Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
  • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
  • F23G7/12—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of plastics, e.g. rubber
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B7/00—Halogens; Halogen acids
  • C01B7/01—Chlorine; Hydrogen chloride
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

• the invention relates to a method for the thermal recycling of old PVC with heat recovery and recovery of anhydrous hydrogen chloride by burning the old PVC, in an oxygen-containing atmosphere, with addition of chlorine in the form of gaseous chlorine and / or chlorinated hydrocarbons, and a device to carry out the method.
• PVC-containing wastes make the thermal recycling more expensive in the previously known processes Chlorine removal or the presence of chlorine or chloride ions in high-temperature gasification significantly disrupt the reaction mechanism of synthesis gas production.
• WO-A 88/08020 teaches in the pyrolysis of plastic waste with PVC components under an inert gas atmosphere to remove the hydrogen chloride by quenching with water.
• JP-A 56/089821 and DE-A 2941393 describe processes for the pyrolysis of waste PVC in which the hydrogen chloride is removed with aqueous bases. In the process according to JP-A 53/060974, the hydrogen chloride is recovered as a 35% aqueous solution.
• the invention relates to a process for the thermal recycling of waste PVC with heat recovery and recovery of anhydrous hydrogen chloride, characterized in that a) the waste PVC is burned in the presence of oxygen, the amount of gaseous chlorine and / or chlorinated hydrocarbons are admixed so that together with the hydrogen or chlorine content of the fuel in the mixture there is a total atomic ratio of hydrogen to chlorine of at least 1: 1, b) the combustion gas with recovery of a large part of the released heat of combustion to 500 to 1000 ° C cools and if necessary after filtering, c) by injecting aqueous hydrochloric acid, the chlorine hydrogen concentration corresponds to the saturation concentration at the prevailing pressures and temperatures, cools to 50 to 120 ° C., the majority of the combustion water formed condenses out and any solid precipitates which occur are filtered off from the aqueous hydrochloric acid by hydrolysis of volatile inorganic compounds, d) further cooling the combustion gas to temperatures of -5 to + 10 ° C. by direct heat exchange,
• the old PVC can be shredded before combustion. It is preferably ground to a grain size of about 1 to 5 mm in order to prevent the burner lance from being moved.
• the old PVC can be conveyed into the combustion chamber using common methods. For example, by pneumatic conveying and atomization with oxygen and, if appropriate, chlorine gas as propellant (FIG. 3), by hydraulic conveyance with water as the transport medium, by injection as a suspension in chlorinated hydrocarbons (FIG. 2) or by extrusion at elevated temperature with conveyance via a screw conveyor ( Figure 4).
• the combustion takes place in a cooled metal combustion chamber.
• the old PVC is preferably reacted with an oxygen source which contains more than 90% by volume of molecular oxygen, particularly preferably at pressures of 3 to 15 bar.
• an excess of oxygen is set such that the combustion gas leaving the combustion chamber has a chlorine content of 0.2 to 2.0% by volume. , most preferably 0.5 to 1.5% by volume.
• the combustion is preferably carried out at a flame temperature of 2000 to 2500 ° C.
• the residence time of the mixture in the combustion chamber is preferably 30 to 60 seconds.
• the admixture of gaseous chlorine and / or highly chlorinated chlorinated hydrocarbons is preferably carried out in such quantities that, together with the hydrogen or chlorine content of the combustible material, the mixture has a total atomic ratio of hydrogen to chlorine of 1.0: 1 to 2, 0: 1, particularly preferably from 1.2: 1 to 1.5: 1.
• chlorinated hydrocarbon admixtures there are in particular compounds which are inevitable in the production of valuable target products, such as high boilers from the production of vinyl chloride or 1,2-dichloropropane from the production of propylene oxide and compounds whose sensible disposal per ⁇ e is extremely problematic or for which there is no further use due to the CFC ban, such as carbon tetrachloride from methane chlorination or from the methyl chloride chlorination which takes place via the intermediate step of methanol esterification or from a C 3 hydrocarbon perchlorination.
• the combustion gases generated in the flame are cooled by indirect cooling to 500 to 1000 ° C, preferably to 700 to 900 ° C.
• the indirect cooling takes place by heat exchange with the double-walled combustion chamber, which is supplied with hot water at a suitable pressure, with recovery of a large part of the released heat of combustion as medium pressure steam.
• the combustion gases are optionally passed through suitable gas filters, for example ceramic filters, in order to separate solid particles which are contained in the old PVC as thermally and chemically stable additives from the combustion gas.
• the combustion gas treated in this way is then passed into a quenching device and there by injecting aqueous hydrochloric acid, the hydrogen chloride concentration of which corresponds to the saturation concentration at the pressures and temperatures present, to 50 to 120 ° C., preferably 80 to 100 ° C. cooled down.
• the aqueous hydrochloric acid is circulated through a buffer tank (gas / liquid separator) and a circuit cooler (water cooler). In this cooling step, most of the combustion water formed condenses out of the combustion gas.
• the solid particles formed by hydrolysis from volatile inorganic compounds, which were formed by chemical reaction from additives in the old PVC during the combustion process, are optionally separated off via a filter located in the quench circuit flow.
• the combustion gas is then cooled in a further direct cooling step to temperatures of -5 to + 10 ° C., preferably 0 to 2 ° C., as a result of which residual water condenses out of the combustion gas stream as hydrochloric acid.
• the burning For this purpose, the make-up gas is introduced from the buffer tank of the first cooling stage into a further washing-cooling circuit, consisting of an indirect heat exchanger, which preferably contains brine at a suitable temperature as the coolant, and a gas / liquid separator.
• the residual water of the combustion gas stream which condenses out as hydrochloric acid in this cooling stage is pumped into the buffer tank of the upstream cooling stage, where the hydrochloric acid is discharged from the system together with the combustion water condensed out in the form of hydrochloric acid.
• the almost water-free (H 2 ⁇ content ⁇ 50 volppm) combustion gas obtained with the process according to the invention consists, in addition to a little (. ⁇ 2.0 vol%) chlorine and excess oxygen, essentially of CO 2 and HC1.
• This hydrogen chloride gas stream can now be recycled in chemical synthesis without further treatment or without separation of inert gas, after aerosol mist separation and preheating above the dew point.
• the hydrogen chloride obtained in the process according to the invention is preferably fed to an ethylene oxychlorination per se or together with hydrogen chloride from a 1,2-dichloroethane pyrolysis plant.
• the process according to the invention for the thermal recycling of old PVC not only achieves considerable savings in the energy-intensive production of chlorine, but rather the majority of the energy content of the polymer molecule, which is introduced via elemental chlorine and ethylene or the intermediate stage vinyl chloride PVC is at the highest possible level, that is, recovered at a technically interesting temperature level.
• Another object of the invention is a device for performing the method according to the invention, which has a combustion unit with a cooling device and two Cooling circuits connected in series are equipped with devices for gas / liquid separation, characterized in that the device for combustion consists of a reactor 3, which is surrounded by a cooling jacket 4, which is connected to a steam drum 5 to recover the combustion energy, and with a burner 2 and a charging device 1 for supplying the reactants to be reacted in the reactor 3 and equipped via line 9 and an optionally interposed gas filter 10, with the quenching device 13 of the first cooling circuit, which, connected in a circuit, with a quench device 13, a gas / liquid separator 15, a quench circuit pump 17, a water meter 21 and optionally a candle filter 18, the separator 15 being connected via line 23 to the separator 24 of the second cooling circuit, which, switched in a circle, with a Ga s / liquid separator 24, a pump 26 and a heat exchanger 27 is equipped, the separator 24 being provided with a line 29 for
• FIG. 1 shows the flow diagram of a preferred embodiment of the device according to the invention.
• the feed mixture consisting of ground old PVC, chlorinated hydrocarbon or water, oxygen and / or chlorine gas, is introduced into the burner 2 in a required ratio of amounts to one another according to FIGS.
• the reaction takes place in the reactor 3 at 8 bar overpressure, in the flame at temperatures up to 2500 ° C. and a residence time of 40 seconds.
• the heat of reaction released by the exothermic reaction is removed by evaporating hot water which is located in the reactor cooling jacket 4. This evaporative cooling takes place via a thermosiphon circuit, a steam / hot water mixture rising into the steam drum 5 via line 7. There is phase separation.
• the generated 20 bar of water vapor is released under pressure control from the steam drum 5 via line 33 into the steam network, while the hot water flows back via line 6 into the reactor cooling jacket.
• boiler feed water is added via line 8 in the amounts in which amounts of water vapor are removed from the system.
• the gaseous reaction mixture cools down and leaves the reactor 3 via line 9 at a temperature of 900-950 ° C.
• inorganic solid particles which are present as additives in the old PVC are separated from the reaction mixture and discharged via line 11.
• the filtered gas mixture passes via line 12 to the quenching device 13, in which the reaction gas is quenched to 80 to 90 ° C. by injecting concentrated hydrochloric acid via line 16.
• the concentrated hydrochloric acid arises from the condensation of water vapor from the reaction mixture, an approximately 40% hydrochloric acid being formed in accordance with the pressure and temperature by dissolving hydrogen chloride gas from the reaction mixture into the water of condensation.
• the mixture of quench liquid / reaction gas reaches the separator 15 via line 14. Phase separation takes place here.
• the liquid phase is pumped in line 16 with the quench liquid circulation pump 17 via a candle filter 18 and the water cooler 21 to the quench 13 with constant cooling in a circuit.
• the gas phase in the separator 15 - consisting essentially of carbon dioxide, hydrogen chloride, excess oxygen, approximately 0.8% by volume of chlorine gas and residual moisture - flows via line 23 to the separator 24, which is filled with concentrated hydrochloric acid, which is fed via line 25 by means of the Pump 26 with cooling in the heat exchanger 27 to -8 to 0 ° C - the heat exchanger 27 is charged with -10 degrees cooling brine - is driven in a circle over the separator 24.
• the residual water condenses out of the reaction mixture, which results in an approximately 42% hydrochloric acid by dissolving in hydrogen chloride gas under the prevailing pressure and temperature conditions.
• hydrochloric acid is pressed in a level-controlled manner depending on the level in the separator 24 via line 28 into the separator 15. The discharge of the entire approx. 40% hydrochloric acid takes place at a level-controlled depending on the level in the separator 15 via line 20.
• the gas mixture which leaves the separator 24 via line 29 contains, in addition to carbon dioxide, excess oxygen, approx. 0.8 vol% chlorine gas and approx. 30 volppm water hydrogen chloride and becomes 30 after passing through an aerosol mist separator - separated hydrochloric acid aerosols Line 34 discharged - and after preheating to 150 ° C in the heat exchanger 31, which is operated with 15 bar steam, pressure-controlled at about 7.5 bar overpressure via line 32 for oxychlorination.
• FIGS. 2 to 4 show preferred embodiments for conveying the old PVC or introducing the reactants into the reactor and the charging device 1.
• Figure 2 Injection of waste PVC as a suspension in chlorinated hydrocarbons or water (hydraulic conveying).
• Milled old PVC from a silo container or the like is fed via line 35.
• the stirrer tank 36 which is equipped with a stirrer motor 37 and stirrer 38 and is pre-filled with appropriate amounts of chlorinated hydrocarbon or water via line 39, with stirring.
• the suspended suspension flows via line 40 to the suction side of the pump 41, which then presses the suspension into the burner 2 via line 42 - the suspension can be pumped in a circle via line 42a.
• Oxygen is fed via line 43 and, if necessary, chlorine gas via line 44 into the burner 2 in the amounts claimed.
• the starting material mixture is ignited at the burner mouth with a fuse or a spark plug, whereupon the reaction according to the invention takes place in the reactor 3, which is surrounded by a cooling jacket 4.
• the reaction products leave the reactor 3 via line 9.
• Ground PVC is added via line 35 to a metering screw 45, which is equipped with a motor 46, and from there it is conveyed via line 47 into line 48, in which oxygen and possibly all or part of the chlorine gas thereof - via line 49 conveyed - as propellant, press the old PVC into burner 2 via line 50.
• Chlorine gas can also flow to burner 2 via line 51.
• the educt mixture is ignited thermally or electrically, whereupon the reaction takes place in the reactor 3, which is surrounded by a cooling jacket 4.
• the reaction mixture leaves reactor 3 via line 9.
• Ground PVC is added to the extruder 52 via line 35 via a filling funnel.
• the extruder 52 is provided with an electric heating coil 53, a screw conveyor 54 and a spray head 55.
• the old PVC is heated, homogenized, plasticized and injected into the burner 2 by means of the transport screw 54 via the spray head 55.
• Oxygen is introduced into the burner 2 via line 56, chlorine gas via line 57 and optionally chlorine hydrocarbon via line 58.
• the educt mixture is ignited electrically or thermally at the burner mouth, whereupon the reaction according to the invention takes place in the reactor 3, which is surrounded by a cooling jacket 4.
• the reaction mixture leaves reactor 3 via line 9.
• the waste PVC had a grain size of 1.5 mm.
• the injection into the burner was carried out pneumatically using the two gas streams.
• the ignition was carried out by means of a spark plug on the burner mouth. The result was a stable flame that temperature of> 2200 ° C. By evaporating hot water in the double jacket of the combustion chamber, the combustion gas cooled to 850 ° C.
• the steam production was 700 kg / h at 20 bar overpressure, ie around 70% of the enthalpy of combustion, which is -3650 kcal / kg PVC conversion, was recovered as medium-pressure steam. In other words, this resulted in a specific steam generation of 5.6 tons of 20 bar steam per ton of burned PVC.
• the flue gases were cooled to 90 ° C. in the first cooling stage by injecting 800 kg / h of 39% hydrochloric acid, which was circulated through a buffer tank and water cooler. 15.1 kg / h of 39% hydrochloric acid condensed out.
• the combustion gas emerging from the buffer tank then had the following composition:
• This gas was cooled to + 1 ° C in a subsequent cooling stage, consisting of hydrochloric acid circuit with a heat exchanger that was cooled with -10 degree brine and a gas / liquid separator, with a further 3.8 kg / h approx. 42% condensed hydrochloric acid.
• This hydrochloric acid was pumped to the 1st buffer tank and there level-controlled with the hydrochloric acid from l. Cooling stage removed from the system. The HCl loss over the discharged hydrochloric acid was 7.5 kg / h.
• the combustion gas leaving the gas / liquid separator had the following composition:
• a mixture of 100 kg / h old PVC with a grain size of 2 mm was used, consisting of 90% hard PVC, 8% soft PVC and 2% vinyl chloride-vinyl acetate copolymers with a 10% vinyl acetate content, and 60 kg / h CCI 4 as a chlorine source in order to set an H / Cl atomic ratio of 1.5.
• the composition of the old PVC mixture was: 82.8% PVC
• the quench cooling circuit was passed over two mutually operated corrosion-resistant candle filters.
• the combustion gas emerging from the buffer container had the following composition:
• the gas emerging from the gas / liquid separator had the following composition:

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Citations (1)

• 1992
  • 1992-07-17 DE DE4223663A patent/DE4223663A1/de not_active Withdrawn
• 1993
  • 1993-07-15 WO PCT/EP1993/001862 patent/WO1994002538A1/de active IP Right Grant
  • 1993-07-15 EP EP93915921A patent/EP0650506B1/de not_active Expired - Lifetime
  • 1993-07-15 DE DE59302701T patent/DE59302701D1/de not_active Expired - Fee Related

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