammonia in a gas phase, the vessel is pressurised (the pressure vessel). Alternatively, ammonia which is streamed into the system, may be in a liquid form (in its aqueous solution), and then the vessel is a regular container for liquids with a pump pumping the aqueous ammonia solution into the phase of the separator and reactor control unit (2). The obtained solid products (fertilisers) are then separated from the liquids and collected. The system of the present invention may further comprise sensors for measuring and controlling pH and temperature of the liquid. The mother liquor may be further recycled by transferring it for feeding a new portion of the suspension in the spray tower. The adsorbing dispersion sprayed in the spray tower may contain the filtered aqueous solution that is recycled from the dry oxidation chamber and contains the dissolved NH.sub.4NO.sub.3 and (NH.sub.4).sub.2SO.sub.4 fertiliser products and ammonium hydroxide.

(66) Another oxidation catalyst that may be used in the system of the present invention is elemental sulphur capable of catalysing the NO.sub.x and SO.sub.x oxidation reaction. In that case, the adsorbing dispersion must contain an oil-water emulsion of sulphur, wherein the organic phase of the emulsion comprises elemental sulphur in saturated heavy mineral oil. Thus, in a particular embodiment, the sprayed adsorbing dispersion may further contain an organic phase comprising elemental sulphur in saturated heavy mineral oil, which acts as an additional oxidation catalyst in the NO.sub.x and SO.sub.x oxidation process.

(67) In other words, when the adsorbing dispersion is an oil-water emulsion of the oxidation catalyst, the mother liquor may be an emulsion containing a filtered aqueous solution recycled from the spray tower and an organic phase comprising elemental sulphur in saturated heavy mineral oil. Said sulphur is capable of catalysing the oxidation reaction of the NO.sub.x and SO.sub.x species.

(68) The sulphur catalyst for the above reaction is prepared by addition of the elemental sulphur into heavy mineral oil at a temperature higher than the melting point of sulphur (119 C.). Dissolution of sulphur in the heavy mineral oil is therefore carried out at elevated temperatures in the range 120-160 C. and results in partial formation of the SO bonds (sulfoxides), which are efficient catalysts in oxidation of (nitrite) NO.sub.2.sup. and (sulphite) SO.sub.3.sup.2 into nitrate (NO.sub.3.sup.) and sulphate (SO.sub.4.sup.2), respectively. The formed water-soluble NO.sub.3.sup. and SO.sub.4.sup.2 ions then undergo a phase transfer diffusing from the organic phase to the aqueous phase (the latter is in contact with the droplets of the mineral oil catalyst) in the spray tower.

(69) Thus, the obtained sulphur oil solution containing the mineral oil, in which the elemental sulphur is dissolved up to saturation, creates an emulsion when mixed with the aqueous solution streamed from the oxidation column. The resultant oil/water emulsion is used along with the aqueous suspension of the oxidation catalyst particles. The organic phase may further comprise various activators that may be added to the oil sulphur solution to increase the solubility of the elemental sulphur, such as diphenyl ether, dichlorobenzene, decabromo-diphenyl ether or Disperbyk-108. These activators are added to the sulphur oil solution to increase the solubility of the elemental sulphur. The sulfoxide appears to be an active species which plays a major role in the oxidation processes. In addition, the catalyst oil phase which is a bad solvent for ionic species may play a role in the efficient migration of the ammonium salts (nitrate and sulphate), their separation from the products upon saturation in the aqueous phase, followed by precipitation as solid salts which are used as fertilisers.

(70) Reference is now made to FIGS. 4a and 4c schematically showing the separating and reactor-controlling unit (2) for the two system configurations shown in FIGS. 1a-1b and 2a-2b of the present invention, respectively. The structure, configuration and components of the separating and reactor-controlling unit (2) depend on whether the adsorbing dispersion constitutes only an aqueous suspension of the oxidation catalyst particles, or the suspension also contains an oil-water emulsion of the emulsified oxidation catalyst. FIGS. 4b and 4d schematically show the separating and reactor-controlling unit (2) for the two system configurations shown in FIGS. 1a-1b and 2a-2b of the present invention, respectively, but where the adsorbing dispersion contains the oil-water emulsion of the catalyst. The stream of the oil-water emulsion obtained in the wet scrubbing process is transferred to the oil-water separator inside the separating and reactor-controlling unit (2) for separating gross amounts of oil from water and suspended solids. Any available oil-water separator may be used for this purpose, for example, an API separator, gravity plate separator, centrifugal separator, hydrocyclone separator, electro-chemical separator or downhole separator. The separated oil is then returned to the spray tower, while the aqueous phase containing dissolved NH.sub.4NO.sub.3 and (NH.sub.4).sub.2SO.sub.4 products is transferred to a crystallisation vessel (not shown in the figure) for further crystallisation and precipitation of NH.sub.4NO.sub.3 and (NH.sub.4).sub.2SO.sub.4 from the aqueous solution. The mother liquor is then recycled back into the spray tower.

(71) In general, the separating and reactor-controlling unit (2) is used for handling liquid streams transferred from the oxidation reactor (1), including a full stream or portion of it, which is called bleed stream. In the unit (2), the streamed adsorbing dispersion with the dissolved and oxidised NO.sub.x and SO.sub.x is allowed to contact with the injected stream of ammonia to produce the ammonium nitrate and ammonium sulphate fertiliser products. This reaction is carried out inside the unit (2), followed by separation of the products from the circulating stream. The unit (2) therefore comprises at least one of the following processing sub-units: a phase separator, crossflow separator, mixer-settler, decanter, tricanter or filter. When the adsorbing dispersion contains an oil-water emulsion, the unit (2) comprises an oil-water phase separator configured to receive said oil-water emulsion from the adsorption and oxidation reactor and separate the oil (organic phase) from water (aqueous phase) containing salts and suspended solid catalyst particles. This separation can be done using gravity or centrifugal separators.

(72) The separating and reactor-controlling unit (2) may further comprise sensors for measuring and controlling temperature and pH of the processed liquids. The flow, temperature and pH feedback control is performed by measuring the present values and relating them to the reference values using various actuators, such as an electric heater (for temperature control), ammonia dosing pump (for pH control), and controlled main pump (for flow control).

(73) Separation of the suspended catalyst particles from the aqueous solution or mother liquor can be carried out by membrane filtration, for example using a crossflow filtration sub-unit. For the filtration process and for the inlet stream, additional pressure pumps may be needed. The aqueous solution containing the dissolved ammonium nitrate and ammonium sulphate products is removed from the system, while the mother liquor, suspended catalyst particles, the organic phase and added water are mixed and steamed back to the oxidation reactor (1) at the bottom or through the nozzles. This way, the adsorbing dispersion containing the catalyst is allowed to circulate inside the system, while the fertiliser products are continuously removed from the system.

(74) In a further embodiment, the combined system of the present invention either comprises a separate oxidation chamber connected to the oxygen concentrator or receives atmospheric air, and consequently designed to receive either a mixture of oxygen-enriched air and flue gas, or flue gas with ambient air, respectively. FIGS. 5a and 5b show the operational diagram of the industrial two-stage system of the present invention in the two configurations defined above, having a separate oxidation chamber (4) containing the oxidation catalyst. This oxidation chamber (4) is configured to either receive an oxygen-enriched air stream and flue gas stream containing NO.sub.x and SO.sub.x (as shown in FIG. 5a) or to receive the flue gas with ambient air (see FIG. 5b), and to carry out the oxidation reaction of these gases with said oxidation catalyst. The wet scrubber (1) in this case may be essentially the same oxidation reactor (1) shown in FIGS. 1a and 1b for the one-stage system of the present invention.

(75) The wet scrubber (1) contains an adsorbing dispersion, receives the streams of the air and flue gas containing the oxidised NO.sub.x and SO.sub.x, adsorbs the streamed gases onto the catalyst particles of the adsorbing dispersion and then carries out the wet scrubbing of said gases. The adsorbing dispersion in this case is recycled in the system the same way as explained above for the one-stage configuration and therefore contains the oxidation catalyst capable of completing the simultaneous oxidation of NO.sub.x and SO.sub.x partially pre-oxidised in the oxidation chamber (4), if necessary.

(76) FIGS. 6a and 6b schematically show the two-stage system of the present embodiment in the two configurations defined above, respectively, wherein the wet scrubber (1) is a spray tower that is capable of spraying the adsorbing dispersion. In the first configuration, shown in FIG. 6a, the oxidation chamber (4) is connected to the oxygen concentrator (not shown here) to receive the air stream enriched with atmospheric oxygen and the stream of a flue gas containing NO.sub.x and SO.sub.x. In the second configuration, shown in FIG. 6b, the oxidation chamber (4) receives the flue gas with ambient air.

(77) The oxidation chamber (4) shown in FIGS. 6a-6b may be either dry, packed with inert solids, such as ceramic beads, promoting a better contact between said air stream and said flue gas stream, or wet with a liquid circulating inside. Consequently, the oxidation chamber (4) is filled with either dry catalyst particles or wet catalyst particles and capable of carrying out the catalytic oxidation of the flue gases by the supplied air. The oxidation chamber (4) may then be refilled with fresh water or with water recycled from the mother liquor left after precipitation or crystallisation of the fertiliser products.

(78) As shown in FIGS. 6a-6b, the gas stream containing oxidised NO.sub.x and SO.sub.x enters from the dry oxidation chamber (4) at the bottom of the spray tower and moves (flows) upward counter current to the adsorbing dispersion, which is sprayed downward from one or more nozzles. Thus, the two-stage system shown in FIGS. 5a-5b and 6a-6b may actually be transformed into a one-stage system, when the oxidation chamber (4) and spray tower (1) are combined together or the oxidation chamber is incorporated into the spray tower.

(79) FIGS. 7 and 8 schematically show the one- and two-stage laboratory systems of the present invention corresponding to those shown in FIGS. 2a and 6a, respectively, and described above. Further, FIG. 9 schematically shows the operational diagram of the one-stage laboratory system fed with synthetic gases, while FIG. 10 schematically shows the operational diagram of the one-stage laboratory system fed with the fuel gases from a diesel engine.

(80) In another embodiment, a method for catalytic oxidation and removal of nitrogen oxides (NO.sub.x) and sulphur oxides (SO.sub.x) simultaneously from a flue gas containing said oxides, comprises:

(81) I. Catalytic oxidation of the NO.sub.x and SO.sub.x contained in the flue gas with oxygen, wherein said catalytic oxidation yields the oxidised NO.sub.x and SO.sub.x, said catalytic oxidation is carried out in the oxidation reactor (1) of the system of claim 1; and

(82) II. Wet-scrubbing of the oxidised NO.sub.x and SO.sub.x with an adsorbing dispersion comprising a solid oxidation catalyst suspended in water, an oxidation catalyst soluble in organic solvent and emulsified in water, or combination thereof, thereby removing the NO.sub.x and SO.sub.x from the flue gas and yielding nitric and sulphuric acids dissolved in water.

(83) The method of the present invention may further comprise at least one of the following steps:

(84) III. Simultaneously removing the nitric and sulfuric acids from water by contacting the adsorbing dispersion with ammonia to produce ammonium nitrate and ammonium sulphate;

(85) IV. Separation, crystallisation and collection of the ammonium nitrate and ammonium sulphate fertiliser products; and

(86) V. Recycling water from mother liquor, said mother liquor is left after precipitation of said ammonium nitrate and ammonium sulphate.

(87) In a specific embodiment, the above process is carried out at the relatively low temperature of about 30-90 C. and pH 4-7. This pH is maintained with ammonium hydroxide injection in order to keep the reaction going and not to create the alkaline solution, from which ammonia gas (NH.sub.3) may evolve.

(88) The combined system of the embodiment is thus built to replace the existing bulky and expensive wet scrubbing systems operating at a relatively high temperature (more than 300 C.) with much smaller, simpler and cheaper combination systems operating at about 30-90 C. This heat originates from thermodynamic equilibrium in the process, and no additional heat is required and applied.

(89) The system of the present invention is available in two configurations as described above (with and without enriching air with oxygen). Another important feature of the present invention is that the process for oxidation of NO.sub.x and SO.sub.x in flue gases is a simple, economic process providing a general method for manufacturing fertilisers, such as ammonium nitrate and ammonium sulphate, by ammonia injection to the oxidised NO.sub.x and SO.sub.x gases.

(90) The combined system of the embodiment and the process carried out therein allow the replacement of the present expensive clean fossil fuels (purified according to environmental regulations and used in power production) with relatively much cheaper nitrogen and sulphur contaminated fossil fuels, which may not be used with existing systems because of their hazardous effect on the environment. Also, the possibility of combined treatment for different types of pollutants at the same facility and at relatively low temperature is of great operational and economic advantage.

(91) While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will now occur to those of ordinary skill in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.