METHOD OF REMOVING SCALE FROM WET OXIDATION TREATMENT APPARATUS

Abstract: A method of removing scale from the surfaces of a fluid treatment apparatus comprises directing a base solution and an acid solution through the fluid treatment apparatus. The fluid treatment apparatus cleaned by the method of the present invention may be a vertical tube wet oxidation treatment apparatus in which an aqueous slurry of organic materials is oxidized in a tube which extends deep into the surface of the earth. Water rinses may be performed between the steps of circulating the aqueous base solution, circulating the aqueous acid solution, and operating the fluid treatment apparatus. The water used for separating the sequential steps is preferably buffered water. The aqueous acid solution is preferably a mineral acid and most preferably nitric acid. The aqueous base solution is preferably potassium hydroxide or sodium hydroxide. The method also contemplates a sectional wash of the apparatus by directing a base or acid solution partially into the apparatus.

Description: The present invention relates to a method of removing scale from the surfaces of a vertical tube reaction apparatus, including the downcomer and riser (alternatively called upcomer) pipe walls, which contact the aqueous phase waste stream treated by the apparatus. The method contemplated herein provides for either complete or partial washing of the system. Innovative vertical tube wet oxidation reaction systems are currently being developed to process various organic materials in an aqueous phase. In the wet oxidation process, complex organic materials in an aqueous phase are converted into water, carbon dioxide, dilute organic acids and a small amount of sterile inert ash. The chemical reaction occurs within a series of vertical concentric tubes which generally extend downwardly into the ground to a depth of from 3,000 feet to 6,000 feet (914.4m to 1828.8m). The fluid to be treated is pumped into one annulus, i.e. the downcomer, formed by adjacent concentric tubes with other reactants for the chemical reaction wherein a fluid head creates pressure and heat is added which facilitates the reaction. The temperature and pressure are greatest in the lower regions of the tubes where the reaction occurs. Following the reaction, the fluid continues its continuous flow upwardly through a second annulus, i.e. the upcomer, where the effluent may be processed further. One example of the chemical reaction is the wet oxidation of municipal wastewater treatment sludges. Oxygen, or air, is added to the influent flow of municipal wastewater treatment sludge which is wet oxidized to form water, carbon dioxide, dilute organic acids and insert ash. The tubes are preheated and temperature controlled by means of a heat exchange system as disclosed in United States Patent No. 4,272,383 of Dr. McGrew, entitled "Method and Apparatus for Effecting Subsurface, Controlled, Accelerated Chemical Reactions". A key to the commercial success of such vertical tube reaction systems is their energy efficiency, realized by applying the natural principles of gravity and thermodynamics to create the heat and pressure required to sustain the reaction. Wet oxidation of the fluid waste stream occurs in the aqueous phase when sufficient oxygen, heat and pressure are present in the system. The wet oxidation reaction is an exothermic reaction which is capable of autogenic operation after the lower portion or reaction zone of the vertical tubes are preheated to the appropriate temperature for oxidation of the waste stream, generally between 300°F and 600°F (149°C and 316°C). The efficiency of this system is also seen in the fact that the pumps injecting the fluid waste stream theoretically only need be large enough to overcome the wall friction and any differential head between the influent and effluent tubes. The vertical tubes are designed to provide sufficient residence time of the fluid waste stream in the reaction zone to complete the oxidation reactions. In the preferred arrangement, the influent and effluent flow paths of the fluid waste stream are separated by a single tube which creates an extremely efficient counterflow heat exchange between the influent and effluent wherein the influent draws heat from the effluent as the influent flows toward the reaction zone. To maintain the extraordinary efficiencies of the system, it is vital that the walls of the tubes remain substantially free of inorganic scale and that no other accumulations or plugging occur. Scale build-up on the walls of the tubes increases the wall friction and reduces the available cross-sectional area through which the fluid waste stream may flow, thereby increasing the load on the pumps circulating the fluid waste stream. Scale build-up on the walls of the vertical tubes also reduces the efficiency of the counterflow heat exchange between the influent and effluent through the walls of the tubes separating the two flows. Similarly, scale accumulations on the wall of the tube adjacent the heat exchange medium reduces the efficency of preheating the reaction zone. One problem to which the present invention is directed is the build-up of layers of inorganic scale on the tube surfaces and plugging of the downcomer with organic material. The scale is in part hard anhydrite scale which is comprised of calcium sulphate (CaSO₄). In the environment of the wet oxidation treatment apparatus, severe pyrolysis, hydrolysis and oxidation reactions occur. In this environment, the retrograde solubility of calcium sulphate results in the precipitation of the calcium sulphate and formation of the anhydrite scale on the tube surfaces which are hottest. With calcium sulphate and other substances which are subject to retrograde solubility, as the heat of a solution increases the solubility decreases. Thus, in the reaction zone, which is et a temperature of approximately 500°F to 600°F (260°C to 316°C), a certain quantity of calcium sulphate will precipitate out of the solution. The formation of anhydrite hard scale in water distillation devices has long been a problem requiring periodic boil out of distillation devices with deionized water. This approach is not appropriate for use in wet oxidation treatment apparatus due to the degree of scale build-up of substances having retrograde solubility at the extremely high temperatures encountered in the reaction zone comprising portions of the vertical tubes at a depth of more than 3,000 feet (914.4m). Mineral acid-type scale removers currently recommended for machine cleaning are relatively ineffective on anhydrite or silicate scales and used alone do not provide the necessary de-scaling action. Alakli cleaners are ineffective on mineral carbonates which also form a component of the scale build-up in the wet oxidation treatment apparatus. Other commercially available descalers have been tried to eliminate the scale build-up in the wet oxidation treatment apparatus, however they are either subject to degradation in the high temperatures of the reaction zone or they are excessively corrosive, which would reduce the useful life of the wet oxidation treatment apparatus. Another problem to which the present invention is directed is the organic and inorganic scaling and resulting plugging of the upper section of the reaction vessel in the downcomer. The formation of plugs in this area greatly increases the pressure drop across the reaction vessel, thereby requiring cleaning before the process can continue effectively. In accordance with a first aspect of the present invention, there is provided a method of removing inorganic scales from surfaces of a substantially vertical tube reaction apparatus having a plurality of nested tubes extending substantially vertically downward into the earth in which a waste stream enters the apparatus in an influent flow and exits the apparatus in an effluent flow, said waste stream undergoing a chemical reaction as it is subjected to pressures and temperatures which increase with the depth of the fluid waste stream in the tubes and which also results in scale build-up, comprising substances having retrograde solubility, on the surface of the tubes as a function of the increase in temperature and pressure of the waste stream in the influent flow and effluent flow, said method being characterised by the steps of: (a) interrupting the influent flow of the waste stream into the tube reaction apparatus; (b) flowing an aqueous sodium hydroxide or potassium hydroxide solution through the tube reaction apparatus to convert a layer of scale into an acid soluble layer; (c) flowing an aqueous nitric acid solution through the tube reaction apparatus to dissolve the acid soluble layer; and (d) resuming the influent flow of the waste stream into the tube reaction apparatus. In accordance with a second aspect of the present invention, there is provided a method of removing scale from surfaces of a substantially vertical tube reaction apparatus having a plurality of nested tubes extending substantially vertically downward into the earth in which a waste stream enters the apparatus in an influent flow and exits the apparatus in an effluent flow and said waste stream undergoes a chemical reaction as it is subjected to pressures and temperatures which increase with the depth of the fluid waste stream in the tubes and which also results in scale build-up, said method being characterised by the steps of: (a) interrupting the influent flow of the waste stream into the tube reaction apparatus; (b) circulating the aqueous hydroxide solution in a first direction through the tube reaction apparatus to convert a layer of scale into an acid soluble layer; (c) circulating the aqueous nitric acid solution in said first direction through the tube reaction apparatus following said aqueous base solution to dissolve the acid soluble layer; (d) recirculating said aqueous acid solution through the tube reaction apparatus in a second direction opposite to said first direction to further dissolve the acid soluble layer; (e) recirculating said aqueous hydroxide solution in said second direction through said tube reaction apparatus following said aqueous acid solution; and (f) resuming the influent flow of the waste stream into the tube reaction apparatus. Preferably, the method of the invention comprises the steps of: (a) interrupting the influent flow of the waste stream into the tube reaction apparatus; (b) pumping an aqueous heated sodium hydroxide or potassium hydroxide solution into the tube reaction apparatus in one direcion to a predetermined depth to dissolve organic matter from the tubes; (c) pumping said aqueous hydroxide solution out of the tube reaction apparatus in a second opposite direction to remove the aqueous base solution and dissolved organic matter; and (d) resuming the influent flow of the waste stream into the tube reaction apparatus. In the above methods, the tubes are preferably concentric, and preferably extend into the earth to a depth exceeding 3,000 feet (914.4m). The method of removing scale build-up provided by this invention is suprisingly well adapted to utilization in a vertical tube wet oxidation treatment apparatus. The method comprises successively introducing into either the downcomer or upcomer various combinations of an nitric acid solution, the hydroxide solution, and water in the flow path through which the fluid waste stream is processed during an interruption in the processing of the fluid waste stream. Removal of anhydrite scale is effected by first pumping the hydroxide solution through the normal flow path of the apparatus at a rate of displacement sufficient to permit the hydroxide solution to convert the anhydrite (CaSO₄) to calcium hydroxide (Ca(OH)₂) and dissolve the complex silicate portions of the scale deposits. The hydroxide solution is displaced from the apparatus and the nitric acid solution is then introduced into the apparatus to dissolve the Ca(OH)₂ and any mineral carbonate scale deposits on the apparatus. This surprisingly effective scale removal technique of the present invention is based in part upon the improved effectiveness of the alkali solution as it is heated to the temperatures and pressures existing in the reaction zone of the vertical tube wet oxidation treatment apparatus. The anhydrite scale is effectively converted into Ca(OH)₂ by the hot alkali solution. Likewise, the effectiveness of the acid solution on the Ca(OH)₂ and the mineral carbonates is intensified as a result of the heat and pressure acting on the acid solution. The method of the present invention may also include a water rinse between successive steps to minimize neutralization of the acid solution by the alkali solution and vice-versa. Also the use of a water rinse prior to introduction of the first de-scaling stop and following the last de-scaling step minimizes interference with normal fluid treatment and permits reuse of the acid and base solutions, if desired. Various modes of circulation and sequencing are contemplated for the descaling process of the present invention. The alkali, acid or water may be directed downwardly through the downcomer and upwardly through the upcomer to a surface reservoir or the descaling materials may be directed downwardly through the upcomer and upwardly through the downcomer to the surface reservoir. Alternatively, the flow of the solutions may be reversed or continuously circulated in a loop through the downcomer and upcomer. Thus, the present invention contemplates a method where the descaling solution is directed downwardly through either the downcomer or upcomer, the descaling solution is directed downwardly through either the downcomer or upcomer and then the flow is reversed, or the descaling solution is continuously circulated in a loop through the downcomer and upcomer. The acid used in the present invention is preferably a strong nitric acid. A dilute caustic of a concentration of approximately 10% has been found effective to remove organic scale such as grease, hair, paper, etc., when utilizing a sectional wash in the downcomer between the surface and approximately 1,000 - 3,000 feet (304.8m - 914.4m) down into the reaction vessel. This technique provides the advantage of an inexpensive and relatively quick way of removing organic scale where plugging typically occurs, thereby minimizing downtime due to a pressure drop across the reaction vessel. By way of example only, specific embodiments of the present invention will now be described, with reference to the following examples. The vertical tube reaction apparatus to which the present method is applied may be used to process waste streams from municipal sludge, pulp and paper manufacturing, industrial and petrochemical waste application and others. While different fluid waste streams have different requirements in relation to further treatment required, degree of oxidation reaction required and tendencies to form different types of scale, a common problem for such fluid treatment systems is the formation of anhydrite scale on the hot metal surfaces of the vertical tube reaction apparatus. The fluid waste stream from a municipal wastewater treatment system is an aqueous solution containing various ions of calcium, silicon and other mineral carbonates. The presence of calcium and sulphate ions in the fluid waste stream results in the formation of anhydrite scale at the high temperatures existing in the reaction zone of the fluid treatment apparatus. Anhydrite (CaSO₄) has the property of retrograde solubility wherein at temperatures of 500°F to 600°F (260°C to 316°C) occuring in the reaction zone, even a minute quantity of calcium sulphate (CaSO₄) will precipitate out of the solution and form hard anhydrite scale on the hot metal surfaces. The process considerations important to effective and efficient operation of the fluid treatment apparatus indicate that the energy used to operate the system and cost of maintenance must be kept to a minimum. The time required for de-scaling the components of the system must be minimized. Also, the material used to remove scale must not cause excessive corrosion of the tubes of the fluid treatment apparatus. Finally, the effluent of the system must not include objectionable, toxic or otherwise undesirable chemical constituents that would cause problems and require additional processing steps. In view of the nature of the types of scale to be removed and the above process considerations, the method of the present invention for removing inorganic and organic scale from the treatment apparatus comprises the steps of interrupting the influent flow of the fluid waste stream into the fluid treatment apparatus. Interruption of the influent flow is accomplished by closing the valve in the influent supply line as disclosed in United States Patent Specification No. 4,272,383, of McGrew. During the time that the influent flow is interrupted, the fluid waste to be treated by the system may be accumulated in an accumulation tank. The time available for the de- scaling operation is limited by the volume of the holding tank as is readily apparent. If the primary constituent of the scale to be removed is in part anhydrite scale (CaSO₄), it is preferred that the initial wash be a base solution, preferably a 10 percent by volume solution of sodium hydroxide (NaOH), liquid caustic, which is pumped into the fluid treatment apparatus, preferably in the influent port of the apparatus. The base solution is pumped through the apparatus and permitted to remain in contact with the surfaces to be de-scaled for a sufficient length of time to permit conversion of the anhydrite deposits to calcium hydroxide. The base solution also is effective in removing complex silicate and aluminium compound deposits found in the fluid treatment apparatus. After converting the anhydrite and removing the complex silicates and aluminium compounds, the base solution may be cycled through the path of the fluid waste stream, preferably to a storage tank. The acid solution is then pumped into the influent port of the apparatus, through the apparatus, and is permitted to remain in contact with the surface to be cleaned a sufficient length of time to dissolve the Ca(OH)₂. The acid solution comprises preferably a ten percent nitric acid solution. The nitric acid combines with the calcium hydroxide to form calcium ions, nitrate ions and water. The acid is also effective in dissolving mineral carbonates, phosphates, fluorides, magnesium compounds and accumulations of organic material that may be found in the fluid treatment apparatus. Depending upon the extent of scale build-up, the steps of circulating the base solution and acid solution may be repeated until the scale is removed or at least reduced to an acceptable level. It is generally preferred to clean the fluid treatment apparatus completely as evidenced by subsequent flow capacity. As described, flow resistance through the reaction vessel may also be impaired by an accumulation of organic materials such as grease, hair, paper, etc., which forms plugs commonly in the downcomer of the vessel. It has been found that if a sectional wash is used consisting of a dilute caustic, such as a 10% by volume solution of sodium hydroxide, which is pumped into the vessel inlet (downcomer) to a depth of approximately 1,000 - 3,000 feet (304.8m to 914.4m) while being heated, the caustic will dissolve the organic materials and some of the metal salts. Flow is then reversed to remove the caustic and dissolved scale materials. A follow-up mineral acid solution may then be pumped into the downcomer to dissolve calcium, magnesium, phosphates, etc., as described above. However, it has been found that a sectional washing using only the dilute caustic reduced the pressure drop across the reaction vessel by approximately 50-60%, and therefore, the follow-up acid wash would not normally be necessary. The de-scaling process of the present invention may be effected in several ways. First, the caustic or acid is directed downwardly through the downcomer or upcomer of the reaction vessel and, after sufficient residence time, cycled to a storage tank. Normally, the caustic would be cycled through the reaction vessel first with the acid being cycled through the vessel afterwards. A water rinse is used between the successive caustic and acid cycling to minimize neutralization of the acid by the caustic or vice versa. Further, a water rinse has been used prior to the introduction of the caustic and following the acid cycling to minimize interference with normal waste fluid treatment in the vessel. Another technique consists of directing caustic through the reaction vessel followed by water until the caustic partially exits the vessel at which time the flow is reversed and water is added in the reverse direction followed by acid. Water is then added again behind the acid in the reverse direction until the acid partially exits the vessel. The direction of flow is again reversed thereby permitting the slugs of caustic, water and acid to be cycled through the vessel in alternate forward and backward flow as desired. Finally, the slugs of caustic, water and acid may be circulated continuously in a loop, i.e., down the downcomer and up the upcomer, or down the upcomer and up the downcomer. EXAMPLES The method of removing inorganic and organic scale from surfaces of a vertical tube reaction apparatus having a plurality of concentric tubes extending vertically downward into the earth to a depth of more than 5,000 feet (1524m) is explained below. The vertical tube reaction apparatus cleaned by the method of the present invention was used to process municipal waste sludge by a wet oxidation reaction. The aqueous base and acid solutions were pumped through the system at a constant flow rate of 60 gallons (272.76 litres) per minute throughout the wash. Examples of use of the method of the present invention in the above apparatus are described below. The time stated is the number of minutes during which the solution was pumped into the apparatus and the pH stated is the average pH of the solution during each wash step. EXAMPLE 1 Time Wash Solution Average pH 45 minutes NaOH pH 11.6 120 minutes HNO₃ pH 0.7 180 minutes NaOH pH 11.1 125 minutes HNO₃ pH 2.2 Result: 635.9 lbs. (288.4kg) of scale removed. EXAMPLE II Time Wash Solution Average pH 90 minutes NaOH pH 10.7 70 minutes HNO₃ pH 3.0 80 minutes HNO₃ pH 0.6 110 minutes NaOH pH 10.1 Result: 5,036.5 lbs. (2284.5 kg) of scale removed. EXAMPLE III Time Wash Solution Average pH 60 minutes NaOH pH 11.3 95 minutes HNO₃ pH 1.7 110 minutes NaOH pH 11.3 100 minutes HNO₃ pH 4.1 Result: 725.9 lbs (329.3 kg) of scale removed. EXAMPLE IV Time Wash Solution Average pH 60 minutes HNO₃ pH 1.0 65 minutes NaOH pH 11.4 100 minutes HNO₃ pH 1.0 80 minutes HNO₃ pH 2.6 Result: 2574.8 lbs (1167.9 kg) of scale removed. EXAMPLE V Time Wash Solution Average pH 45 minutes NaOH pH 11.9 60 minutes HNO₃ pH 1.4 137 minutes NaOH pH 11.8 173 minutes HNO₃ pH 2.1 Result: 267.6 lbs (121.4 kg) of scale removed. EXAMPLE VI Time Wash Solution Average pH 30 minutes NaOH pH 11.8 75 minutes HNO₃ pH 1.0 140 minutes NaOH pH 11.6 130 minutes HNO₃ pH 2.7 Result: 580.8 lbs (263.4 kg) of scale removed. The effectiveness of the method of terms of total quantity of inorganic scale removed varied in the above examples for various reasons, such as the length of time between scale removal operations, type of scale to be removed and other factors. The most effective example is Example II above wherein an extended NaOH wash of 90 minutes was followed by an extended HNO₃ wash for 150 minutes which was followed by a 110 minute NaOH wash. The use of the reaction vessel for waste fluid treatment preceded the wash procedure of Example II by approximately two weeks while some of the other wash examples were preceded by shorter waste fluid processing in the reaction vessel. The total amount of scale removed in pounds (kg), total distribution in percent and quantity in pounds (kg) of each component of the scale soluble in NaOH and HNO₃ for each of the above examples is shown on the following Tables I-VI. The above data shows the preferential removal of sulphate during the caustic wash resulting from the conversion of anhydrite to calcium hydroxide. Aluminium is also primarily removed during the caustic wash stop. Removal of calcium, magnesium, phosphate and fluoride occurs primarily during the acid wash step. To increase the effectiveness of the acid and base wash solutions, a water rinse step should be performed between successive steps. Water rinse may also be used after the interruption of the fluid waste stream flow just prior to the acid and base wash scale removal steps and before recommencing the waste stream flow. The water rinse may be potable water, however, it has been found that by using buffered water, in particular the effluent of the fluid treatment system, there is less redeposition of scale on the fluid treatment apparatus surfaces. This is due to the fact that the potable water includes calcium and other ions that may restart scale formation while the buffered water, or effluent, has a lower concentration of ions which may reform scale on the fluid treatment apparatus. The method of removing scale by providing alternate forward and backward flow through the reaction vessel is further described and illustrated in the example below. Alternate Forward and Backward Flow of Caustic and Acid Wash Inlet Fluid Direction Flow Time (min) NaOH (10%) forward 70 Water forward 60 (water flow until caustic starts exiting vessel, then reverse flow) Water reverse 17 HNO₃ (10%) reverse 130 Water reverse 120 (water flow in reverse direction until acid sampled for 80 minutes) HNO₃ forward 50 Water forward 3 NaOH forward 8 Water forward 180 (water flow until last of acid out of reaction vessel) Amount of Scale Removed Using Alternate Flow of Caustic and Acid Caustic Acid Acid Caustic Ca (mg/l) 146 23000 6980 143 Mg (mg/l) 32 1245 153 17.5 Al (mg/l) 4293 2076 1744 990 Fe (mg/l) 4.8 166 324 12.9 Phosphate (mg/l) 3260 14350 1085 2000 Sulfate (mg/l) 5480 445 4000 45 Fluoride (mg/l) 330 260 25 5 Si (mg/l) 63.9 404 132 31 Result: 3,598 lbs. (1632 Kg) of scale removed. Having described the preferred method of the present invention, it will be understood that various modifications may be made to the invention disclosed herein within the purview of the appended claims. As described, the method may be used with various fluid treatment apparatus and may be applied to different types of slurries, however, the inventions are particularly adapted for use in vertical tube wet oxidation reaction fluid treatment apparatus such as may be used for wet oxidation of municipal wastewater sludge.

Claims: A method of removing residue which comprises scale or organic material from surfaces of a substantially vertical tube reaction apparatus for processing waste sludge having a plurality of nested tubes extending substantially vertically downward into the earth of the type in which a waste stream enters the apparatus in an influent flow and exits the apparatus in an effluent flow, in a manner in which the waste stream undergoes a chemical reaction as it is subjected to pressures and temperatures which increase with the depth of the fluid waste stream in the tubes and which also results in residue buildup on the tube walls, the method being characterised by the steps of: (a) interrupting the influent flow of the waste stream into the substantially vertical tube reaction apparatus; (b) flowing an aqueous sodium hydroxide or potassium hydroxide solution through the tube reaction apparatus to convert a layer of scale into an acid soluble layer; (c) flowing an aqueous nitric acid solution through the tube reaction apparatus to dissolve the acid soluble layer; and (d) resuming the influent flow of the waste stream into the substantially vertical tube reaction apparatus. A method according to claim 1, wherein the hydrostatic column of aqueous hydroxide solution, which is formed in the substantially vertical tube reaction apparatus, forms an acid soluble layer in the substantially vertical tube reaction apparatus and further characterised by the steps of: (a) flowing an aqueous nitric acid solution into the substantially vertical tube reaction apparatus after the removal of the aqueous hydroxide solution from the substantially vertical tube reaction apparatus; (b) forming a hydrostatic column of the aqueous nitric acid solution in the substantially vertical tube reaction apparatus, the aqueous acid solution exerting a preselected fluid pressure such that the acid soluble layer in the substantially vertical tube reaction apparatus is in contact with the aqueous acid solution under the pressure of the hydrostatic column to substantially dissolve the acid soluble layer from the tube; and (c) removing from the substantially vertical tube reaction apparatus the aqueous acid solution having the dissolved acid soluble layer therein. A method according to claim 1 or claim 2, wherein the scale comprises one or more of mineral carbonates; anhydrite and complex silicates, which form the scale on the surfaces of the fluid treatment apparatus. A method according to claim 3, wherein the aqueous hydroxide solution converts anhydrite into calcium hydroxide and removes deposits of complex silicates, and the aqueous nitric acid solution removes the calcium hydroxide formed by the hydroxide solution and removes deposits of mineral carbonates. A method according to any of claims 1 to 4, further comprising intermediate water rinse step(s) between successive steps. A method according to claim 5, wherein the water circulated through the fluid treatment apparatus between successive steps is buffered water. A method as claimed in any of claims 1 to 6, wherein the buffered water is from the waste stream itself. A method according to any of claims 1 to 7, wherein the aqueous base solution is used at between 149°C and 316°C (300°F and 600°F). A method according to any of claims 1 to 7, wherein the aqueous acid solution is used at between 260°C and 316°C (500°F and 600°F). A method according to any of claims 1 to 9, wherein the waste stream is diluted municipal waste.

Inventors: ATWOOD, MARK TREVOR, CARLSON, FRANK BERGER, PETERSCHECK, HERMANN WALTER
Applicants: WASTE TREATMENT PATENTS & RESEARCH N.V.
Application year: 1986
Main classification: C02F5
IPC codes: B01J19, C09K8, C02F5, C02F11, C23G1