AU667303B2 - Process and device for processing free-flowing organic waste materials containing noxious substances - Google Patents

Abstract

Method and equipment for preparing fluid organic waste products, containing reusable or harmful constituents. A multi-stage single-duct reactor is used in which an exchange of energy (e.g. of thermal energy) with the waste product takes place and the waste product is at least partly converted into a gas phase. After each stage the harmful constituents from it are sepd. into a sump, in each stage the necessary activation energy (previously determined experimentally) is applied, and after the last stage the required product is condensed. The reactor throughput is kept constant by the regulator (7). At the end of this first stage (2) there is a separator (8) for the product entering the sump (10) and the product changed into a gas phase. The latter product leaves through the pipe (11) and its temp., measured at (12), is communicated to the burner control so that the burner is kept at a constant temp. The second and third stages (16,17) are similar to the first stage, but the third stage has no dosing arrangement for additional chemicals. From the third stage, the product goes to a condenser (18) and discharge pump (19). A vacuum pump (20) provides for the necessary underpressure in the system. USE/ADVANTAGE - This is an improvememnt on a single-duct reactor in (P 38 20 317.0-45) has an increased range of use and is easier to construct. Also, it enables two valuable constituents, such as used mineral and vegetable oils, to be sepd.

Description

OPI DATE 21/12/92 APPL4. 1ID 16536/92 ,PAO,1P DATE 28/01/93 PCT NBER PCT/EP92/00933 AU9216536 INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWESENS (PCI (51) internationale Patentklassifikation 5(11) lnterntioiiale Veriiffentlichungsnummer: WO 92/19705 ClOM 175/00, BOIJ 19/24 Al (43) Internationales Ver~ffentlichungsdatum: 12. November 1992 (12,11.92) (21) Internationales Aktenzeichen: PCT/EP92/00933 (74) Anwalt: BCH LING, Joachim; Obere Harditstrage 4, D- 5920 Bad Berleburg 13 (DE).

(22) Internationales Anmneldedatumn: 29. April 1992 (29.04.92) (81) Restimmungsstaatcn: AT (europilisches Patent), AU, BE Priorltiitsdaten: (europfiisches Patent), BR, CA, CH (europflisches Pa- P 41 14 883.5 7. Mai 1991 (07.05.91) DE tent), DE (europfiisches Patent), DX (europ~1isches Patent), ES (europ'disches Patent), FR (europflisches Patent), GB (europllisches Patent), GR (europttisches Pa- Haupit-/Stammnanmieldungen oder Haupt-/stamimpatente tent), IT (europiiisches Patent), JP, KR, LU (europfli- (63) Teilfortsetzung sches Patent), MC (europflisches Patent), NL (europJius 894,140 (CIP) sches Patent), SE (europllisches Patent), US 16. Januar 1990 (16.01.90) us 559,985 (CIP) Juli 1990 (30.07.90) Veriiffeitlicht Mil intenationalein Reeherchenberich.

(71)(72) Anmnelder und Erfinder: SCHON, Christian, 0. [DE/ MtglnetnAsrthnudEkaug DE]; R16merstraBe 1, D-7590 Achern 18 7 3 0 3 (54) Title: PROCESS AND DEVICE FOR PROCESSING FREE-FLOWING ORGANIC WASTE MATERIALS CONTAI- NING NOXIOUS SUBSTANCES (54) llezcichnung: VERFAH-REN UND VORRIGHTUNG ZUM AUFARBEITEN SCHXDLICHE BESTANDTEILE ENT- HALTENDER FLIESSFXHIGER ORGANISCHER ABFTALLSTOFFE (57) Abstract The invention starts from a known process of the inventor and a suitable device for processing organic waste materials containing noxious or polluting substances in a single-tube reactor. Energy, in particular heat energy, is exchanged with the waste material through the tube, the waste material is at least partly converted to a gaseous phase and the flow of energy and the time for which the waste material is exposed to the latter (residence time) is regulated so as to establish the activation energy required to remove the noxious substances, To improve this process, in particular regarding the potential applications and profitability, the invention proposes that the process be carried out in several steps. After each step, noxious substances are removed and in each step the parameters which determine the activation energy (energy, residence) are re-established.

(57) Zusariiienfassung Ausgehend von einem bekatn;en Verfahren des Erlinders und einer Vorrichtung zum Durchfilhren dieses Verfahrens, bei wvelchem zumn Aufarbeiten scifldlide oder umweltbelastende Bestandteile enthaltender organischer Abfallstoffe in einem Em-.

rohrrcaktor durch das Rohr emn Energieaustausch, insbesondere thermischer Encrgie, mit dem Abfallstoff erfolgt, wobei der Abfalistoff weaigstens teilweise in eine gnaiftrmige Phase flberftlhrt wird und der Energieflull und die Zeit, wllhrend welcher der Abfallstoff diesem ausgesetzt ist (Verweildauer), derart geregelt ist, dali sich die fir die Abtrennung der schlldlichen Stoffe erforderliche Aktivierungsenergie einstelit, wird zur Verbesserung dieses Verfahrens insbesondere bezilglich Anwendungsm8glichkeit und Wirstchaftlichkeit erfindungsgemdl vorgeschlagen, das Verfahren in mehreren Stufen durchzufflhren, wohei nach jeder Stufe schildllche Stoffe abgeschieden und in jeder Stufe die Festlegung der die Aktivierunbienergie bestimmenden Parameter (Energie, Verweildatier) von neuem eingeregelt wird.

-1- Tbh invention relates to a process and an apparatus for processing flowable materials containing reusable or noxious and environmentally-polluting components, e.g. used oils, preferably chlorine-containing, by employing a multi-stage single tube reactor adapted to be charged by a conveyance means and in which an energy exchange, in particularly of thermal energy, takes place through the tube with the waste material, wherein the waste material is at least partly converted into a gaseous phase and the energy flow and the time during which each molecule of the waste material is subjected to such energy flow is so regulated that the activation energy for bond splitting between the respective molecules or atoms of the components and the reusable materials as required for the separation of the noxious and/or environmentally-polluting components is brought about.

Flowable organic waste materials are intended to denote liquid waste materials in a general sense in this context which jointly with undesirable t/xic or environmentally harmful components contain reusable raw materials. For example in the case of used oil a re-utilisation of the oil in the form of new oil is to be made possible i.e. from which e.g. the impurities present in old oil and derived from combustion engines have been removed. Also included are hydrocarbon compounds containing chlorine and sulphur as well as sump products as are obtained in the form of distillation residues in known processing plants and which are to be further processed.

In the processing of such media extremely noxious and environmentally harmful substances such as e.g. chlorine, dioxins, polychlorinated biphenyls (PCB) polyaromatic hydrocarbons (PAH or the like are released as well as additives as are added to mineral oil products such as manganese, tungsten, iron or stabilisers, etc., all of which can be separated from the substances to be Sprocessed only with great difficulty or not at all. Other waste materials contain -2essentially only such toxic substances which, however, cannot be separated from one another for purposes of ready disposal, i.e. cannot be separated into their individual components which may then be disposed of more readily or which may be suitable for conversion into different products. For that reason even nowadays many hundreds of thousands of tons of such substances are still dumped into the sea annually. It is to be expeced that due to the future increased employment of oils of vegetable origin inter-mixtures of mineral and vegetable used oils will arise in practice, the separation and processing for reuse of which has hitherto been technically not feasible.

By the same inventor who is also the inventor of the present application it has already been proposed to process such substances in accordance with the process referred to in the introduction hereof. Such a process is for example known from German Patent Applications P 38 20 317.0 45 and P 38 41 844.4. By this process it is already possible, due to the use of a single tube reactor to perform an environmentally friendly disposal of such toxic and noxious substances. The reason is that by means of such single tube reactor the product can be controlled with extraordinary product homogeneity over the entire tube cross-section accurately to tenths degrees C and by regulating the flow velocity for a given tube length to a dwell period of the product at a predetermined temperature accurately to within milli-seconds. The dwell period in this context is understood to mean the period during which the product whilst flowing through the reactor is subjected to a particular parameter, i.e. in particular a certain temperature or energy exposure. Accordingly the single tube reactor permits each particle down to molecular size to be exposed to identical adjustable parameters, permitting the molecules, respectively atoms, of the product to be treated in a pre-designated manner.

-3- There is, however, scope to improve this already quite satisfactory process even further, to broaden its field of applications and/or to render it even more economical. Furthermore there exists a need for the separation of two valuable components into two individual components to be made possible such as e.g. in the case of mixtures of mineral and vegetable used oils.

The invention provides a process as set out in the opening paragraph wherein after each stage the noxious components separated off in that stage are separated off in a sump, and wherein, in each stage, the previously experimentally determined and, optionally,' modified activation energy required for the respective product is, in each case newly adjusted by means of energy application regulated for the respective stage. After the last stage the desired product is preferably at least partly condensed. The condensation may be carried out either as a total or as a partial condensation or even by way of fractional condensation. In order to overcome the pressure losses in the overall system provision is made for the required onveyance means (pumps turbo-blowers, etc.).

Accordingly there exists quite readily the facility that exists in the second stage the activation energy is lower than in the first stage and that correspondingly energy is withdrawn from such stage in a regulated fashion, e.g. by cooling. It is decisive that in each stage the energy is so adjusted that an optimal reaction is attained, A reaction is considered optimal which complies with customary requirements respectively which ensures an optimal disposal. This may be in terms of quality, e.g. in the case of used oil if noxious contaminants are removed and the lubricating properties are good. It is even possible to influence the quality of the product, e.g. the degree of refining of used oil, either by virtue of the percentage content of sodium or by modifying the activation energy or the p;i:>,dwell In quantitative terms it is optimal if, e.g. in the case of PCBs (Nj -4sodium or by modifying the activation energy or the dwell time. In quantitative terms it is optimal if, e.g. in the case of PCBs (polychlorinated biphenyls) these are removed down to below the permissible values prescribed by the authorities.

In order to attain this it may also be advaitageous to recondense, at least at the beginning of a following stage the product converted into a gaseous phase and subsequently to re-gasify it, where a vacuum pump is advantageously connected between the condensation zone and the gasification zone, by way of a liquid separator. In this context it is advantageous for the energy introduction to be regulated separately in individual sections within a given stage between two separators for the noxious contaminants, i.e. for example one section for condensation, one for the subsequent re-conversion into the gaseous phase and optionally a further one forl a reaction involving the metered introduction of auxiliary chemicals. These auxiliary chemicals maay be introduced in individual stages as a function of the product and in accordance with process requirements or disposal requirements along the length of the reactor. The auxiliary chemicals perform various functions, which also depend on the temperatures at which the flowing product is maintained.

Moreover in the present invention the same forms of energy can be employed for modifying the activation energy as are mentioned in the above mentioned patents of the same inventor, e.g. providing a flow around the tubes by means of a liquid or gaseous heating- or cooling-medium or even by bombardment with elementary particles by high-energy electron-, proton- or neutron-radiation in the Megarad range, high voltage of the order of 10,000 to 100,000 volts, ion implantation by suitable ionisation, i.e. electro-magnetic oscillation excitation above the Megahertz range, preferably in the Gigahertz range, etc.

SUBSTITUTION PAGE Regulating the energy effect in each stage can proceed in a known manner in that the temperature at the end of the stage is measured and that the energy to be introduced or withdrawn is regulated accordingly. In particular if at least two parallel tube reactors are provided it is of particular advantage in the context of the invention for the regulation of the energy exposure at constant energy flow to proceed by way of regulation of the flow velocity in each pipe stage, i.e. by influencing the effective duration of such energy flow acting onto the flowing product. The constant energy flow may be generated by a centrally regulated energy source. In that manner unavoidable inaccuracies in the tube diameters or variations in properties of tube inner surfaces with a view to the high accuracy of control of the energy flow onto the flowing product required for the process according to the invention can be compensated for.

In a further embodiment of the invention provision is further made for the introduction of a hydrogenation procedure in one stage, preferably the second stage.

According to an alternative embodiment of the invention, applicable to certain products in a two-stage process, the second stage may also be performed as a fractional condensation, as described in the above-mentioned printed publications of the inventor.

An apparatus for carrying out the process in accovdance with the invention inruding a plurality of stages connected in series is characterised by a reactor, in which the tube of each stage has a ratio of length to diameter of at least 200 1 a length of 1000 em and a diameter of 5 cm) with a minimum diameter of mm, in which after each stage a separator for separating the separated noxious substances in a sump is provided, and devices for regulating the flow velocity and the temperature of each stage. For a length of 100 m the tube diameter may, for example, be 0,5 m or less, however it is also possible for a length of 700 m to provide a diameter of 0,5 m.

SUBS'rIrUTION PAGE -6- The diameters may also vary along the length.

After the last stage a condensing means is preferably provided even for a fractional condensation. The pipes of the individual stages may take the form of double-walled tubes which can be acted upon by a heating- or cooling-medium as the case may be, or the pipes may be surrounded by a heating space in which, e.g. by means of flue gases heated by a burner flow around and heat up the pipes.

In the case of using the above-mentioned high-energy electron-, proton- or neutron-radiation or electro-magnetic oscillations in the Gigahertz range up to nano-m wave-length, e.g. UV-light etc., the possibilities according to the state of the art are available for introducing these into the reactor space, such as, e.g. in the case of high-frequency fields the provision of quartz windows in the tube wall through which magnetic coils act upon the flowing medium. Again the afore-mentioned older patent rights are referred to in this context.

In the separator means may be ins, diled such as, e.g. high-voltage charging means or baffles as are known in gas technology for the separation of dusts and contaminants. The same applies also to built-in devices such as those used for the agglomeration of aerosols.

Since it may be desirable in certain cases to re-convert the product in at least one stage into a liquid phase, an intermediate condenser is advantageously installed in this position by means of which the gaseous product may once again be liquefied, in order to be re-converted into the gaseous phase in a section following this stage.

In exceptional cases it is even possible for the product, in the gaseous phase from the outset, to be fed in, probably with impurities, and by the same token the purified product may emerge from the reactor, in gaseous or partly gaseous form, for further processing.

S SUBSTITUTION PAGE d "f -7purified product may emerge from the reactor for further processing in gaseous or partly gaseous form.

The invention will be explained further in the following by way of examples with reference to the drawings. There is shown in Fig. 1 a diagram of the apparatus according to the invention, including a threestage reactor, Fig. 2 a diagram of the apparatus according to the invention, including two parallel three-stage reactors, Fig, 3 a diagram of a four-stage apparatus according to the invention including reactor stages each in the form of a double tube, Fig. 4 a diagram of an alternative embodiment of the tube rector according to the invention, Fig. 5 a detail of Fig. 4 including an alternative embodiment of this detail an4, Fig. 6 a diagram of a further embodiment of the reactor suitable in particular for hydrogenation.

In the example according to Fig. 1 the product to be processed, e.g. a used oil is conveyed by means of a conveyance pump 1 into the first stage 2 of the tube reactor 3 which passes through a heating chamber 4. The heating chamber 4 is heated by means of a burner 5, the combustion gases emerging at 6 from the chamber 4. The throughput amount of product in the tube reactor 3 is regulated to a constant level by way of regulator 7. At the end of the first stage 2 of the -8tube reactor a separator 8 for the sump products separated off in that stage is provided which sump products are discharged into the sump 10 at 9 whilst the product which in the first stage has been converted into a gaseous phase emerges at 11 from the separator 8. At that locality the temperature of the product is measured at 12 and reported to a burner control for regulating the burner to constant temperature. In this position auxiliary chemicals may optionally be injected as indicated by broken line arrows 13. The product emerging from the separator 8 is passed by way of the pipeline 14 into the second stage 16 of the tube reactor. A conveyance means 15 may be provided to support the conveyance. The second stage and the third stage are identical to the first stage with regard to heating and separation means, but with the difference that in the illustrated example no means for the injection of auxiliary chemicals is provided in the third stage. The finally treated product is withdrawn after the third stage by way of a condenser 18 and a withdrawal pump 19, The condenser 18 may for example be designed for a fractional condensation as illustrated in the above-mentioned patents of the same inventor.

A vacuum pump 20 takes care of the required reduced pressure in the system.

The working example according to Fig. 2 represents an apparatus according to the invention including two parallel tube reactors in each stage. The product which here as well is introduced by a conveyance pump 1 is split in a first stage 21 into two reactor lines 22 and 23 which both pass parallel to one another through the heating chamber 4 heated by means of the burner 5 and are there subjected to heating. As distinct from the working example according to Fig. 1 the temperature of the heating gases is here, however, regulated to a constant value by the regulator 24 which takes measurements in the outlet 6 for the hot gases. However, regulators 25 and 26 regulate separately the flow velocity of the Sproduct in the two reactor lines 22 and 23 by way of valve 27 and 28. Auxiliary chemicals may be metered into the wo eactor lines 22 and 2 in the posions ,chemicals may be metered into the two reactor lines 22 and 23 in the positions -9indicated by broken line arrows 29. At the end of both reactor lines 22 and 23 a common separator 30 is provided from where separated sump products are discharged into the sump 31 whilst the gaseous product enters into the next stage 34 by way of a duct 32 and optionally a conveyance means 33. This stage and the next following stage 35 are generally of identical design to the first stage 21.

Here as well the product emerging from the third stage is passed by way of the pump 37 to a known condensation procedure including a condenser 36. A vacuum pump 38 provides reduced pressure in the system. In Fig. 3 a four-stage apparatus is illustrated in which the reactor tube part 40 of each stage 41,42,43 and 44 is surrounded at a distance therefrom each by a temperature control jacket 45, provision being made for the flow of the heating medium in countercurrent separately through the gap between each reactor tube part and jacket the heating medium entering at 46 and being discharged at 47. Each stage is individually regulated to a constant temperature individually fixed for each stage by a temperature regulator 48, the flow velocity is regulated by a regulator 49 at the inlet 50 into the reactor. At the end of each stage one separator each 51,52,53 respectively 54 for the respectively separated noxious components in each stage is provided to discharge into the respectively associated sump 55,56,57 respectively 58. In the ilustrated example the feed means 59 respectively 60 in the second and third stage are each provided with metering pumps 61 for the metering of auxiliary chemicals thereinto. A pipe duct passes from the separator 54 of the last stage 44 to a condenser 63 with withdrawal pump 64, known per se. A vacuum pump 65 takes care here as well of the required reduced pressure in the system. In the individual stages special means 66 for gas conveyance may optionally be provided.

t In the working example according to Fig. 4 a four-stage pipe reactor is illustrated 10 with differently designed stages, the temperature controls of which each proceed by way of a heating medium passed through double-walled pipes as will be explained more fully in what follows. The product to be treated, introduced by a feed pump 1 into the tube reactor 70 first flows through a first stage 71 taking the form of a reactor and surrounded at a distance by a temperature control jacket for the temperature medium. In this section regulated by a temperature regulator 73 the product is converted into a gaseous phase. The flow velocity is highly accurately regulated by a regulator 74. At the end of this stage 71 a separator 75 is once again provided for passing the noxious substances separated in this first stage into the sump 76. In the second stage 77, a section 78 for a condensation and subsequent liquid separation 79 is firstly provided from which a duct 80 passes to a vacuum pump (not illustrated). The section 78 for the condensation is enveloped by a temperature control jacket 81, the temperature in this region being individually regulated by the regulator 82. Prior to the next section 83 in which the product is once again returned to a gaseous phase and which is enveloped by a temperature jacket 84 including an individual regulator a conveyance pump 86 is provided. The next following and last reactor section 87 of this stage is enveloped by a temperature regulating jacket 88 with an individual regulator 89 for the heating temperature. Ducts 91 for injecting auxiliary chemicals, connected to a metering pump 90 pass into this reactor section. At the end of the stage 77 a separator 92 is again provided with a sump 93 for accommodating the noxious substances separated in this stage 77. The next stage 94 is designed identically in principle as the stage 77, whereas in this working example the last stage 95 comprises merely a reactor section 96 including a temperature control jacket 97 and a temperature regulator 98. At the end of the tube reactor a separator 99 is provided from which once again noxious substances are discharged into a sump 100 whereas the product is discharged by way of a condenser 101 and a suction pump 102. In addition a vacuum pump 103 takes care of adequately reduced pressure in the system.

E

,I

S11- Fig. 5 illustrates a detail of an alterative embodiment in the region of the separator 79 of Fig. 4. In that case a side fraction for gases which are undesired in the final product is withdrawn by way of the duct 80 and the condenser 104.

Condensed liquid is withdrawn by way of a separator 105 and pump 106 whilst the duct 107 leads to a vacuum pump which is not illustrated. This arrangement may be provided in identical manner and at th corresponding position in the stage 94 of Fig. 4.

Yet another working example is illustrated in Fig 6 for the hydrogenation of dewatered used oil. The used oil introduced by way of the pump 1 is converted into a gaseous phase in the first reactor stage 109 including the reactor tube 110, the temperature control jacket 111 and the temperature regulator 112. Noxious components are discharged by way of the separator 113 into the sump 114. In the next stage 115 including the reactor part 116, the temperature control jacket 117 and the temperature regulator 118, red mud is metered into the apparatus by way of a metering pump 119 whereas hydrogen is introduced by way of pipe ducts for the hydrogenation. Further noxious components are separated by way of the separator 121. In the last stage 122, including the ieactor tube 123, b.eachng earth is metered in by way of the metering pumps 124 The reactor end is provided, in the same manner as in the example according to Fig. 4, with a separator 99, a sump 100, a condenser 101 and a vacuum pump 103. Optional means for increasing the gas pressure are denoted as 125.

The invention will be further elucidated with reference to the following examples: Example A: When processing chlorinated used oil the additives present in the first stage at

Y

l l v It*1 12 about 420 °C in the sump become so reactive that metal salts are formed in which part of the sulphur and the chlorine is bound. In order to support this reaction it is possible, for example, to feed an alkaline earth metal oxyhydride, e.g.

slaked lime, e.g. along the length of the tube reactor, and this is then separated off after the first stage. In the second stage, e.g. at about 3100 C, sodium is fed along the length of the tube reactor to achieve a controlled refining of the used oil. For this purpose the sodium content depends largely on the sodium chloride content as well as the desired degree of refining of the oil. For ordinary used oil this may be in the region of At the same time the conversion of the chlorine components into NaCI takes place. After this second stage the sump product is separated off. In the third stage bleaching earth is metered in at about 340 "C for optically brightening the oil.

Example B In the second stage a hydrogenation is carried out, there being in this stage intermixed about 0,5 to 1% Bayer-mass (red mud) to serve as catalyst as well as along the length of the reactor about 10 to 15% of hydrogen based on reactive oil.

Example C An intermixture of mineral and vegetable origin used oils is to be separated aid treated, more particularly using an apparatus according to Fig. I with three stages. In the first stage 2 the mixture is heated to about 200 to 250 In the separator 8 of this stage the vegetable oil is separated from the mixture. In the second stage 16 the temperature of the product is cooled at least to 100' C. In the separator 8' of this second stage the mineral oil is separated off. In the next stage 17 a further cooling takes place to 20 down to 0 °C or even lower and here -13the noxious substance such as, e.g. acrolein is separated off which "an be burnt in the plant, without problems, to yield pure carbon dioxide. The vacuum pump takes care that the entire process is carried out at a reduced pressure of about mbar.

4

Claims (4)

1. Process for processing free-flowing organic waste materials containing noxious and environmentally harmful constituents, using a multi-stage single-tube reactor which can be loaded by a conveyor means and in which energy, is exchanged with the waste material through the tube, the waste material being at least partly converted into a gaseous phase and the flow of energy and the time for which each molecule of the waste material is subjected to this flow of energy being regulated so as to establish the activation energy required to break the bond between the respective molecules or atoms of the g o: constituents and the reusable substances in order to remove the noxious or environmentally harmful constituents, the activation energy required for the respective product being determined and optionally modified in advance by way S. of experiment beIng re-established in each stage by the application of energy

9. regulated in the respective stage, wherein after each stage, the noxious fractions removed in that stage are separated off into a sump. *o 2. Process according to claim 1, wherein after the last stage, the respective product is at least partly condensed. 3. Process according to claim 1 or claim 2, wherein auxiliary cemicals are supplied along the length of the reactor depending on the respective product and on the process requirements. 4. Process according to claim 2 or claim 3, wherein fractionating condensation is effected after the last stage. Process according to any one of claims 1 to 4, wherein the 22/12/95LI'7324.C.M1J4 15 product converted into a gaseous phase is recondensed at least once at the beginning of a subsequent stage and then is converted bFck into a gaseous phase and that undesired gaseous fractions are separated off between this condensation and subsequent regasification. 6. Process according to claim 5, wherein after condensation, a side fraction is drawn off for gases undesirable in the end product. 7. Process according to any one of claims 1 to 6, wherein when processing spent oil, the degree of refining is controlled by adding sodium and/or by varying the activation energy and residence time. r* .3 Q 8. Process according to any one of claims 1 to 7 wherein the *o application of energy is regulated by controlling the energy supplied or withdrawn, 9. Process according to any one of claims 1 to 7, with at least two parallel tube reactors, wherein the application of energy is regulated with a constant flow of energy by controlling the duration of the exposure of the flowing medium to this flow of energy. Process according to any one of claims 1 to 9, wherein a hydrogenation process is initiated from one stage.

11. Device for carrying out the process according to any one of claims 1 to 10, with a plurality of stages arranged one behind the other, in which the tube of each stage has a length to diameter ratio of at least 200 1 with a minimum diameter of 10 mm and regulating means are provided for regulating the flow rate and the temperature of each stage and a separator for 2U212/951.P17324C,CLM,

16- separating the noxious constituents removed into a sump is provided after aach stage. 12. Device according to claim 11, wherein a condensation device is provided after the last stage. 13. Device according to claim 11 or claim 12, wherein an intermediate condenser for the product in the gaseous phase is provided in at least one stage. 14. Device according to any one of claims 11 to 13, wherein the 9. 9 9 individual reactor stages are designed as double-walled tubes which can each be a regulated individually and can be acted upon by a heating or cooling medium. 9 15. Device according to any one of claims 11 to 14, wherein a 9 conveyor means is provided after each stage. 16. Process for processing free-flowing organic waste materials substantially as hereinbefore described with reference to the accompanying drawings. 9 9i D A T ED this 22nd day of December 1995. CHRISTIAN 0. SCHON By his Patent Attorneys: CALLINAN LAWRIE 2112/9SLP7324.CLM,16