EP0784661A1 - Procede pour la recuperation de matieres premieres synthetiques et de composants de carburants provenant de matieres plastiques hors d'usage ou de dechets - Google Patents
Procede pour la recuperation de matieres premieres synthetiques et de composants de carburants provenant de matieres plastiques hors d'usage ou de dechetsInfo
- Publication number
- EP0784661A1 EP0784661A1 EP95935425A EP95935425A EP0784661A1 EP 0784661 A1 EP0784661 A1 EP 0784661A1 EP 95935425 A EP95935425 A EP 95935425A EP 95935425 A EP95935425 A EP 95935425A EP 0784661 A1 EP0784661 A1 EP 0784661A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- depolymerizate
- patent application
- reactor
- coal
- waste plastics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000008569 process Effects 0.000 title claims abstract description 41
- 239000004033 plastic Substances 0.000 title claims abstract description 29
- 229920003023 plastic Polymers 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- 239000000446 fuel Substances 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 title claims abstract description 8
- 239000003245 coal Substances 0.000 claims abstract description 15
- 239000010426 asphalt Substances 0.000 claims abstract description 13
- 238000004939 coking Methods 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000004568 cement Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 24
- 238000011010 flushing procedure Methods 0.000 description 20
- 239000000571 coke Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen halides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/005—Coking (in order to produce liquid products mainly)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
Definitions
- the invention relates to a process for obtaining chemical raw materials and / or liquid fuel components from waste or waste plastics according to patent application P 43 11 034.7 and the use of a depolymerizate produced by this process.
- the subject of patent application P 43 11 034.7 is a process in which the old or waste plastics are depolymerized at elevated temperature, possibly with the addition of a liquid auxiliary phase, a solvent or solvent mixture, and the resulting gaseous and condensable depolymerization products (condensate) and a pumpable viscous depolymerization bottom product (depolymerized product) is drawn off in separate substreams and condensate and depolymerized product are worked up separately from one another.
- the process parameters are preferably selected so that the highest possible proportion of condensate is produced.
- a depolymerizate in an amount of between 15 and 85% by weight, based on the plastic mixture used, depending on the composition and the particular requirements in that of the bottom phase hydrogenation, pressure gasification, smoldering (pyrolysis) and / or others Processes and uses of product streams to be supplied can be divided.
- a condensate in an amount of 10 to 80, preferably 20 to 50 wt .-%, based on the plastic mixture used, which boils in a range between 25 ° C and 520 ° C and up to about 1,000 ppm can contain organically bound chlorine.
- the condensate can be z. B. by hydrotreating on firmly arranged commercially available Co-Mo or Ni-Mo catalysts into a high-quality synthetic crude oil (syncrude) or also directly in chlorine-tolerant chemical-technical or refining processes as a hydrocarbon-containing base substance.
- the hydrogen chloride can, for. B. wash out with water from the gas stream to obtain a 30% aqueous hydrochloric acid.
- the residual gas can be hydrogenated in a bottom phase hydrogenation or in a hydrotreater from the organically bound chlorine and z. B. the refinery gas processing.
- the individual product streams in particular the condensate, can subsequently be reprocessed in the sense of raw material recycling, eg. B. used as raw materials for olefin production in ethylene plants.
- An advantage of the process according to the invention is that inorganic secondary constituents of the old or waste plastics are concentrated in the sump phase, while the condensate not containing these constituents can be processed further in less complex processes.
- temperature and residence time it can be achieved that on the one hand a relatively high proportion of condensate is formed and on the other hand the viscous depolymerizate of the bottom phase remains pumpable under the process conditions.
- a useful approximation can be that an increase the temperature by 10 ⁇ C with an average residence time increases the yield of the products passing into the volatile phase by more than 50%.
- the residence time dependence for two typical temperatures is shown in FIG. 6.
- the preferred temperature range for the depolymerization for the process according to the invention is 150 to 470 ° C. A range from 250 to 450 ° C. is particularly suitable.
- the residence time can be 0.1 to 20 hours. A range from 1 to 10 h has proven to be generally sufficient.
- the pressure is a less critical variable. So it may be preferable to carry out the process under negative pressure, e.g. B. if volatile components have to be deducted for procedural reasons. Relatively high pressures are also practicable, however, they require more equipment. In general, the pressure should be in the range from 0.01 to 300 bar, in particular 0.1 to 100 bar.
- the method can preferably be good at normal pressure or slightly above z. B. run up to about 2 bar, which significantly reduces the outlay on equipment. In order to degas the depolymerizate as completely as possible and to further increase the proportion of condensate, the process is advantageously carried out under a slight negative pressure down to about 0.2 bar.
- the depolymerization can be carried out in a conventional reactor, e.g. B. a stirred tank reactor, which is designed for the corresponding process parameters, such as pressure and temperature. Suitable reactors are described in the unpublished German patent applications P 44 17 721.6 and P 44 28 355.5.
- the contents of the reactor are preferably moved over a circuit system connected to the reactor.
- this circuit system comprises an oven / heat exchanger and a powerful pump. The advantage of this method is that a high circulation flow through the external furnace / heat exchanger means that the temperature increase required for the material in the circulation system remains low, on the one hand, and favorable transmission conditions in the furnace / heat exchanger enable moderate wall temperatures.
- the reactor is designed in such a way that the extraction device for the circulation (circulation system) lies in a rising section for the essentially liquid reactor content.
- the rate of climb essentially determined by the dimensioning of the climb and the dimensioning of the circulating current, particles with a higher sinking rate, which are the cause of the erosion, can be kept out of circulation.
- the riser section within the reactor is designed in the form of a tube which is mounted essentially vertically in the reactor (cf. FIG. 1).
- the riser can also be realized in that a partition divides the reactor into segments (cf. FIG. 2).
- the tube or the partition does not close with the reactor cover, but protrude beyond the fill level.
- the tube or partition are so far away from the reactor floor that the reactor contents can flow into the riser unhindered and without major turbulence.
- the removal device for the depolymerizate is preferably attached in the lower area, in particular at the bottom of the reactor.
- the reactor is preferably tapered downward in the bottom region, e.g. B. conical running, or in an advantageous embodiment as a conical jacket standing on its tip.
- Figure 1 shows such a device in the sense of an embodiment.
- waste and waste plastic is converted from storage container (13) via addition device (18) by means of a gas-tight metering device (14).
- B. introduced by pneumatic means.
- a cellular wheel sluice, for example, is well suited as such a metering device.
- the depolymerizate together with the inert substances contained can be removed via device (7) at the bottom of the reactor.
- the addition of the plastic and the removal of the depolymerizate is advantageously carried out continuously and is designed in such a way that a certain fill level (3) of the reactor contents is maintained. Gases and condensable products are drawn off from the head region of the reactor via device (4).
- the reactor contents are pumped (5) for gentle heating in the furnace / heat exchanger (6) and recirculated into the reactor (1) via an inflow (17).
- the tube (20) is arranged vertically, which forms a riser (2) for the reactor recycle stream.
- the depolymerizate stream taken from the reactor is 10 to 40 times smaller than the circulating stream.
- This depolymerization stream is z. B. driven over a wet mill (9) to bring the inert components contained therein to a size permissible for further processing.
- the depolymerized material stream can also be passed through a further separation device (8), where it is largely freed from the inert constituents. Suitable separation devices are, for example, hydrocyclones or decanters.
- the inert constituents (11) can then be removed separately and, for example, recycled.
- part of the depolymerization stream passed through the wet mill or via the separating device can also be returned to the reactor via a pump (10).
- the rest of the processing is z. B. Swamp phase hydrogenation, smoldering or gasification fed (12). Part of the depolymerizate can be taken directly from the circulatory system via a line (15) and fed to further processing.
- FIG. 2 shows a similarly constructed reactor as in FIG. 1, with the difference that the riser is not formed by a tube, but by a re Actuator segment, which is separated from the rest of the reactor content by a partition (19).
- the inert components (11) discharged via the separating device (8) mainly consist of aluminum, which can be recycled in this way.
- the removal and recycling of aluminum also opens up the possibility of completely recycling composite packaging.
- the recycling can take place together with plastic packaging. This offers the advantage that a separation of these packaging materials can be omitted.
- Composite packaging usually consists of paper or cardboard combined with a plastic and / or aluminum foil. The plastic part is liquefied in the reactor, the paper or cardboard is broken down into primary fibers, which follow the liquid due to their low tendency to sedimentation. The aluminum can largely be obtained separately. After depolymerization, plastic and paper are recycled.
- FIG. 3 shows a depolymerization system with two containers which can be operated at different temperature levels.
- the first depolymerization container (28) is equipped, for example, with a stirrer (33) in order to be able to quickly mix the old and waste plastics supplied via the lock (31) into the hot depolymerizate present.
- the downstream second depolarization tank (1) corresponds to the reactor from FIG. 1.
- the circuit for gentle heating, consisting essentially of pump (5) and furnace / heat exchanger (6), is therefore low in solids.
- the depolymerizate, including the solid components, is drawn off at the bottom of the reactor.
- the solid / liquid ratio at the removal device (7) of the container (1) can be between 1: 1 and 1: 1000.
- the removal device (7) is immediately followed by a drop section (21) with a branch (22) attached essentially at right angles thereto.
- Falling section (21) and branch (22) are designed in a preferred embodiment as a T-shaped tube.
- the branch can additionally be equipped with mechanical separation aids (23).
- a stream of organic constituents of the depolymerizate, which are essentially liquid under the present conditions, can be derived via branch (22).
- the depolymerizate is sent to further processing via pump (27) or can at least partially be returned to reactor (1) via line (32).
- the amount derived can be up to a thousand times the amount of solids discharged. In extreme cases and temporarily if necessary, nothing can be derived via branch (22). By determining the amount of depolymerized material drawn off via branch (22), suitable flow conditions can be guaranteed for the safe discharge of the solids. At the same time, the derived current should be dimensioned such that solid particles are not entrained to any appreciable extent if possible.
- the ratio of the amount of solids discharged to the amount derived is preferably 1:50 and 1:200.
- the drop section (21) or the downpipe is provided with a lock (24) at the lower end.
- An addition device (25) for flushing oil is attached above this lock.
- FIG. 5 shows an alternative in terms of process engineering, in which a separating device (26) is connected directly after the falling section (21). An addition device (25) for flushing oil is preferably attached to this.
- Flushing oil with a higher density than that of the depolymerizate is added via the addition device (25) in an amount which causes a low upward flow velocity of the liquid within the falling distance between the addition device (25) and the branch (22). This ensures that the drop section (21) or the downpipe below the branch (22) is always filled with relatively fresh flushing oil. In this part of the drop section (21) there is a so-called stable stratification with flushing oil. If nothing is diverted via branch (22), the flushing oil rises into the drop section (21) and ultimately reaches the reactor (1).
- the predominantly inorganic solid particles contained in the depolymerizate pass through the part of the drop section (21) filled with flushing oil.
- the organic depolymerizer constituents still adhering to the solid particles are washed off or dissolved in the flushing oil.
- the difference in density between the depolymer and rinsing oil should be at least 0.1 g / ml, preferably 0.3 to 0.4 g / ml.
- the depolymerizate has a density of around 0.5 g / ml at a temperature of 400 ° C.
- a suitable flushing oil z. B a heated to about 100 ° C vacuum gas oil with a density of about 0.8 g / ml can be used.
- the length of the portion of the drop section (21) filled with flushing oil is dimensioned such that the solid particles at the lower end of the drop section (21) are at least largely free of adhering organic depolymer components. It is also dependent on the type, composition, temperature and the amounts of the depolymerizate and the flushing oil used. The person skilled in the art can determine the optimal length of the part of the drop section (21) filled with flushing oil by relatively simple tests.
- the solid particles are discharged with a part of the flushing oil via lock (24).
- Lock (24) is used for the pressure-related separation of the preceding and the following system part.
- a cellular wheel sluice is preferably used.
- other types of locks e.g. B. Taktschleu ⁇ sen are suitable for this purpose.
- the mixture discharged has a solids content of about 40 to 60% by weight.
- the lock (24) expediently is followed by a further separating device (26) for separating flushing oil and solid particles.
- a scraper conveyor or a conveyor screw is preferably used as the separating device (26). These are directed obliquely upwards in the conveying direction. An angle to the horizontal of 30 to 60 ° is preferred, in particular approximately 45 °.
- FIG. 5 shows another process variant.
- the solid particles pass through the separating device (26) immediately after passing the falling section (21). About a gas cushion, e.g. B. from nitrogen, and the addition of flushing oil is set in the separating device (26) a desired liquid level (34).
- the solid particles, largely freed from flushing oil, are then passed through the lock (24), e.g. B. a rotary feeder or cycle lock, carried out.
- a drainage screw (26) is shown schematically in FIG. 3 and can act as a suitable separating device.
- a flushing oil with a lower density e.g. B. a middle distillate oil.
- the low-viscosity, light flushing oil can be separated from the solid particles more easily and without major difficulties, at least to a large extent.
- the used flushing oil can be discharged via line (29), or at least partially introduced into the depolymerizate derived via branch (22).
- the separating device (26) preferably works here under atmospheric conditions. The solid particles separated in this way are discharged via line (11) and can be recycled.
- the solid matter discharged via line (11) mainly consists of metallic aluminum, which can then be used for subsequent material recycling of this material.
- Figure 4 shows an enlarged section of Figure 3, the T-shaped arrangement of the drop section (21) and branch (22). Also shown are mechanical separation aids (23) and the flow conditions shown schematically with arrows.
- the depolymerizate After the gas and condensate have been separated off, the depolymerizate is easy to handle, since it remains readily pumpable above 200 ° C. and, in this form, is a good starting material for the subsequent process steps and other uses.
- the depolymerizate can also be solidified by means of a so-called cooling belt and thus brought into a solid form.
- a so-called cooling belt are suitable for.
- B. Endlos ⁇ bands made of stainless steel. They usually run under tension over cylindrical pulleys or pulleys.
- the product can, for example, be applied as a film in the front area of the cooling belt by means of a broadband nozzle. Cooling liquid is sprayed onto the underside of the cooling belt, but the product is not wetted.
- the depolymerizate can be cooled from above by supply air.
- the solid film formed can at the end of the cooling belt z. B. be broken by means of a routing crushing roller or by means of a lattice crusher. For subsequent processing or storage, it has proven to be advantageous if the fragments are not larger than the size of the palm of a hand. If necessary. the fragments can be further crushed z. B. be ground.
- the depolymerizate can be introduced in pumpable form directly into the subsequent process stages or can be used for other purposes. If intermediate storage is necessary, this should be done in tanks in which the depolymerizate is kept at temperatures at which it remains easy to pump, usually above 200 ⁇ C. If longer storage is desired, the depolymerizate is a good choice to store in solid form. In broken form, the depolymerizate can be transported and stored analogously to the fossil fuel hard coal and can be used in subsequent processes and uses.
- the present invention relates to a further development of the subject matter of patent application P 43 11 034.7, in particular the use and further processing of the depolymerizate object of the patent.
- a depolymerisate is preferably used which is at least largely freed of coarser inorganic solid particles, in particular metallic aluminum.
- At least a partial stream of the depolymerizate is subjected to coking together with coal.
- coal is suitable for the production of high quality coke.
- a coke for example metallurgical coke
- Suitable coals are, for example, the baking fat coal from the Ruhr area or gas coal. Such baking coals are available in limited quantities and are more expensive than, for example, boiler coal.
- At least a partial stream of the depolymerizate is subjected to thermal utilization.
- Thermal recycling is understood to mean the oxidation of a substrate using the resulting heat. Because of its high energy content and its relatively low chlorine content compared to old or waste plastics with a high degree of homogeneity, the depolymerizate is a suitable fuel for use in power plants of all kinds and in cement plants.
- the depolymerizate can be both liquid at temperatures above 200 ° C via lances, for. B. be injected as a substitute for heavy fuel oil or in solid form, for. B. broken or ground.
- At least a partial stream of the depolymerizate is used as a reducing agent in a blast furnace process.
- the depolymerizate can also be used here as a substitute for heavy heating oils which are usually used for this purpose.
- the relative low chlorine content of the depolymerizate of less than 0.5% by weight proves to be a particular advantage.
- the depolymerizate produced by a process according to the main application can therefore advantageously be used as a binding additive in the coking of coal, as a reducing agent in blast furnace processes and as a fuel in combustion plants, power plants and cement plants.
- the depolymerizate prepared by a process of patent application P 43 11 034.7 can be used as an additive to bitumen and bituminous products.
- Polymer-modified bitumen is used in many areas of the construction industry, especially in roof sealing materials and in road construction.
- the polymers contained in the depolymerizate improve the properties of the bitumen such as toughness, elasticity and abrasion resistance. Because of its residual reactivity, the depolymerisate forms chemical bonds when it is heated together with bitumen and bitumen derivatives. This is partly the cause of the property improvements mentioned and desired.
- This modification can improve the cold flexibility as well as the stability of the bi-containing material.
- An improvement in the elastic properties of the bitumen and in the adherence to the mineral filling material can also be achieved by adding polymers.
- the chemical reaction with the bitumen also has the advantage that, for. B. no segregation can take place in hot storage or this is severely restricted.
- the residual reactivity of the depolymerizate can be increased by introducing functional groups, for example using the processes according to European patent applications EP 0 327 698, EP 0436 803 and EP 0 537 638. If necessary.
- the bitumen or bituminous products modified in this way can also contain crosslinking agents (cf. EP 0 537 638 A1).
- a stirred tank reactor with 80 m * content which is provided with a circulation system with a capacity of 150 m * / h
- 5 t / h of mixed agglomerated plastic particles with an average grain diameter of 8 mm were pneu ⁇ matically registered.
- the mixed plastic was material that comes from a household collection of the Dual System Germany (DSD) and typically contained 8% PVC.
- the plastic mixture was depolymerized in the reactor at temperatures between 360 ° C and 420 ° C. Four fractions were formed, the quantity distribution of which is shown in the table below as a function of the reactor temperature:
- the depolymerizate stream (III) was drawn off continuously.
- the viscosity of the polymer was 200 mPas at 175 ° C.
- Depolymerizate from the processing of waste plastics from household collections of the DSD according to Example 1 was mixed into a coking coal in different proportions. The mixtures were coked in a test coke oven.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Processing Of Solid Wastes (AREA)
- Coke Industry (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4435238 | 1994-10-04 | ||
DE4435238A DE4435238A1 (de) | 1993-04-03 | 1994-10-04 | Verfahren zur Gewinnung von Chemierohstoffen und Kraftstoffkomponenten aus Alt- oder Abfallkunststoffen |
PCT/EP1995/003901 WO1996010619A1 (fr) | 1994-10-04 | 1995-10-02 | Procede pour la recuperation de matieres premieres synthetiques et de composants de carburants provenant de matieres plastiques hors d'usage ou de dechets |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0784661A1 true EP0784661A1 (fr) | 1997-07-23 |
EP0784661B1 EP0784661B1 (fr) | 1998-07-22 |
Family
ID=6529787
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95935425A Expired - Lifetime EP0784661B1 (fr) | 1994-10-04 | 1995-10-02 | Procede pour la recuperation de matieres premieres synthetiques et de composants de carburants provenant de matieres plastiques hors d'usage ou de dechets |
Country Status (24)
Country | Link |
---|---|
US (1) | US5789636A (fr) |
EP (1) | EP0784661B1 (fr) |
JP (1) | JP3462216B2 (fr) |
CN (1) | CN1159821A (fr) |
AT (1) | ATE168714T1 (fr) |
AU (1) | AU688145B2 (fr) |
BG (1) | BG63346B1 (fr) |
BR (1) | BR9509235A (fr) |
CA (1) | CA2201777A1 (fr) |
CZ (1) | CZ101897A3 (fr) |
DE (1) | DE59502919D1 (fr) |
DK (1) | DK0784661T3 (fr) |
ES (1) | ES2120770T3 (fr) |
FI (1) | FI971375L (fr) |
GR (1) | GR3027760T3 (fr) |
HU (1) | HUT77197A (fr) |
NO (1) | NO971486L (fr) |
NZ (1) | NZ294602A (fr) |
PL (1) | PL185814B1 (fr) |
RO (1) | RO118134B1 (fr) |
RU (1) | RU2151163C1 (fr) |
SK (1) | SK283104B6 (fr) |
WO (1) | WO1996010619A1 (fr) |
ZA (1) | ZA958364B (fr) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2001282964A1 (en) * | 2000-07-27 | 2002-02-13 | E.I. Du Pont De Nemours And Company | Transformation of polymers to useful chemicals by oxidation |
ES2224863B1 (es) * | 2003-07-07 | 2006-12-16 | Consejo Sup. De Invest. Cientificas | Procedimiento para la utilizacion de plasticos de desecho como fuente nutritiva carbonada de microorganismos de interes biotecnologico industrial. |
ITTP20030002A1 (it) * | 2003-10-09 | 2005-04-10 | Giovanni Maurizio Di | Processo ossidoriduzione per riciclare qualsiasi frazione rifiuto:fanghi, scarti industriali, agroalimentari, macellazione, ittici, ecc. in biostabilizzato sterile e/o polixano espanso isolante termoacustico, in innovativo impianto mobile o fisso con |
DE102004038220B4 (de) * | 2004-08-05 | 2009-07-23 | Proton Technology Gmbh I.Gr. | Thermische Biomassenverölung |
UA90089C2 (ru) * | 2006-02-08 | 2010-04-12 | Григорий БЕРЕЗИН | Способ производства кокса из неспекающихся марок угля и устройство для его осуществления |
ES2294964B1 (es) * | 2007-04-27 | 2009-04-16 | Sistemas De Reciclaje Y Energia, S.L | Sistema y proceso de reciclado de plasticos. |
US20100065410A1 (en) * | 2008-09-17 | 2010-03-18 | Jianguo Li | High temperature separable continuous residue discharging system and method of using the same |
US8317980B2 (en) * | 2008-09-17 | 2012-11-27 | Nantong Tianyi Environment And Energy Technology Limited Corporation | Reactor for converting waste materials into fuel, a feeding system for feeding waste materials into the reactor, and methods for converting waste materials into fuel |
WO2011144322A2 (fr) * | 2010-05-17 | 2011-11-24 | Dieter Wagels | Procédé et installation de dépolymérisation de matières contenant des hydrocarbures |
CN102344823B (zh) * | 2011-09-06 | 2014-01-01 | 六盘水师范学院 | 一种温和条件下使煤与废塑料共液化的方法 |
PL422836A1 (pl) * | 2017-09-14 | 2019-03-25 | Polymer Energy Polska Spółka Z Ograniczoną Odpowiedzialnością | Dodatek w postaci preparatu do stałych paliw biomasowych i odpadów biomasowych a także do uzdatnionych mułów i flotów węglowych oraz osadów ściekowych i paliw formowanych z odpadów, przeznaczony zwłaszcza do procesów spalania, współspalania, zgazowania i odgazowania paliw stałych |
TWI694064B (zh) * | 2018-09-26 | 2020-05-21 | 遠東新世紀股份有限公司 | 對苯二甲酸的製造方法及其系統 |
BE1026748B1 (nl) * | 2018-10-31 | 2020-06-04 | Montair Process Tech | Systeem en werkwijze voor het pyrolyseren van organisch afval |
US11852258B2 (en) * | 2020-12-31 | 2023-12-26 | Tapcoenpro, Llc | Systems and methods for purging an isolation valve with a liquid purge medium |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2202903B1 (de) * | 1972-01-21 | 1972-11-30 | Karwat Ernst Dr Ing | Verfahren zur Beseitigung und Verwertung von Kraftfahrzeugreifen-Altmaterial |
JPS51135901A (en) * | 1975-05-21 | 1976-11-25 | Mitsui Cokes Kogyo Kk | Process for producing coke |
DE2530229A1 (de) * | 1975-07-07 | 1977-01-27 | Helmut Dr Ing Wuerfel | Verfahren zur umwandlung von altreifen, gummi und/oder anderen kunststoffen |
FR2512032B1 (fr) * | 1981-09-01 | 1983-12-16 | Bruss Ti Kirova | Procede d'obtention d'un ramollissant pour melanges caoutchoucs et de mazout |
US5061363A (en) * | 1990-10-09 | 1991-10-29 | The United States Of America As Represented By The United States Department Of Energy | Method for co-processing waste rubber and carbonaceous material |
US5364996A (en) * | 1992-06-09 | 1994-11-15 | Texaco Inc. | Partial oxidation of scrap rubber tires and used motor oil |
DE4311034A1 (de) * | 1993-04-03 | 1994-10-06 | Veba Oel Ag | Verfahren zur Gewinnung von Chemierohstoffen und Kraftstoffkomponenten aus Alt- oder Abfallkunststoff |
-
1995
- 1995-10-02 AT AT95935425T patent/ATE168714T1/de not_active IP Right Cessation
- 1995-10-02 WO PCT/EP1995/003901 patent/WO1996010619A1/fr not_active Application Discontinuation
- 1995-10-02 NZ NZ294602A patent/NZ294602A/xx unknown
- 1995-10-02 CN CN95195455A patent/CN1159821A/zh active Pending
- 1995-10-02 BR BR9509235A patent/BR9509235A/pt not_active IP Right Cessation
- 1995-10-02 JP JP51140996A patent/JP3462216B2/ja not_active Expired - Fee Related
- 1995-10-02 DK DK95935425T patent/DK0784661T3/da active
- 1995-10-02 ES ES95935425T patent/ES2120770T3/es not_active Expired - Lifetime
- 1995-10-02 PL PL95319453A patent/PL185814B1/pl unknown
- 1995-10-02 SK SK419-97A patent/SK283104B6/sk unknown
- 1995-10-02 HU HU9701864A patent/HUT77197A/hu unknown
- 1995-10-02 CZ CZ971018A patent/CZ101897A3/cs unknown
- 1995-10-02 RU RU97107616/04A patent/RU2151163C1/ru not_active IP Right Cessation
- 1995-10-02 CA CA002201777A patent/CA2201777A1/fr not_active Abandoned
- 1995-10-02 AU AU37448/95A patent/AU688145B2/en not_active Ceased
- 1995-10-02 RO RO97-00648A patent/RO118134B1/ro unknown
- 1995-10-02 US US08/809,711 patent/US5789636A/en not_active Expired - Fee Related
- 1995-10-02 DE DE59502919T patent/DE59502919D1/de not_active Expired - Fee Related
- 1995-10-02 EP EP95935425A patent/EP0784661B1/fr not_active Expired - Lifetime
- 1995-10-04 ZA ZA958364A patent/ZA958364B/xx unknown
-
1997
- 1997-04-02 NO NO971486A patent/NO971486L/no not_active Application Discontinuation
- 1997-04-03 FI FI971375A patent/FI971375L/fi unknown
- 1997-04-18 BG BG101423A patent/BG63346B1/bg unknown
-
1998
- 1998-08-27 GR GR980401939T patent/GR3027760T3/el unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9610619A1 * |
Also Published As
Publication number | Publication date |
---|---|
CZ101897A3 (en) | 1997-08-13 |
JPH10506662A (ja) | 1998-06-30 |
SK283104B6 (sk) | 2003-02-04 |
BG63346B1 (bg) | 2001-10-31 |
HUT77197A (hu) | 1998-03-02 |
PL185814B1 (pl) | 2003-08-29 |
AU688145B2 (en) | 1998-03-05 |
NO971486D0 (no) | 1997-04-02 |
ZA958364B (en) | 1996-05-13 |
EP0784661B1 (fr) | 1998-07-22 |
FI971375A0 (fi) | 1997-04-03 |
FI971375L (fi) | 1997-06-03 |
BG101423A (en) | 1997-12-30 |
CN1159821A (zh) | 1997-09-17 |
PL319453A1 (en) | 1997-08-04 |
DE59502919D1 (de) | 1998-08-27 |
NO971486L (no) | 1997-05-22 |
DK0784661T3 (da) | 1998-11-16 |
US5789636A (en) | 1998-08-04 |
RO118134B1 (ro) | 2003-02-28 |
WO1996010619A1 (fr) | 1996-04-11 |
RU2151163C1 (ru) | 2000-06-20 |
JP3462216B2 (ja) | 2003-11-05 |
BR9509235A (pt) | 1997-10-21 |
SK41997A3 (en) | 1997-09-10 |
CA2201777A1 (fr) | 1996-04-11 |
ES2120770T3 (es) | 1998-11-01 |
ATE168714T1 (de) | 1998-08-15 |
GR3027760T3 (en) | 1998-11-30 |
NZ294602A (en) | 2000-01-28 |
AU3744895A (en) | 1996-04-26 |
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