Title of Invention	HIGH-SPEED CHAMBER MIXER FOR CATALYTIC OIL SUSPENSIONS AS A REACTOR FOR THE DEPOLYMERIZATION AND POLYMERIZATION OF HYDROCARBON-CONTAINING RESIDUES IN THE CIRCULATION TO MIDDLE DISTILLATE
Abstract	Production of diesel oil from hydrocarbon-containing residues in an oil circulation with separation of solids and product distillation for the diesel oil product by energy input with a high-speed chamber mixer and the use of fully crystallized catalysts that consist of potassium-, sodium-, calcium-, and magnesium-aluminum silicates, wherein the energy input and conversion occur primarily in the high-speed chamber mixer.

Title of Invention

HIGH-SPEED CHAMBER MIXER FOR CATALYTIC OIL SUSPENSIONS AS A REACTOR FOR THE DEPOLYMERIZATION AND POLYMERIZATION OF HYDROCARBON-CONTAINING RESIDUES IN THE CIRCULATION TO MIDDLE DISTILLATE

Abstract

Production of diesel oil from hydrocarbon-containing residues in an oil circulation with separation of solids and product distillation for the diesel oil product by energy input with a high-speed chamber mixer and the use of fully crystallized catalysts that consist of potassium-, sodium-, calcium-, and magnesium-aluminum silicates, wherein the energy input and conversion occur primarily in the high-speed chamber mixer.

Full Text	HIGH-SPEED CHAMBER MIXER FOR CATALYTIC OIL SUSPENSIONS AS A REACTOR FOR THE DEPOLYMERIZATION AND POLYMERIZATION OF HYDROCARBON-CONTAINING RESIDUES IN THE CIRCULATION TO MIDDLE DISTILLATE The invention concerns a method and a device for the extraction of hydrocarbon vapor from residues in the temperature range of 230-3 80 °C in the hot oil circulation with a single-stage or multistage mixing chamber, which realizes a pump with extremely low efficiency on the delivery side and the production of up to 95% vacuum on the intake side. In the process, the extracted hydrocarbons are depolymerized, deoxygenized and freed of the inorganic components of the molecule, such as halogens, sulfur and heavy metal atoms. A depolymerization system with a hot oil circulation is known from German Patent No. 100 49 377 and German Published Patent Application No. 103 56 245.1. Here too, ion-exchanging catalysts are used in the hot oil circulation. The heat of reaction is supplied by heat transfer through the wall or by conduction by a pump with factional heat. The disadvantage of these methods and devices in the case of German Patent No. 100 49 377 is the excessive temperature at the wall during the heat transfer, which results in pyrolytic reactions, and in the case of German Patent Application No. 103 56 245.1, the short residence time in a pump of less than one second, which is insufficient for the reaction of the residue with the catalyst oil. The actual reaction must then take place in the downstream equipment, which is possible only at significantly higher temperatures than if the reaction could take place relatively completely with a longer residence time in the pump. Other disadvantages are the high pressure that develops in the pump and that can lead to clogging in the downstream, necessarily narrower, pipes, the possible cavitation in the pump intake zone, especially in the case of substances that contain solids, and the possible clogging of the intake zone if this suction intake is not possible with relatively high negative pressure. All of these disadvantages are now eliminated by the surprisingly discovered high-speed chamber mixer, and thus the quality of the process and the product and the safety of the plant are decisively improved. In this regard, the use of a system with rolls for the suction of gases in the application for realizing a hot oil circulation is completely novel. Specifically, only the principle of the liquid ring vacuum pump was previously known, according to which gases can be compressed to atmospheric pressure, and up to about 1.5 bars of overpressure can be used as a compressor. What was not known and what was surprisingly discovered is that this principle for the conveyance of liquids and liquid/gas mixtures can be used as a mixing reactor. By utilizing the extremely low efficiency and the production of mixing and frictional energy between the catalyst oil and the hydrocarbon-containing residue feed, this system is the ideal energy-transfer unit for the method and the device for the production of diesel oil from residues. This basic principle thus represents only a framework, which becomes the high-speed chamber mixer of the invention by virtue of the completely new design of the components for the load oil instead of gas. Thus, compared to the previous pumps in German Patent Application No. 103 56 245.1, an overpressure in the delivery line of 6-100 bars becomes a pressure load of 0.5-2.0 bars, and the maximum negative pressure in the intake line of 0.1 bar to avoid cavitation becomes a possible negative pressure of 0.95 bar, i.e., a 95% vacuum- The high-speed chamber mixer with the connecting pipelines, the volume flow control valve and a separator forms a hot oil circulation, which, with the action of the molecularly fine, 100% crystalline catalyst, extracts the hydrocarbons from the preheated and dewatered hydrocarbon-containing residues, and at the same time, depending on molecular length, the extracted hydrocarbons are depolymerized, polymerized, deoxygenized and freed of the inorganic components of the molecule, such as halogens, sulfur and heavy metal atoms. The product results from the reaction temperature of 250-320°Cin the middle distillate range, diesel fuel for use in diesel engines. The basis of this process is the possible fast reaction process with intensive energy input with sufficient residence time, as is possible only in a high-speed chamber mixer. Pumping systems achieve only a very small fraction of this residence time and thus do not achieve the necessary reaction conditions and the low reaction temperatures associated therewith. In this process, of course, the goal is to keep the interval between the pyrolysis temperature and the catalytic depolymerization temperature as large as possible, i.e., to achieve the lowest possible reaction temperature. In this regard, measurements showed that the average temperature with the high-speed chamber mixer is 60°C lower than with the same system but different conveyance systems, for example, a pumping system with centrifugal impellers. This results in a decisive improvement compared to the previously known systems, such as the system described in German Patent Application No. 103 56 245.1, especially with respect to the quality and odor of the product that is produced. The uniformity of the middle distillates that are produced, which is apparent in the compressed curve of the gas chromatogram, the reduced energy input and, finally, in the completeness of the reaction, is significantly increased. The selectivity of the process increases significantly, i.e., the yield of middle distillate increases, and the fraction of separated carbon drops in the case of plant feedstocks. The fractions of light products (odorous substances) are almost completely avoided. Figure 1 shows the elements of the method. A primary oil circulation is formed by the high-speed chamber mixer 1, its intake line 2 from the separator, and the return line to the separator 3. The separator 3 is a cyclone separator, which is formed by one or more venturi tubes 4, which are attached tangentially into the tank on the delivery side, and the return lines located below in the cylindrical part. The conical part 5 located below there serves to collect deposits of solid residues 6, which consist of the inorganic constituents. A pressure of 0.5-2.0 bars overpressure is obtained on the delivery side, depending on the size of the high-speed chamber mixer 1, and a pressure of 0.9-0.05 bars absolute, i.e., a 10% to 95% vacuum, is obtained on the intake side, depending on the solids content. An automatically controlled discharge valve 7 is installed below the separator 3, i.e., below the conical part. This discharge valve 7 opens as a function of the temperature, i.e., as a function of the fraction of the inorganic constituents 6 of the material deposited there and thus allows the residue slurry 6 with the inorganic constituents to flow off into a pressure worm 8. The pressure worm 8 has a filter wall 9, through which the oil constituent 10 is returned, and thus forms a residue cake 11 towards the top, which enters a second conveyance device 12 with external heating. This conveyance device 12 has a nozzle 13 at the end, by which the inorganic solid residue, heated to 400-500°C, enters a storage tank 14, which has a connecting line 15 to the separator. The evaporated middle distillates 16 are returned to the process through this connecting line 15. A vapor tank 17 is located above the separator 3. The purification elements of the vapor tank 17 consist of one or more distillation trays 18 with a reflux channel 19, a heater 20 and insulation 21 around the tank, into which preferably exhaust gas 22 from the power generator 23 is introduced. This vapor tank 17 is connected with a condenser 24, which is cooled with cooling water from the cooling circulation 25. The condenser 24 has partition plates 26. This results in the formation of chambers with overflows 27 to allow water to settle. In the front part, these chambers are connected by a line 28 with a water and pH tank 29, which has a device 30 for measuring the pH, a conductivity cell 31 arranged above the pH meter 30, and a drain valve 32. The amount of water in the tank is automatically controlled by the drain valve 32 as a function of the level 31. The pipeline 33, which allows the condensate to be drained into the distillation system 34, is installed in the rear part of the condenser 24. The distillation system consists of the heat transfer medium circulation 35 between the circulation evaporator 36 of the distillation system and the exhaust gas heat exchanger of the power generator with the connecting pipeline 37 and the circulation pump 38, the distillation system 34, the distillation charges 39, with the bubble trays 40, the condenser 41 and the product discharges 42 and 43. The product discharge 42 from the condenser serves as the fuel supply of the power generator 23 via the line 44, and the reflux valve 45 serves to feed the product reflux 46 into the upper distillation tray. The product discharge 43 from the upper column trays 47 of the distillation system 34 serves the purpose of discharging the final product. This fraction generally contains 70-90% of the total amount of product. The product that is removed is replaced by the addition of feedstock in the feed section 48. The feed section 48 consists of the feed hopper 49 with the metering device 50 for catalyst, the metering device 51 for the neutralizing agent lime or soda, the liquid residue feed 52 and the solid residue feed 53. The metering device 50 for the catalyst is usually connected with a big-bag emptying device 54, which is controlled by the temperature measuring device 55 after the high-speed chamber mixer. If the heat transferred in the high-speed chamber mixer 1 is not sufficiently converted to the1 middle distillate product, and if the temperature rises above a limit, then the addition of catalyst in the metering device 50 increases. The metering device 51 for the neutralizing agent is controlled by the pH sensor 30. If the pH falls below an input limit of around 7.5, the feed amount in the metering device 51 increases. The added amounts of feed residues 52 and 53 are likewise metered as a function of the level gage 56 in the separator 3. This ensures that the high-speed chamber mixer 1 always receives liquid mixtures from the separator 3 and that the system is prevented from running dry. It also ensures that the various feed materials and the associated variation of the reaction rates are always compensated by variable addition, and the process is not interrupted. About 0.4 kWh of power for the cracking, evaporation and heating from the input temperature of 250°C to the reaction temperature of 300°C are needed in the oil circulation per kg of evaporated diesel oil in the case of waste oil and tars. If plastics are used as feed materials, the required power is almost twice as high, since these materials are fed in cold, and energy for melting is additionally required. In this regard, the addition of the catalyst is fundamentally important to the process. This catalyst is a sodium-aluminum silicate. The doping of a fully crystallized Y-molecule with sodium was determined to be optimum only for the plastics, bitumen and waste oils. For biological feedstocks, such as fats and biological oils, doping with calcium was found to be optimum. For reactions with wood, doping with magnesium is necessary to produce high-quality diesel oil. For highly halogenated compounds, such as transformer oil and PVC, it is necessary to dope with potassium. The product of the system is diesel oil, because the product discharge from the circulation at 300-400°C leaves no other, lighter products behind in the system. 10% of this product is used to generate the process energy requirements in the form of electric current in a power-generating unit, and the portion used to generate power is the lighter fraction of the product obtained from the condenser. The product from the column thus does not have a lighter boiling fraction and completely satisfies the tank storage standards. Another advantage of this energy conversion is the simultaneous solution of the problems with the gas emerging from the vacuum pump, which is conveyed into the intake air. In addition, the generator satisfies the conditions of the combined heat and power generation, since the thermal energy of the exhaust gases is used to predry and preheat the feedstock. The device of the invention is explained with reference to Figure 2: The high-speed chamber mixer 101 has an intake line 102, which is connected with the separator 103 by a pipeline. It is designed for a negative pressure of 0.95 bar. The separator 103 is a cyclone separator, which is formed by one or more venturi tubes 104, which are attached tangentially into the tank on the delivery side, and the return lines located below in the cylindrical part. The conical part 105 located below there has a discharge orifice 106 with a discharge valve 107. A pressure line that is designed for an overpressure of 0.5-1.5 bars is arranged on the delivery side of the high-speed chamber mixer. An automatically controlled discharge valve 7 is installed below the separator 103, i.e., below the conical part. This discharge valve 107 has a temperature sensor, which is designed for a switching temperature of 100-150°C. A pressure worm 108 is arranged below there, which is designed to convey residue slurry from the discharge valve and has a temperature resistance of 200°G The pressure worm 108 has a filter wall 109 with an oil outlet 110 and an upper pressure worm part for the residue cake 111 and a connecting pipeline to a second conveyance device 112 with external heating. This conveyance device 112 has a nozzle 113 at the end. The worm wall is designed for a temperature of 400-500 °C, which is produced by the external heater, e.g., an electric heater. The downstream storage tank 114 also has temperature resistance up to 400°C and is designed as a solids tank. The tank 114 has a connecting line 115 to the separator for returning the evaporated hydrocarbon vapor. A vapor tank 117 is located above the separator 102. The purification elements of the vapor tank 117 consist of one or more distillation trays 118 with a reflux channel 119, a heater 120 and insulation 121 around the tank, with an exhaust gas connecting line 122 to the power generator 123, by which exhaust gas is introduced into the tank. This vapor tank 117 is connected with a condenser 124. The condenser has a connecting line by which it is connected with cooling water from the cooling circulation 125. The condenser 124 has partition plates 126. This results in the formation of chambers with overflows 127. In the front part, these chambers are connected by a line 128 with a water and pH tank 129, which has a device 130 for measuring the pH, a conductivity cell 131 arranged above the pH meter 130, and a drain valve 132. The water level measurement by conductivity measurement is automatically controlled by the drain valve 132 as a function of the level 131. The pipeline 133, which allows the condensate to be drained into the distillation system 134, is installed in the rear part of the condenser 124. The distillation system consists of the heat transfer medium circulation 135 between the circulation evaporator 136 of the distillation system and the exhaust gas heat exchanger of the power generator with the'connecting pipeline 137 and the circulation pump 138, the distillation system 139, with the bubble trays 140, the condenser 141 and the product discharges 142 and 143. The product discharge 142 from the condenser has a connecting line to the fuel supply tank of the power generator 144 , and the reflux valve 145 serves to feed the product reflux 146 into the upper distillation tray. The product discharge 143 from the upper column trays 147 of the distillation system 134 serves the purpose of discharging the final product. This line generally carries 70-90% of the total amount of product. The product removal line has an additional line for the addition of feedstock, which is located in the feed section 148. The feed section 148 consists of the feed hopper 49 with the metering device 150 for catalyst, the metering device 151 for the neutralizing agent lime or soda, the liquid residue feed 152 and the solid residue feed 153. The metering device 150 for the catalyst is usually connected with a big-bag emptying device 154, which is controlled by the temperature measuring device 155 after the high-speed chamber mixer. If the heat transferred in the high-speed chamber mixer 101 is not sufficiently converted to the middle distillate product, and if the temperature rises above a limit, then the addition of catalyst in the metering device 150 increases. The metering device 151 for the neutralizing agent is controlled by the pH sensor 130. If the pH falls below an input limit of around 7.5, the feed amount in the metering device 151 increases. The added amounts of feed residues 152 and 153 are likewise metered as a function of the level gage 156 in the separator 103. This ensures that the high-speed chamber mixture 101 always receives liquid mixtures from the separator 103 and that the system is prevented from running dry. It also ensures that the various feed materials and the associated variation of the reaction rates are alwavs compensated by variable addition, and the process is not interrupted. About 0.4 kWh of power for the cracking, evaporation and heating from the input temperature of 250°C to the reaction temperature of 300°C are needed in the oil circulation per kg of evaporated diesel oil in the case of waste oil and tars. If plastics are used as feed materials, the required power is almost twice as high, since these materials are fed in cold, and energy for melting is additionally required. In this regard, the addition of the catalyst is fundamentally important to the process. This catalyst is a sodium-aluminum silicate. The doping of a fully crystallized Y-molecule with sodium was determined to be optimum only for the plastics, bitumen, and waste oils. For biological feedstocks, such as fats and biological oils, doping with calcium was found to be optimum. For reactions with wood, doping with magnesium is necessary to produce high-quality diesel oil. For highly halogenated compounds, such as transformer oil and PVC, it is necessary to dope with potassium. The product of the system is diesel oil, because the product discharge from the circulation at 300-400°C leaves no other, lighter products behind in the system. 10% of this product is used to generate the process energy requirements in the form of electric current in a power-generating unit, and the portion used to generate power is the lighter fraction of the product obtained from the condenser. The product from the column thus does not have a lighter boiling fraction and completely satisfies the tank storage standards. Another advantage of this energy conversion is the simultaneous solution of the problems with the gas emerging from the vacuum pump, which is conveyed into the intake air. In addition, the generator satisfies the conditions of the combined heat and power generation, since the thermal energy of the exhaust gases is used to predry and preheat the feedstock. Figure 3 shows the central unit of the method of the invention and the device of the invention, the high-speed chamber mixer. 201 denotes the housing. 202 denotes the intake side with the flange. 203 and 204 denote the chambers contained in the high-speed chamber mixer. The chambers have different sizes in the standard design and the same size in the special design. Roller wheels 205 and 206 run eccentrically in the chambers and have 3 reinforcing ribs at the beginning, in the middle and at the end. The roller wheels are driven by the shaft 207, which is connected at one end with an electric motor or diesel engine 208. The shaft 207 is supported in special bearings 209, 210, 211, 212 made of sintered hard metal in clamping rings. A ball bearing 213 and a sealing bearing 214 are mounted at the end of the shaft. The housing is held together by the tightening screws 215. The discharge outlet 216 is connected with the flange 217. The flow plate cam is located between the two running wheels. The invention is explained in greater detail with reference to a specific embodiment. A high-speed chamber mixer with 120 kW of drive power conveys 2,000 L/h of intake oil through an intake line (2) and 300 kg of residual material in the form of waste oil and bitumen through the material feed (3), for a total of 2,300 L/h, into the delivery line (5), which opens tangentially into the separator (6) with a diameter of 800 mm. The high-speed chamber mixer (1) is connected with the separator by a connecting pipeline with a diameter of 200 mm. An automatically controlled control valve (55), which controls the pressure in the downstream apparatus, is installed in the connecting pipeline. The separator (3) has a diameter of 1,000 mm, and on the inside it has a venturi tube (4), which has a cross section at its narrowest point of 100 x 200 mm, lies against the inside wall, and likewise decreases the remaining overpressure and increases the separation effect. Above the separator, there is a safety tank (17) with a diameter of 2,000 mm. The separator has a level control device (56) with an oil level gage. The product vapor line for the diesel oil vapor that is produced is located at the top of the safety tank (17) and runs to the condenser, which has a capacity of 100 kW. A line with a diameter of 1.5 inches runs from the condenser to the distillation system (40) with a column diameter of 300 mm. All of the tanks are provided with flue gas external heating to facilitate the heatup phase. The pressure worm (8) with a diameter of 250 mm is located below the separator (17). It provides for the separation of the constituents of the feedstocks that cannot be converted to diesel oil. The pressure worm (8) is connected with the reducing pipe and valve (7) with a diameter of 80 mm. A temperature measuring device (6) is located at the base of the separator (17). It starts the operation of the pressure worm (8) when the temperature drops below a limit due to insulation by the residue. The pressure worm (8), which has a diameter of 80 mm and a conveying capacity of 10-20 kg/h, has a filter component (9) inside the tank, which allows the liquid fractions to flow back into the separation tank (8), and an electrically heated low-temperature carbonization component (13) outside the separation vessel (8) with a heating capacity of 45 kW, which allows the residual oil fractions to evaporate from the press cake. An increase in temperature to 500 C is provided for this purpose. The oil vapors escaping from the low-temperature carbonization worm (13) are conveyed to the safety tank (17) through the vapor line (16). List of Reference Numbers Figure 1: 1. high-speed chamber mixer 2. intake line of the high-speed chamber mixer 3. separator 4. venturi tubes 5. conical part of the separator 6. solid residue (slurry) 7. discharge valve 8. pressure worm 9. filter wall 10. product vapor return line 11. residue cake 12. heated worm 13. nozzle 14. hot product storage tank 15. product vapor return line 16. middle distillates 17. vapor tank 18. distillation tray 19. reflux channel 20. heater 21. insulation 22. exhaust sas line 23. power generator 24. condenser 25. cooling circulation 26. partition plates 27. overflow 28. water drain line 29. water and pH tank 30. pH meter 31. conductivity cell 32. drain valve 33. diesel oil pipeline 34. vacuum pump 35. heat transfer medium circulation 36. circulation evaporator 37. pipeline 38. circulation pump 39. distillation system 40. bubble trays 41. condenser 42. product discharge, generator 43. product discharge, final product 44. line to the power generator 45. reflux valve 46. product reflux 47. upper column trays 48. feed section for the addition of feedstock and residue 49. feed hopper 50. metering device for catalyst 51. metering device for neutralizing agent 52. liquid residue feed 53. solid residue feed 54. big-bag emptying device 55. temperature measuring device after the high-speed chamber mixer 56. level gage Figure 2: 101. high-speed chamber mixer 102. intake line of the high-speed chamber mixer 103. separator 104. venturi tubes 105. conical part of the separator 106. solid residue (slurry) 107. discharge valve 108. pressure worm 109. filter wall 110. product vapor return line 111. residue cake 112. heated worm 113. nozzle 114. hot product storage tank 115. product vapor return line 116. middle distillates 117. vapor tank 118. distillation tray 119. reflux channel 120. heater 121. insulation 122. exhaust gas line 123. power generator 124. condenser 125. cooling circulation 126. partition plates 127. overflow 128. water drain line 129. water and pH tank 130. pH meter 131. conductivity cell 132. drain valve 133. diesel oil pipeline 134. distillation system 135. heat transfer medium circulation 136. circulation evaporator 137. pipeline 138. circulation pump 139. distillation system 140. bubble trays 141. condenser 142. product discharge, generator 143. product discharge, final product 144. power generator 145. reflux valve 146. product reflux 147. upper column trays 148. feed section for the addition of feedstock and residue 149. feed hopper 150. metering device for catalyst 151. metering device for neutralizing agent 152. liquid residue feed 153. solid residue feed 154. big-bag emptying device 155. temperature measuring device after the high-speed chamber mixer 156. level sage Figure 3: 201. housing of the high-speed chamber mixer 202. intake side with flanae 203. chamber 1 in the high-speed chamber mixer 204. chamber 2 in the high-speed chamber mixer 205. eccentric roller mixer in chamber 1 206. eccentric roller mixer in chamber 2 207. drive shaft 208. electric motor or diesel engine 209. special bearing with sealing bearing left, 210. special bearing with ball bearing left 211. special bearing with ball bearing right 212. special bearing with sealing bearing right 213. friction bearing for flow plate cam 214. sealing bearing 215. tightening screws 216. discharge outlet 217. discharge flange 218. flow plate cam

Full Text

HIGH-SPEED CHAMBER MIXER FOR CATALYTIC OIL SUSPENSIONS AS A
REACTOR FOR THE DEPOLYMERIZATION AND POLYMERIZATION OF
HYDROCARBON-CONTAINING RESIDUES IN THE
CIRCULATION TO MIDDLE DISTILLATE
The invention concerns a method and a device for the extraction of hydrocarbon vapor from residues in the temperature range of 230-3 80 °C in the hot oil circulation with a single-stage or multistage mixing chamber, which realizes a pump with extremely low efficiency on the delivery side and the production of up to 95% vacuum on the intake side. In the process, the extracted hydrocarbons are depolymerized, deoxygenized and freed of the inorganic components of the molecule, such as halogens, sulfur and heavy metal atoms.
A depolymerization system with a hot oil circulation is known from German Patent No. 100 49 377 and German Published Patent Application No. 103 56 245.1. Here too, ion-exchanging catalysts are used in the hot oil circulation. The heat of reaction is supplied by heat transfer through the wall or by conduction by a pump with factional heat.
The disadvantage of these methods and devices in the case of German Patent No. 100 49 377 is the excessive temperature at the wall during the heat transfer, which results in pyrolytic reactions, and in the case of German Patent Application No. 103 56 245.1, the short residence time in a pump of less than one second, which is insufficient for the reaction of the residue with the catalyst oil. The actual reaction must then take place in the downstream equipment, which is possible only at significantly higher temperatures than if the reaction could take place relatively completely with a longer residence time in the pump.
Other disadvantages are the high pressure that develops in the pump and that can lead to clogging in the downstream, necessarily narrower, pipes, the possible cavitation in the pump

intake zone, especially in the case of substances that contain solids, and the possible clogging of the intake zone if this suction intake is not possible with relatively high negative pressure.
All of these disadvantages are now eliminated by the surprisingly discovered high-speed chamber mixer, and thus the quality of the process and the product and the safety of the plant are decisively improved. In this regard, the use of a system with rolls for the suction of gases in the application for realizing a hot oil circulation is completely novel. Specifically, only the principle of the liquid ring vacuum pump was previously known, according to which gases can be compressed to atmospheric pressure, and up to about 1.5 bars of overpressure can be used as a compressor. What was not known and what was surprisingly discovered is that this principle for the conveyance of liquids and liquid/gas mixtures can be used as a mixing reactor. By utilizing the extremely low efficiency and the production of mixing and frictional energy between the catalyst oil and the hydrocarbon-containing residue feed, this system is the ideal energy-transfer unit for the method and the device for the production of diesel oil from residues. This basic principle thus represents only a framework, which becomes the high-speed chamber mixer of the invention by virtue of the completely new design of the components for the load oil instead of gas. Thus, compared to the previous pumps in German Patent Application No. 103 56 245.1, an overpressure in the delivery line of 6-100 bars becomes a pressure load of 0.5-2.0 bars, and the maximum negative pressure in the intake line of 0.1 bar to avoid cavitation becomes a possible negative pressure of 0.95 bar, i.e., a 95% vacuum-
The high-speed chamber mixer with the connecting pipelines, the volume flow control valve and a separator forms a hot oil circulation, which, with the action of the molecularly fine, 100% crystalline catalyst, extracts the hydrocarbons from the preheated and dewatered

hydrocarbon-containing residues, and at the same time, depending on molecular length, the extracted hydrocarbons are depolymerized, polymerized, deoxygenized and freed of the inorganic components of the molecule, such as halogens, sulfur and heavy metal atoms. The product results from the reaction temperature of 250-320°Cin the middle distillate range, diesel fuel for use in diesel engines.
The basis of this process is the possible fast reaction process with intensive energy input with sufficient residence time, as is possible only in a high-speed chamber mixer. Pumping systems achieve only a very small fraction of this residence time and thus do not achieve the necessary reaction conditions and the low reaction temperatures associated therewith. In this process, of course, the goal is to keep the interval between the pyrolysis temperature and the catalytic depolymerization temperature as large as possible, i.e., to achieve the lowest possible reaction temperature.
In this regard, measurements showed that the average temperature with the high-speed chamber mixer is 60°C lower than with the same system but different conveyance systems, for example, a pumping system with centrifugal impellers. This results in a decisive improvement compared to the previously known systems, such as the system described in German Patent Application No. 103 56 245.1, especially with respect to the quality and odor of the product that is produced.
The uniformity of the middle distillates that are produced, which is apparent in the compressed curve of the gas chromatogram, the reduced energy input and, finally, in the completeness of the reaction, is significantly increased. The selectivity of the process increases significantly, i.e., the yield of middle distillate increases, and the fraction of separated carbon drops in the case of plant feedstocks. The fractions of light products

(odorous substances) are almost completely avoided.
Figure 1 shows the elements of the method.
A primary oil circulation is formed by the high-speed chamber mixer 1, its intake line 2 from the separator, and the return line to the separator 3. The separator 3 is a cyclone separator, which is formed by one or more venturi tubes 4, which are attached tangentially into the tank on the delivery side, and the return lines located below in the cylindrical part. The conical part 5 located below there serves to collect deposits of solid residues 6, which consist of the inorganic constituents.
A pressure of 0.5-2.0 bars overpressure is obtained on the delivery side, depending on the size of the high-speed chamber mixer 1, and a pressure of 0.9-0.05 bars absolute, i.e., a 10% to 95% vacuum, is obtained on the intake side, depending on the solids content. An automatically controlled discharge valve 7 is installed below the separator 3, i.e., below the conical part. This discharge valve 7 opens as a function of the temperature, i.e., as a function of the fraction of the inorganic constituents 6 of the material deposited there and thus allows the residue slurry 6 with the inorganic constituents to flow off into a pressure worm 8.
The pressure worm 8 has a filter wall 9, through which the oil constituent 10 is returned, and thus forms a residue cake 11 towards the top, which enters a second conveyance device 12 with external heating. This conveyance device 12 has a nozzle 13 at the end, by which the inorganic solid residue, heated to 400-500°C, enters a storage tank 14, which has a connecting line 15 to the separator. The evaporated middle distillates 16 are returned to the process through this connecting line 15.
A vapor tank 17 is located above the separator 3. The purification elements of the vapor tank 17 consist of one or more distillation trays 18 with a reflux channel 19, a heater 20

and insulation 21 around the tank, into which preferably exhaust gas 22 from the power generator 23 is introduced. This vapor tank 17 is connected with a condenser 24, which is cooled with cooling water from the cooling circulation 25. The condenser 24 has partition plates 26.
This results in the formation of chambers with overflows 27 to allow water to settle. In the front part, these chambers are connected by a line 28 with a water and pH tank 29, which has a device 30 for measuring the pH, a conductivity cell 31 arranged above the pH meter 30, and a drain valve 32. The amount of water in the tank is automatically controlled by the drain valve 32 as a function of the level 31.
The pipeline 33, which allows the condensate to be drained into the distillation system 34, is installed in the rear part of the condenser 24. The distillation system consists of the heat transfer medium circulation 35 between the circulation evaporator 36 of the distillation system and the exhaust gas heat exchanger of the power generator with the connecting pipeline 37 and the circulation pump 38, the distillation system 34, the distillation charges 39, with the bubble trays 40, the condenser 41 and the product discharges 42 and 43.
The product discharge 42 from the condenser serves as the fuel supply of the power generator 23 via the line 44, and the reflux valve 45 serves to feed the product reflux 46 into the upper distillation tray. The product discharge 43 from the upper column trays 47 of the distillation system 34 serves the purpose of discharging the final product. This fraction generally contains 70-90% of the total amount of product.
The product that is removed is replaced by the addition of feedstock in the feed section 48. The feed section 48 consists of the feed hopper 49 with the metering device 50 for catalyst, the metering device 51 for the neutralizing agent lime or soda, the liquid residue feed

52 and the solid residue feed 53.
The metering device 50 for the catalyst is usually connected with a big-bag emptying device 54, which is controlled by the temperature measuring device 55 after the high-speed chamber mixer. If the heat transferred in the high-speed chamber mixer 1 is not sufficiently converted to the1 middle distillate product, and if the temperature rises above a limit, then the addition of catalyst in the metering device 50 increases.
The metering device 51 for the neutralizing agent is controlled by the pH sensor 30. If the pH falls below an input limit of around 7.5, the feed amount in the metering device 51 increases. The added amounts of feed residues 52 and 53 are likewise metered as a function of the level gage 56 in the separator 3.
This ensures that the high-speed chamber mixer 1 always receives liquid mixtures from the separator 3 and that the system is prevented from running dry. It also ensures that the various feed materials and the associated variation of the reaction rates are always compensated by variable addition, and the process is not interrupted.
About 0.4 kWh of power for the cracking, evaporation and heating from the input temperature of 250°C to the reaction temperature of 300°C are needed in the oil circulation per kg of evaporated diesel oil in the case of waste oil and tars. If plastics are used as feed materials, the required power is almost twice as high, since these materials are fed in cold, and energy for melting is additionally required.
In this regard, the addition of the catalyst is fundamentally important to the process. This catalyst is a sodium-aluminum silicate. The doping of a fully crystallized Y-molecule with sodium was determined to be optimum only for the plastics, bitumen and waste oils. For biological feedstocks, such as fats and biological oils, doping with calcium was found to be

optimum. For reactions with wood, doping with magnesium is necessary to produce high-quality diesel oil. For highly halogenated compounds, such as transformer oil and PVC, it is necessary to dope with potassium.
The product of the system is diesel oil, because the product discharge from the circulation at 300-400°C leaves no other, lighter products behind in the system. 10% of this product is used to generate the process energy requirements in the form of electric current in a power-generating unit, and the portion used to generate power is the lighter fraction of the product obtained from the condenser.
The product from the column thus does not have a lighter boiling fraction and completely satisfies the tank storage standards. Another advantage of this energy conversion is the simultaneous solution of the problems with the gas emerging from the vacuum pump, which is conveyed into the intake air.
In addition, the generator satisfies the conditions of the combined heat and power generation, since the thermal energy of the exhaust gases is used to predry and preheat the feedstock.
The device of the invention is explained with reference to Figure 2:
The high-speed chamber mixer 101 has an intake line 102, which is connected with the separator 103 by a pipeline. It is designed for a negative pressure of 0.95 bar. The separator 103 is a cyclone separator, which is formed by one or more venturi tubes 104, which are attached tangentially into the tank on the delivery side, and the return lines located below in the cylindrical part.
The conical part 105 located below there has a discharge orifice 106 with a discharge valve 107. A pressure line that is designed for an overpressure of 0.5-1.5 bars is arranged on

the delivery side of the high-speed chamber mixer. An automatically controlled discharge valve 7 is installed below the separator 103, i.e., below the conical part. This discharge valve 107 has a temperature sensor, which is designed for a switching temperature of 100-150°C.
A pressure worm 108 is arranged below there, which is designed to convey residue slurry from the discharge valve and has a temperature resistance of 200°G The pressure worm 108 has a filter wall 109 with an oil outlet 110 and an upper pressure worm part for the residue cake 111 and a connecting pipeline to a second conveyance device 112 with external heating.
This conveyance device 112 has a nozzle 113 at the end. The worm wall is designed for a temperature of 400-500 °C, which is produced by the external heater, e.g., an electric heater. The downstream storage tank 114 also has temperature resistance up to 400°C and is designed as a solids tank. The tank 114 has a connecting line 115 to the separator for returning the evaporated hydrocarbon vapor.
A vapor tank 117 is located above the separator 102. The purification elements of the vapor tank 117 consist of one or more distillation trays 118 with a reflux channel 119, a heater 120 and insulation 121 around the tank, with an exhaust gas connecting line 122 to the power generator 123, by which exhaust gas is introduced into the tank. This vapor tank 117 is connected with a condenser 124. The condenser has a connecting line by which it is connected with cooling water from the cooling circulation 125. The condenser 124 has partition plates 126.
This results in the formation of chambers with overflows 127. In the front part, these chambers are connected by a line 128 with a water and pH tank 129, which has a device 130 for measuring the pH, a conductivity cell 131 arranged above the pH meter 130, and a drain

valve 132. The water level measurement by conductivity measurement is automatically controlled by the drain valve 132 as a function of the level 131.
The pipeline 133, which allows the condensate to be drained into the distillation system 134, is installed in the rear part of the condenser 124. The distillation system consists of the heat transfer medium circulation 135 between the circulation evaporator 136 of the distillation system and the exhaust gas heat exchanger of the power generator with the'connecting pipeline 137 and the circulation pump 138, the distillation system 139, with the bubble trays 140, the condenser 141 and the product discharges 142 and 143.
The product discharge 142 from the condenser has a connecting line to the fuel supply tank of the power generator 144 , and the reflux valve 145 serves to feed the product reflux
146 into the upper distillation tray. The product discharge 143 from the upper column trays
147 of the distillation system 134 serves the purpose of discharging the final product. This line
generally carries 70-90% of the total amount of product.
The product removal line has an additional line for the addition of feedstock, which is located in the feed section 148. The feed section 148 consists of the feed hopper 49 with the metering device 150 for catalyst, the metering device 151 for the neutralizing agent lime or soda, the liquid residue feed 152 and the solid residue feed 153.
The metering device 150 for the catalyst is usually connected with a big-bag emptying device 154, which is controlled by the temperature measuring device 155 after the high-speed chamber mixer. If the heat transferred in the high-speed chamber mixer 101 is not sufficiently converted to the middle distillate product, and if the temperature rises above a limit, then the addition of catalyst in the metering device 150 increases.
The metering device 151 for the neutralizing agent is controlled by the pH sensor 130.

If the pH falls below an input limit of around 7.5, the feed amount in the metering device 151 increases. The added amounts of feed residues 152 and 153 are likewise metered as a function of the level gage 156 in the separator 103.
This ensures that the high-speed chamber mixture 101 always receives liquid mixtures from the separator 103 and that the system is prevented from running dry. It also ensures that the various feed materials and the associated variation of the reaction rates are alwavs compensated by variable addition, and the process is not interrupted.
About 0.4 kWh of power for the cracking, evaporation and heating from the input temperature of 250°C to the reaction temperature of 300°C are needed in the oil circulation per kg of evaporated diesel oil in the case of waste oil and tars. If plastics are used as feed materials, the required power is almost twice as high, since these materials are fed in cold, and energy for melting is additionally required.
In this regard, the addition of the catalyst is fundamentally important to the process. This catalyst is a sodium-aluminum silicate. The doping of a fully crystallized Y-molecule with sodium was determined to be optimum only for the plastics, bitumen, and waste oils.
For biological feedstocks, such as fats and biological oils, doping with calcium was found to be optimum. For reactions with wood, doping with magnesium is necessary to produce high-quality diesel oil. For highly halogenated compounds, such as transformer oil and PVC, it is necessary to dope with potassium.
The product of the system is diesel oil, because the product discharge from the circulation at 300-400°C leaves no other, lighter products behind in the system.
10% of this product is used to generate the process energy requirements in the form of electric current in a power-generating unit, and the portion used to generate power is the

lighter fraction of the product obtained from the condenser.
The product from the column thus does not have a lighter boiling fraction and completely satisfies the tank storage standards. Another advantage of this energy conversion is the simultaneous solution of the problems with the gas emerging from the vacuum pump, which is conveyed into the intake air. In addition, the generator satisfies the conditions of the combined heat and power generation, since the thermal energy of the exhaust gases is used to predry and preheat the feedstock.
Figure 3 shows the central unit of the method of the invention and the device of the invention, the high-speed chamber mixer. 201 denotes the housing. 202 denotes the intake side with the flange. 203 and 204 denote the chambers contained in the high-speed chamber mixer. The chambers have different sizes in the standard design and the same size in the special design. Roller wheels 205 and 206 run eccentrically in the chambers and have 3 reinforcing ribs at the beginning, in the middle and at the end.
The roller wheels are driven by the shaft 207, which is connected at one end with an electric motor or diesel engine 208. The shaft 207 is supported in special bearings 209, 210, 211, 212 made of sintered hard metal in clamping rings. A ball bearing 213 and a sealing bearing 214 are mounted at the end of the shaft. The housing is held together by the tightening screws 215. The discharge outlet 216 is connected with the flange 217. The flow plate cam is located between the two running wheels.
The invention is explained in greater detail with reference to a specific embodiment. A high-speed chamber mixer with 120 kW of drive power conveys 2,000 L/h of intake oil through an intake line (2) and 300 kg of residual material in the form of waste oil and bitumen through the material feed (3), for a total of 2,300 L/h, into the delivery line (5), which opens

tangentially into the separator (6) with a diameter of 800 mm.
The high-speed chamber mixer (1) is connected with the separator by a connecting pipeline with a diameter of 200 mm. An automatically controlled control valve (55), which controls the pressure in the downstream apparatus, is installed in the connecting pipeline.
The separator (3) has a diameter of 1,000 mm, and on the inside it has a venturi tube (4), which has a cross section at its narrowest point of 100 x 200 mm, lies against the inside wall, and likewise decreases the remaining overpressure and increases the separation effect. Above the separator, there is a safety tank (17) with a diameter of 2,000 mm. The separator has a level control device (56) with an oil level gage.
The product vapor line for the diesel oil vapor that is produced is located at the top of the safety tank (17) and runs to the condenser, which has a capacity of 100 kW. A line with a diameter of 1.5 inches runs from the condenser to the distillation system (40) with a column diameter of 300 mm. All of the tanks are provided with flue gas external heating to facilitate the heatup phase.
The pressure worm (8) with a diameter of 250 mm is located below the separator (17). It provides for the separation of the constituents of the feedstocks that cannot be converted to diesel oil. The pressure worm (8) is connected with the reducing pipe and valve (7) with a diameter of 80 mm. A temperature measuring device (6) is located at the base of the separator (17). It starts the operation of the pressure worm (8) when the temperature drops below a limit due to insulation by the residue.
The pressure worm (8), which has a diameter of 80 mm and a conveying capacity of 10-20 kg/h, has a filter component (9) inside the tank, which allows the liquid fractions to flow back into the separation tank (8), and an electrically heated low-temperature carbonization

component (13) outside the separation vessel (8) with a heating capacity of 45 kW, which allows the residual oil fractions to evaporate from the press cake. An increase in temperature to 500 C is provided for this purpose. The oil vapors escaping from the low-temperature carbonization worm (13) are conveyed to the safety tank (17) through the vapor line (16).

List of Reference Numbers
Figure 1:
1. high-speed chamber mixer
2. intake line of the high-speed chamber mixer
3. separator
4. venturi tubes
5. conical part of the separator
6. solid residue (slurry)
7. discharge valve
8. pressure worm
9. filter wall
10. product vapor return line
11. residue cake
12. heated worm
13. nozzle
14. hot product storage tank
15. product vapor return line
16. middle distillates

17. vapor tank
18. distillation tray
19. reflux channel
20. heater

21. insulation
22. exhaust sas line
23. power generator
24. condenser
25. cooling circulation
26. partition plates
27. overflow
28. water drain line
29. water and pH tank
30. pH meter
31. conductivity cell
32. drain valve
33. diesel oil pipeline
34. vacuum pump
35. heat transfer medium circulation
36. circulation evaporator

37. pipeline
38. circulation pump
39. distillation system
40. bubble trays
41. condenser
42. product discharge, generator
43. product discharge, final product

44. line to the power generator
45. reflux valve
46. product reflux
47. upper column trays
48. feed section for the addition of feedstock and residue
49. feed hopper
50. metering device for catalyst
51. metering device for neutralizing agent
52. liquid residue feed
53. solid residue feed
54. big-bag emptying device
55. temperature measuring device after the high-speed chamber mixer
56. level gage
Figure 2:
101. high-speed chamber mixer
102. intake line of the high-speed chamber mixer
103. separator
104. venturi tubes
105. conical part of the separator
106. solid residue (slurry)
107. discharge valve
108. pressure worm

109. filter wall
110. product vapor return line
111. residue cake
112. heated worm
113. nozzle
114. hot product storage tank
115. product vapor return line
116. middle distillates
117. vapor tank
118. distillation tray
119. reflux channel
120. heater
121. insulation
122. exhaust gas line
123. power generator
124. condenser
125. cooling circulation
126. partition plates

127. overflow
128. water drain line
129. water and pH tank
130. pH meter
131. conductivity cell

132. drain valve
133. diesel oil pipeline
134. distillation system
135. heat transfer medium circulation
136. circulation evaporator
137. pipeline
138. circulation pump
139. distillation system
140. bubble trays
141. condenser
142. product discharge, generator
143. product discharge, final product
144. power generator
145. reflux valve
146. product reflux
147. upper column trays
148. feed section for the addition of feedstock and residue
149. feed hopper
150. metering device for catalyst
151. metering device for neutralizing agent
152. liquid residue feed
153. solid residue feed
154. big-bag emptying device

155. temperature measuring device after the high-speed chamber mixer
156. level sage
Figure 3:
201. housing of the high-speed chamber mixer
202. intake side with flanae
203. chamber 1 in the high-speed chamber mixer
204. chamber 2 in the high-speed chamber mixer
205. eccentric roller mixer in chamber 1
206. eccentric roller mixer in chamber 2
207. drive shaft
208. electric motor or diesel engine
209. special bearing with sealing bearing left,
210. special bearing with ball bearing left
211. special bearing with ball bearing right
212. special bearing with sealing bearing right
213. friction bearing for flow plate cam
214. sealing bearing
215. tightening screws
216. discharge outlet
217. discharge flange
218. flow plate cam

Documents:

1290-CHE-2006 CORRESPONDENCE OTHERS 05-01-2010.pdf

1290-CHE-2006 CORRESPONDENCE OTHERS 27-08-2009.pdf

1290-CHE-2006 FORM-3 05-01-2010.pdf

1290-CHE-2006 OTHER PATENT DOCUMENT 05-01-2010.pdf

1290-CHE-2006 CLAIMS GRANTED.pdf

1290-che-2006 correspondence others 03-08-2009.pdf

1290-CHE-2006 EXAMINATION REPORT REPLY RECIEVED 03-08-2009.pdf

1290-CHE-2006 FORM 18.pdf

1290-CHE-2006 FORM 2.pdf

1290-CHE-2006 FORM 3.pdf

1290-CHE-2006 OTHER DOCUMENT 03-08-2009.pdf

1290-CHE-2006 PCT SEARCH REPORT 03-08-2009.pdf

1290-CHE-2006 PETITIONS.pdf

1290-CHE-2006 POWER OF ATTORNEY.pdf

1290-che-2006-abstract.pdf

1290-che-2006-claims.pdf

1290-che-2006-correspondnece-others.pdf

1290-che-2006-description(complete).pdf

1290-che-2006-drawings.pdf

1290-che-2006-form 1.pdf

1290-che-2006-form 3.pdf

1290-che-2006-form 5.pdf

1290-che-2006-priority-document.pdf

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Patent Number

238155

Indian Patent Application Number

1290/CHE/2006

PG Journal Number

5/2010

Publication Date

29-Jan-2010

Grant Date

21-Jan-2010

Date of Filing

25-Jul-2006

Name of Patentee

KOCH, CHRISTIAN

Applicant Address

SCHULSTRASSE 8, 96155 BUTTENHEIM. GERMANY

Inventors:

#	Inventor's Name	Inventor's Address
1	KOCH, CHRISTIAN	SCHULSTRASSE 8, D-96155 BUTTENHEIM. GERAMANY

PCT International Classification Number

C10G,C10G07/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10 2005 056 735.5	2005-11-29	Germany