A PROCESS FOR OBTAINING FERRIC OXIDE AND AMMONIUM SALTS, AND APPARATUS FOR CARRYING OUT SAID PROCESS

Abstract: Ferric oxide and ammonium salts are prepared from aqueous iron salt solutions (e..g. liquid industrial waste) and from gaseous ammonia. In a reaction vessel (5) an iron salt containing aqueous solution (2) is reacted as a dew or spray with a NH₃-stream (9). The amount of NH₃ is at least stoichiometric in relation to the corresponding iron salts and free acid. After oxidizing and drying of the reaction product by oxidizing gases (3) and (4) at a temperature above the sublimation and/or decomposition temperature of the ammonium salt (pref. 350-600°), the ferric oxide is separated (14) and the ammonium salt is recovered by flash coding (27) in combination with an absorber washing column (19) and a crystallizer (11). In case of a vertical reaction vessel the gases are preferably horizontally and tangentially introduced to cause the formation of a cyclic movement of the gases. Suitable waste solutions are based on hydrochloric or sulfuric acid and contain iron chlorides and sulphates. The obtained ferric oxide is of the pigment type and has different shades of violet.

Description: The present invention relates to a process for obtaining ferric oxide and ammonium salts from aqueous solutions of iron salts which have been prepared for such purposes, or from liquid industrial waste containing the same. The invention further relates to an apparatus for carrying out said process. Chlorides and/or sulphates are preferred amongst the iron salts. Iron oxide of mineral origin has been used in ancient times in its red, yellow and brown varieties. With the object of improving the quality and, particularly, the dyeing power of oxides, techniques for the obtention of synthetic oxides have been developed since the XIXth century. One of the earliest methods was to obtain red oxide from the calcination of ferrous sulphate crystals resulting from the exhausted scaling liquors. The sulphate was decomposed into red ferric oxide and sulphurous anhidride, and the resulting oxide showed a poor quality and, particularly, a high acidity. Later on,a method become known for obtaining yellow oxide, which is a hydrated ferric oxide, by the wet method. In large vertical reaction vessels, scrap steel was submerged into a slurry of an iron hydroxide and ferrous sulphate solution, air oxidized and heated. The thus obtained yellow oxide was subjected to calcination in rotating ovens to yield a range of red ferric oxides of higher quality than the former oxides. This is one of the methods still presently employed. About 1950, a method was found for obtaining red ferric oxide directly by the wet method, without calcination. This method is similar to that already mentioned for synthetic yellow: in a vertical cylindrical reacting vessel, scrap steel is introduced into a slurry of a particular gel of iron hydroxide (separately prepared by reaction of ferrous sulphate with caustic soda under air bubbling) and a ferrous sulphate solution; air is blown into the mass and it is heated. The quality of the product obtained by this method is excellent. A certain amount of bibliography and patents of the most varied origins exist which describe methods for obtaining iron oxides. Most of that is represented by a solution for the recovery of scaling liquors. Some of them are described briefly hereinbelow: 1. Gaseous hydrogen chloride bubbling into a ferrous chloride solution, thus lowering the solubility of this compound which precipitates, is separated and calcinated to recover the hydrogen chloride and results in ferric oxide by air oxidation. 2. In US-A-2 642 334 which issued in 1953, the addition of sodium hydroxide solution into the scaling liquor with sulphuric acid causes the ferric oxide to precipitate (by oxidation with the air oxygen). The ferric oxide is filtered off, and the filtrate is treated with calcium oxide to precipitate calcium sulphate. The latter is in turn filtered off, and the waste liquid recycled since it is a sodium hydroxide solution. 3. A ferrous sulphate solution is treated with warm air, which evaporates the waste water, and yields ferric oxide. 4. According to US-A-3 153 575 (1964), a scaling liquor is sprayed with sulphuric acid and the waste water is evaporated by continuously feeding in hot gases. Ferrous sulphate results which is calcinated to give ferric oxide and sulphur dioxide. 5. According to the method disclosed by US-A-2 433 498 (1947), heptahydrated ferrous sulphate crystals are subjected to calcination to give ferric oxide, sulphur dioxide, sulphur trioxide and water. 6. By the addition of a sodium hydroxide solution to the scaling liquor, ferrous hydroxide is precipitated and then oxidized with air to yield ferric oxide. 7. According to Indian Patent 42,281 (1949), ammonia and air streams are passed through the scaling liquor. Ferric oxide precipitates which is separated by sedimentation. The ammonia is recovered from the ammonium sulphate waste solution by treatment with magnesium oxide. 8. US-A-2 529 874 (1950) discloses a process for obtaining ammonium salts and magnetic iron oxide from ferrous salt solutions. Said process is carried out in aqueous phase and the resulting iron oxides are brownish. 9. In US-A-2 605 169 (1952), an air-ammonia mixture is bubbled into ferrous chloride solutions from exhausted scaling liquor up to all of the iron being caused to precipitate. The precipitate is filtered off, washed, dried and calcinated. The dry product basically consists of ferric oxide. The resulting ammonium chloride is almost free of iron. Finally, other important methods exist which are being employed worldwide and start from exhausted steel sheet scaling solutions. These methods were developed with the object of recovering the acids for their recyclation and avoiding pollution by the effluents involved. Those processes are: The Ruthner process for iron chloride and the Surgi process for iron sulphate. In these processes, the ferrous sulphate is sprayed in a reaction vessel at high temperature in the presence of steam and air, thus causing hydrolysis of the same. In this manner, the hydrochloric or sulphuric acid is recovered to give iron oxide. The thus obtained oxides are inadequate for pigments due to their low dyeing power, violet shade, the remaining acidity and the high soluble salts contained therein. The process according to the invention, starting from the reaction of iron chlorides or sulphates with ammonia, is different from the Ruthner and Surgi processes in several respects: 1. Ammonium chlorides, sulphates and sulphites and ferric oxide are obtained rather than hydrochloric or sulphuric acid and ferric oxide. 2. The ferric oxide is a pigment-type one, and its shade can be varied even in the same equipment by changes in the operating conditions. 3. The ferric oxide is obtained almost free of soluble salts in view of the residual ammonium chloride or sulphate being evaporated. 4. The reaction is carried out in excess ammonia and permits working under chemically much milder conditions than the Ruthner or Surgi processes which work with hydrolysis of the ferrous chloride or sulphate, resulting in hydrochloric or sulphuric acid. Equipment is thus cheaper. 5. The method of the present invention avoids the difficult filtration of the iron oxide precipitate, as in the wet route method, and the washing of the soluble salts of this precipitate. Comparing the process of the invention with other known processes which are carried out in aqueous phase, it should be noted that it has the advantage of not needing to carry out the water evaporation step to provide dry products. It is furthermore cheaper in connection with the reactants and equipment being employed. Particularly, it is a novel process since no prior art process is known which employs a spray of ferrous chloride or sulphate solution in the presence of gaseous ammonia in the bottom of a reaction vessel. This invention relates to the treatment of iron salt solutions to produce iron oxides having different shades of violet (browns, reds and violets) and, more particularly, to the preferable utilization of chlorides or sulphates, including especially those resulting from the scaling in iron roll-out processes. The process leads to the production of pigment-type red iron oxide in its several shades; further, pure ammonium chloride, sulphate and sulphite result as by-products. Many industrial processes yield iron chloride as waste product, but the problem is to find a use or recovery process for the same, not only due to the financial loss but also to the problems derived from the pollution of natural sources by said waste. The present invention is intended to solve the problem by a process wherein the iron chloride or sulphate is converted to ammonium chloride or sulphate and sulphite and ferric oxide. As the raw material: waste solutions based on hydrochloric or sulphuric acid and containing iron chlorides or sulphates are subjected to the treatment. The object of the present invention is to provide a process enabling the simultaneous and separate recovery of iron salts and ammonium salts contained in the feed solution in the form of ammonium chloride or sulphate and sulphite, and ferric oxide, respectively. The preferred working process and apparatus according to the invention described hereinbelow are employed for achieving that purpose. Specifically, the process of the invention refers to obtaining ferric oxide and ammonium salts from aqueous iron (ferrous and/or ferric) salt solutions which have been prepared for that purpose or coming from liquid industrial waste containing the same, which comprises: a) reacting in a reaction vessel a dew or drop-spray of an aqueous iron salt solution (preferably, ferrous or ferric iron chlorides and/or sulphates) or of liquid industrial waste containing the same at a concentration of at least 5 wt %, with an ammonia stream in an at least stoichiometric ratio in relation to the iron salts, corresponding to an excess enough to neutralize the free acidity, when it occurs, thus producing particles of an aggregate of ammonium salts and hydrated iron oxides; b) oxidizing and drying said particles by simultaneously or separately contacting them with at least one gaseous stream, an oxidizing means being at least a component thereof, at a temperature not lower than the sublimation temperature of the corresponding ammonium salt(s), under its partial pressure in the gaseous mixture; c) recovering the sublimated ammonium salt(s) from said vehicle gases; d) recovering the resulting ferric oxide. The reaction is carried out at temperatures related to pressure to achieve the separation of the ammonium chloride. For instance, when working under atmospheric temperature and pressure, the temperature should not be lower than the sublimation temperature of the chloride under said conditions. The process preferably comprises the steps of spraying the aqueous solution in a reaction vessel into which gaseous ammonia and air (oxygen) are introduced, said reaction vessel being at a temperature between 80 and 900°C, either by prior heating of the feed gases or external heating through its walls. This results in the formation of solid ferric oxide and vaporized ammonium chloride, sulphate or sulphite, which are partially separated in the reaction chamber itself depending on their physical condition and then completely separated by conventional gas-solid separation methods. An important advantage of the present invention is that the ammonium chloride, sulphate or sulphite are separated from the ferric oxide in vapor form thus facilitating obtaining the latter free of impurities. This desirable condition is achieved by the temperature reached by the products before leaving the reaction chamber, which is higher than the sublimation temperature of said ammonium salts. Another important achievement is that the whole reaction occurs rapidly, which fact facilitates the continuous production of ferric oxide. Additionally, the final quality is such that no further purification is required and direct use is possible in every application - which is actually hardly achieved with the known industrial processes. An important fact with the invention also resides in the said ferric oxide being obtained directly, free of impurities, and in the form of a very fine powder, in several shades - which is achieved by an adequate regulation of the operating conditions, especially of the temperature, and of the oxidizing ability of the gaseous means since red-violaceous shades are obtained as the temperature rises and light brown and red-orange shades are achieved with low temperatures. This renders the process highly versatile and permits of the different qualities intended for commercial use being obtained. Figure 1 shows schematically the preferred equipment permitting the process to be carried out under the conditions of the present application - which does not mean a particular restriction of the invention. Within the scope of the invention, Figure 2 illustrates in detail the reaction vessel with which the said equipment is built up and which also constitutes a part of this invention. Dryers, for instance of a similar mechanical structure, are known but their object is not identical. The reaction vessel of this invention makes it possible for reactions to take place in aerosol phase wherein liquids and/or gases and/or solids are involved. Considering the scheme of Figure 1, the raw material (iron chloride, sulphate or sulphite solution in water), having a concentration comprised between 5 wt % and that of the solution saturation at the selected temperature, is conducted through line (2) up to a continuous reaction vessel (5) tailored to produce several physical and chemical transformations leading to the production of ferric oxide as main product and ammonium chloride, sulphate or sulphite as by-products. The reaction vessel comprises a zone wherein the spray or dew of the iron chloride or sulphate solution reacts in an atmosphere, mainly of gaseous ammonia, fed through line (1). This zone works at temperatures between 40 and 400°C, thus permitting a contact time of the mist droplets with the gaseous stream of 0.1 to 10 seconds. The ammonia is injected in such a manner that the dispersed solution is surrounded. Once the gaseous ammmonia and the dispersion droplets have reacted, the latter will enter the evaporation zone. In this section, a mixture of warm air and combustion gases (or either of them alone) is injected through line (3) to evaporate the aqueous solvent and to produce solid particles consisting of an aggregate of corresponding ammonium salt and iron oxides having different degrees of oxidation and hydration. At this height of the reaction vessel, a further stream of warm air and combustion gases, or either of them separately, are introduced horizontally through (4) and tangential to the vessel wall with the purpose of completing the dehydration of the solid aggregates and the oxidation of the ferrous oxide to ferric oxide and facilitating the separation of the solid products. The temperature at which this process is complete ranges from 350 up to 900°C, and the contact time between the solid particles and the warm gases should not be lower than one second. The section bottom is preferably conical and designed in such a manner to obtain a cyclonal effect with the injected gases and an outlet therefor by means of a central intake leading them together with fine particles to a solid-gas separation system. The latter can be constituted by a battery of cyclones, as shown in (7), or by any other equipment of conventional use in said step. The ferric oxide separated in (5) and (7) through lines (6) and (8), respectively, is collected by means of a conventional solid transportation system (14) which conducts it through (18) to the storage and packaging steps. The gaseous stream separated by cyclones (7) contains water, combustion gases, air and the corresponding ammonium salts and/or decomposition products thereof and still carries a small quantity of fine particles. A large number of wellknown alternatives is known for the separation of these products. The scheme of Figure 1 illustrates one of these alternatives, wherein the remaining fine particles of iron oxide are eliminated by the use of a washing tower (9). Prior to this step, the gaseous stream is cooled to allow this production alternative by injection of sprayed water through (27), thus making it possible for the solid ammonium chloride, sulphate or sulphite to precipitate as gas-entrainable microcrystals. In tower (9), there is employed as washing stream fed through (13) a non-saturated ammonium chloride, sulphate or sulphite which absorbs the gaseous ammonium chloride, sulphate or sulphite mixed with the gases coming from the battery of cyclones and holds the fine particles of ferric oxide. This solution is pumped while warm through a filter (10) to separate the pigment residues and is introduced into a crystallizer (11). The remaining gases, mainly composed of nitrogen, water, carbon dioxide and oxygen, are released to the atmosphere through (17). The last-mentioned equipment permits the crystallization of the corresponding ammonium salts to occur by cooling the solution coming from the washing tower. On the filter (12), the ammonium salt crystals are separated through (19) from the mother liquors deplete of ammonium chloride, sulphate or sulphite and recirculated through (13) to the washing tower for further recovering ammonium salt. During the filtration, the crystals are optionally subjected to a water wash. The solid product is conducted to a conventional drying step prior to its storage and/or packaging. The filtered recirculated product can be partially drained, and water can be added in its place. The crystallization could be effected by means of any known method, for instance a crystallization caused by evaporation of the solution water, or any other similar alternative. For obtaining ammonium salts whose quality is not affected by the presence of iron oxide, some cooling and solid recovery step can be included at the outlet of the gases coming from the cyclones (7), and always by conventional methods, either by a wet method similar to that employed in the tower (9), or by a dry method such as, for instance, cyclones, sleeve filters, electrostatic precipitators, etc. Figure 2 illustrates a novel reaction vessel which is a further object of the present invention and which represents the reaction vessel (5) of Figure 1 of the equipment conceived for the production of iron oxide from ferrous salt solutions. The main body is constituted by a vertical cylinder having a conical bottom (23), the upper section of the cylinder having a cover (26) bearing two main devices: 1. In the central portion of the cover, a locking system permitting the passage through a line (2) which conducts the ferrous salt solution towards the main body where it is to be sprayed. At its end, this line has a device (24) permitting the spraying of the solution in very small drops having a mean size lower than 200 µm. 2. Surrounding the spraying device (24), a perforated toroidal ring (25), whereby a gaseous ammonia stream is introduced through line (1). This device permits of an ammonia-rich atmosphere being created which surrounds the cloud of dispersed droplets of the liquid solution; thus, a first zone is created in the reaction vessel wherein the dispersed solution absorbs ammonia, precipitating the ferrous hydroxide. The cylindrical body is formed by several coupling modules (20) (21) (22) for regulation of the total reactor height, and the location of each of them thereby permitting different uses. The modules such as (22) contribute only to increase the reactor height, and therefore they increase the stay time in the area in which they are located. The module of type (21) has a surrounding sleeve for receiving through the conduit (3) a flow of hot air, combustion gases or both which enter the cylindrical body through a plurality of perforations located along the perimeter. Said device allows hot gases to enter for drying the drops containing the precipitated ferrous hydroxide and generated according to the above-mentioned description. At the same time, such a module is positioned in such a manner that depending on the size of the drops which are formed by the pulverization, it allows said drops to totally absorb the ammonia required for the ferrous hydroxide precipitation before completing their path. At the central part of the cylindrical main body and after hot gases have entered through the distribution system (21), the steps of drying, ammonium salt vaporization and decomposition and oxidation of ferrous hydroxide, which converts to ferric oxide, then take place. The module of type (20) has a tangential hot gases inlet (4) designed for completing the process described above and in order to give the gases and the solids a helicoidal movement for their primary separation by means of a cyclonic effect produced by the conical bottom (23) and the outlet centre opening (19). Placed at the bottom (6), there is a butterfly or rotary valve or another device for the periodic or continuous removal of the accumulated solids. The gases evacuated through (19) are led to a cyclonic system in order to complete the separation of solids. The equipment can be made of stainless steel AISI 316L, AISI 316 titanium-rich, Hastelloy C, or other metals or metallic alloys corrosion-resistant to acids and chlorides and/or sulphates and sulphites. It can also be made of carbon steel sheet or other materials, its interior portion being coated with metallic corrosion-resistant surfaces, or with refractory materials, with or without intermediate layers that separate them from the external cover. The ferric oxide obtained can be used for paints, cements, ceramics, plastics, rubber, paper, cosmetics, electronic purposes, etc. The resulting ammonium chloride can be obtained with suitable qualities for use as fertilizers, for electrical batteries or piles, the cleaning previous to a welding, galvanizing and for pharmaceutical purposes, etc. The resulting ammonium sulphite quality is suitable for photography. EXAMPLE 1 It was performed using the apparatus of the present invention. A volume of 317.5 kg/h of a 30% ferrous chloride solution at 25°C was introduced into the reactor (5) through the spraying system (24) with the size of the drops being from 10 to 12 µm; simultaneously, gaseous ammonia (25) was incorporated at the rate of 26 kg/h and hot air was injected at different heights: via the upper line (3) near the sprayer (1130 kg at 1065°C) for transporting the water vapour generated within the reactor and for almost total drying of the hydrated iron oxide, and via the lower line (4) (850 kg at 1020°C), the temperature of the reactive mass is raised above 350°C to effect the ammonium chloride sublimation, the iron oxide oxidation and its complete dehydration. The hot air injected into the lower part (4) was introduced tangentially to produce a cyclonic movement within the reactor which helps the separation of the ferric oxide from the remaining gases (air, water, vapour, ammonium chloride). After leaving the reactor, the gaseous mass with residues of fine ferric oxide particles was passed through the cyclones (7)-(8); the emerging hot gases were then cooled (27) by means of water injection at ambient temperature to produce a "flash" (adiabatic) whose mixture (ammonium chloride crystals, fine particles of ferric oxide and gases) passed to an absorption tower or "scrubber" (9) where a water flow circulated which dissolved the ammonium chloride. Once saturated, the solution was filtered (19) in order to separate the ferric oxide from fine particles, and the ammonium chloride solution crystallized by cooling (11). Under these conditions, a total of 1.37 kg of ammonium chloride and 1.06 kg of ferric oxide per minute were obtained. The ammonium chloride was obtained in the form of crystals and the rest remainded in the mother liquor (which was recycled). The ferric oxide was obtained in (6), (7), (8) and in the filter sludge (19). Similarly, but with the temperature above 350°C, darker ferric oxides can be obtained with the same efficiency; the colour turns to violet as the temperature increases. Likewise, replacing the ferrous chloride solution by an industrial waste, as in an exhausted pickling liquor (of hydrochloric acid), it is previously necessary to react with metallic iron in order to neutralize the free hydrochloric acid and to adjust the concentration to 30 wt %. A similar result was obtained when the procedure was repeated. EXAMPLE 2 100 ml of the solution of 33% ferrous chloride at 25°C was pulverized over a period of a minute with an air flow within a conduit having a diameter of 25 cm and a length of 1.70 m wherein gaseous ammonia circulates at a rate of 9 g/min. The conduit is opened to the atmosphere and warmed externally so that its interior temperature reaches 400°C. The outlet of said horizontal pipe is provided with a surface at ambient temperature where pure ammonium chloride crystals sublimed. Within the warmed pipe, the red salt-free ferric oxide decanted due to gravity. 30 g of ammonium chloride and 22.3 g of ferric oxide were obtained per minute. EXAMPLE 3 An exhausted solution of pickling hydrochloric acid was neutralized by heating it on scrap, at 80°C and the concentration was adjusted to 33%. Said solution was filtered and fed under the same conditions as in Example 2 with similar results. EXAMPLE 4 100 ml solution of 25 wt % ferrous sulphate at 40°C was pulverized over a period of a minute under the same conditions as in Example 1 except that: a) the interior temperature was not lower than 550°C, b) the amount of ammonia was adjusted between the stoichiometric ratio and an excess of 5%. The reaction gases were collected and dissolved in water to obtain a solution of ammonium sulphates and sulphites whose ratios vary according to the conditions of ammonia excess, temperature within the pipe and humidity. The ferric oxide remained within the pipe. EXAMPLE 5 An already exhausted solution of sulphuric acid from the pickling of iron and whose concentration had been adjusted to 25 wt % of ferrous sulphate, was subjected to the conditions of Example 4 with similar results.

Claims: Process for obtaining ferric oxide and ammonium salts from aqeuous iron (ferrous and/or ferric) salts solutions which have been prepared for that purpose or coming from liquid industrial waste containing the same, characterised in that it comprises: a) reacting in a reaction vessel a dew or spray in the form of droplets of an aqueous iron salts solution or liquid industrial waste containing them, at a concentration of at least 5g% w/w, with an ammonia stream in an at least stoichiometric ration in relation with the corresponding iron salts and an excess enough to neutralize the free acidity, if occurs, thus producing particles of an aggregate of ammonium salts and hydrated iron oxides; b) oxidizing and drying said particles by simultaneously or separately contacting them with at least a gaseous means, an oxidizing means being at least a component thereof, at a temperature not lower than the sublimation and/or decomposition temperature of the corresponding ammonium salt(s), at its partial pressure in the gaseous mixture; c) recovering the sublimated ammonium salt(s) from the vehicle gases; d) recovering the obtained ferric oxide. Process according to claim 1, characterised in that the concentration of the starting iron salts in the form of iron chloride solution is selected within the range of 5 wt % up to the saturation concentration at the selected temperature, the preferred range being 25 to 50 wt % and the concentration of the ferrous and/or ferric sulphate as iron salt is selected in the same manner, the preferred range being 30% to 60%. Process according to claim 1, characterised in that the gaseous ammonia stream is added in a ratio of up to 5% excess in relation to the said stoichiometric ratio, once the free acidity excess, when it occurs, has been neutralized. Process according to claim 1, characterised in that in step a), the starting temperatures of the liquid reactants - aqueous solution of ferrous and/or ferric salts - are selected between 0 and 150°C, the preferred range being between 20 and 40°C, and the starting temperature of the gaseous ammonia is selected between -33°C and 220°C, the preferred range being between 20 and 40°C. Process according to claim 1, characterised in that the temperature of step b) is within the range of 350 to 600°C. Process according to claim 1, characterised in that the reaction is carried out in a vertical cylindrical reactor, another gaseous means is horizontally and tangentially introduced in step (b) to maintain the temperature above the sublimation temperature of the corresponding ammonium salt(s) at the partial pressure in the gaseous mixture, within the range of 350-900°C, the preferred range being 350 to 600°C and wherein a cyclonic movement is produced due to the shape of the bottom part of the reactors to allow the said salts to be entrained by the gases and to separate the main portion of the ferric oxide from said ammonium salts. Process according to claim 1, characterised in that the ammonium salt(s) in step b) are sublimated and entrained by the employed gaseous means when the reaction is carried out horizontally for step a). Process according to claim 6, characterised by flash (adiabatically) cooling the emerging gaseous stream by introduction of sprayed water to take up its heat of evaporation. Apparatus for obtaining ferric oxide and ammonium salts according to the preceding claims; characterised by comprising a vertical cylinder (5) which is selectively formed by a plurality of coupling cylindrical modules (20), (21), (22) regulating the height of the different sections of the reaction vessel, the upper end of the upper module being hermetically sealed by a sealing system (26) connected to a pipe (2) followed by a spraying device (24) surrounded by a toroidal ring (25) which is perforated and which is connected to an external tube (1); at least a second module (21) being provided which has a plurality of holes on its surface and which is surrounded by an outer sleeve connected to a tube (3); and at least a third module (20) with a horizontal and tangential inlet (4) for a gas stream which produces a helicoidal gaseous movement in a conical bottom (23) provided with a discharge tube (19) opening into the inner space of the cylinder at the upper end of said conical bottom.

Inventors: ESCOLAR, LUIS, NUPIERI, HELIO
Applicants: QUIMICA SUDAMERICANA S.A.
Application year: 1987
Main classification: C01G49
IPC codes: C01C1, C01G49, C09C1