EP2227438A1

EP2227438A1 - Process and device for generating middle distillate from hydrocarbonaceous energy sources

Info

Publication number: EP2227438A1
Application number: EP08869687A
Authority: EP
Inventors: Erhard Tschirner
Original assignee: Bio-Energy-Holding AG; BIO ENERGY HOLDING AG
Current assignee: Bio-Energy-Holding AG; BIO ENERGY HOLDING AG
Priority date: 2008-01-05
Filing date: 2008-12-22
Publication date: 2010-09-15
Also published as: NZ585824A; AU2008346505A1; RU2010132854A; CA2709755A1; CO6310985A2; ZA201003672B; JP2011511098A; RU2470863C2; DE102008003209B3; MX2010007385A; BRPI0820816A2; US20100270209A1; WO2009086908A1

Abstract

The invention relates to a process for generating middle distillate (2) from hydrocarbonaceous energy sources (1), wherein at least one hydrocarbonaceous energy source (1), if appropriate at least one catalyst (1a) and if appropriate at least one filler (1b) are fed as input material (12) to a reactor (11) which contains a process oil mixture (54), wherein a process oil mixed stream (56) is removed from the reactor (11) and heated to a process temperature between 150°C and 400°C, preferably between 350°C and 380°C, wherein the heated process oil mixed stream (67, 68) is fed to a degasser (37), wherein vaporous middle distillate (2) is separated in the degasser (37) from the heated process oil mixed stream (67, 68) and wherein a process oil mixed stream (55) which is expanded from the vaporous middle distillate (2) is recirculated from the degasser (37) to the process oil mixture (54) which is present in the reactor (11).

Description

Process and device for producing middle distillate from hydrocarbon-containing energy sources

The invention relates to a method and a device for producing middle distillate from hydrocarbon-containing energy sources.

From the prior art, it is known not to release the fuels contained in residues in the form of hydrocarbons by reaction with oxygen by the combustion or gasification, but to release them by catalytic treatment with exclusion of air in the oil bath in material form and recover as valuable material. This serves to avoid the formation of CO ₂ in the residue disposal and the production of fuels or fuels from the residues.

The residue in the form of renewable resources, such as wood and plant parts, waste products, such as plastics, animal and vegetable waste, waste oils and other organic raw materials, which contain a preferably high proportion of hydrocarbons and because of their energetic utilization as recyclables or energy sources can be referred to remain in an oil bath until, by molecular dehydration, molecular polymerization and molecular shortening (depolymerization / de-oiling) these hydrocarbons can be separated as hydrocarbon vapor.

From DE 100 49 377 C2 discloses a process for the treatment of plastics, fats, oils and other hydrocarbon-containing wastes, wherein a catalyst of sodium aluminum silicates in a circulation evaporator in the circulation in a high-boiling hydrocarbon, such as thermal oil, base oil or bunker C Oil is stirred and in the reactor part under the distillation unit plastics, fats, oils and other hydrocarbons waste are added. The reaction site for the sulfurization reaction is a recirculation evaporator system consisting of a tube-bundle evaporator heated with flue gas and a reactor connected to two tubes which performs the input and output functions. On the reactor, a distillation column is arranged, which receives the catalytically cracked product in vapor form and in the actual product diesel, fraction for the

BESTATIGUNGSKOPIE Gas production and reflux are separated into the reactor for another catalytic cracking reaction. By burning below the circulation evaporator hot flue gas is generated and passed through the flue gas tubes of the circulation evaporator. In the circulation evaporator, the hot flue gases cool, wherein in the lower part of the circulation evaporator on the inside of the tubes, where the catalyst-containing oils with the molten residues reach the tubes, temperatures of about 430 to 470 ° arise, resulting in a selective catalytic cracking of the residues leads to a hydrocarbon vapor.

The high temperature of the hot flue gases leads to the formation of reaction coke, which reacts with the sodium-doped aluminum silicate to form a non-reactive residue, which pollutes the system and stops the reaction. This reaction mixture of the catalyst and the reaction coker connects to the walls of the recycle evaporator and the reactor to a hard residue and requires a high cleaning effort in short maintenance intervals. An economical operation of the known method is therefore only possible to a limited extent. Moreover, only low yield levels of the calorific value of the input materials are achieved.

EP 1 538 191 A1 discloses a process for producing diesel oil from hydrocarbon-containing residues in an oil circuit with solids separation and product distillation for the diesel product, the main energy application and thereby the main heating being effected by one or more pumps and the flow energy of the pump should be braked by a counter-rotating agitator and converted into heat. An active heat input by heating through the wall is not provided in this method. Instead, the heat is not transported through the wall, but released directly in the reaction system. The agitator also serves to completely clean the surfaces arranged in the circuit. The technical implementation of the known from EP 1 538 191 Al method is problematic. Moreover, it is difficult to set a process stability. Moreover, the method described above is characterized by a low yield of the calorific value of the input materials. DE 10 2005 056 735 B3 discloses a high-performance chamber mixer for catalytic oil dispersions as a reactor for the depolymerization and polymerization of hydrocarbon-containing residues to middle distillate. The energy input and conversion takes place predominantly in the high-performance chamber mixer, wherein the pumping efficiency of the high-performance chamber mixer is low, ie the introduced energy is for the most part converted into mixing and friction energy. This method also has low process stability.

The object of the present invention is to provide a process for the production of middle distillate from hydrocarbon-containing energy sources, which is cost-effective, requires low process complexity and ensures high process stability on the one hand and a high yield of the calorific value of the energy sources used on the other hand.

To achieve the above object, it is provided in a method of the type mentioned above that at least one hydrocarbon-containing energy carrier, optionally at least one catalyst and optionally at least one additive, wherein the additive can be a neutralizer, as input material a process oil mixture containing reactor are fed, wherein a process oil mixture stream discharged from the reactor and to a process temperature between 150 ⁰ C to 400 ⁰ C, preferably between 350 ⁰ C to 380 ⁰ C, is heated, wherein the thus heated process oil mixture stream is fed to a degasser, wherein in the degasser vaporous middle distillate, namely vaporous hydrocarbon compounds in the boiling range of the middle distillate fraction of the petroleum, are separated from the heated process oil mixture stream and wherein one of the vaporous middle distillate relieved process oil mixture stream from the degasser to the process oil mixture present in the reactor is recycled.

In the invention, it is initially provided to heat the discharged from the reactor process oil mixture stream outside of the reactor to temperatures of at most 400 ⁰ C, preferably of at most 350 ⁰ C to 380 ⁰ C, so that the formation of reaction coke is reduced. The heating takes place gradient minimized. In this context, the invention According to the process of the invention, during the heating of the process oil mixture, temperature peaks, such as occur during the heating of the process oil mixture in the process known from DE 100 49 377 C2 to the tube bundles of the evaporator, can be excluded by suitable process control during heat transfer. During the heating of the process oil mixture, the maximum temperature should be maintained over the entire flow cross-section will always be less than 400 ⁰ C, preferably less than 380 ⁰ C. As a result of the lower coke formation thus caused, the cleaning effort can be reduced and the maintenance intervals can be extended, which contributes to a high economic efficiency of the method according to the invention. Incidentally, the invention does not provide a process oil mixture cycle in the proper sense: In the invention, the middle distillate vapor released from the heated process oil mixture is separated in the degasser and only the process oil mixture relieved of the vaporous middle distillate is fed back into the reactor. By means of a suitable design of the degaser, the yield in the process according to the invention can be significantly increased compared to the known processes.

Preferably, at least part of the heated process oil mixture stream can be applied from above into the degasser and split at internals of the degaser into a plurality of partial streams, wherein the partial streams then flow off in a Rie selfilmströmung to the reactor. Preferably, a substantially smooth falling film flow is formed in the degasser with negligible bubble formation, with the partial streams of the process oil mixture flowing down like a filament. In connection with the invention, it has surprisingly been found that a quiet surface of the falling film flow contributes to a high degree of yield of the calorific value of the energy carrier used, wherein a drop-shaped outflow of the process oil mixture by the degasser is undesirable and preferably largely precluded by corresponding constructive design of the internals is. A portion of the heated process oil mixture stream may also be introduced tangentially into the degasser, preferably below the internals, and flows downwardly in the form of a rotary flow on a container inner wall of the degasser toward the reactor. By dividing the heated process oil mixture stream into a first partial stream introduced from above into the degasser onto the internals and into a tangential into the degasser below the first partial stream Internals introduced second partial flow is a large surface of the process oil mixture produced in the degasser, which leads to a high release of vaporous middle distillate in the degasser.

According to the device, the degasser accordingly has an upper distribution chamber and a lower degassing chamber, wherein flow-dividing and surface-enlarging internals are provided for dividing a process oil mixture stream and for increasing the surface area of the process oil mixture stream, and wherein, preferably, the process oil mixture stream is centered in the dicing space from the top of the internals is aufgebbar. The degassing space can moreover have at least one inlet for a process oil mixture stream such that the process oil mixture stream can be introduced tangentially into the degasser and flows downwards in the direction of the reactor as a rotational flow on a container inner wall of the degassing space. The inlet into the degassing space is preferably arranged below the flow-conducting and surface-enlarging internals of the dicing space. The structural design of the degasher according to the invention is characterized by a high self-cleaning force and is low maintenance, whereby maximizing the surface of the process oil mixture flowing through the degasser is ensured with a correspondingly high yield of vaporous middle distillate.

The main energy input during the heating of the discharged from the reactor process oil mixture stream to a process temperature of preferably be- see 350 ⁰ C to 380 ⁰ C is carried out according to the invention by indirect heat transfer from a preferably liquid heat carrier in at least one static mixer with integrated heat exchanger device. According to the device, the static mixer can be designed as a mixed heat exchanger with a plurality of tube bundles for a heat transfer medium, in particular for a thermal oil, and mixing elements between the tube bundles for turbulent mixing of the process oil mixture. At the same time, therefore, there is heating and intensive mixing of the process oil mixture stream to be heated, it being possible for a turbulent mixture of the process oil mixture to form in the static mixer. In addition, an indirect heat transfer of the process oil mixture contained in the reactor may be provided, wherein a heat transfer from a preferably liquid heat carrier, such as a hot thermal oil, carried on the process oil mixture through an outer wall of the reactor. The thermal oil which can be used for heating the process oil mixture stream in the static mixer and for heating the process oil mixture contained in the reactor, should preferably have a maximum temperature of less than 400 ⁰ C, in particular less than 380 ⁰ C, to Avoiding or reducing the formation of reaction coke, which ultimately simplifies maintenance.

According to the device, the reactor can have an upper cylindrical wall section, wherein, preferably, the upper wall section is designed as a double-walled cylinder having a reactor inner wall and a reactor outer wall and wherein, more preferably, a guide device for a heat carrier mounted spirally on at least one reactor wall is provided in the double jacket is. The upper wall portion has an upper inlet port and a lower inlet port for a heat carrier, wherein the heat carrier spirally flows down the reactor inner wall along. As a result, an additional energy input or a cooling of the process oil mixture in the reactor is possible.

The process oil mixture stream steam-relieved from the middle distillate can be diverted into the reactor as it exits the degasser, preferably creating a tangential rotational flow on the reactor wall. The process oil mixture in the reactor is mixed statically.

In an upper inlet region of the reactor, internals are preferably provided for the flow diversion of the relieved process oil mixture returned from the degasser into the reactor, the internals being designed to produce a tangential wall flow along the reactor wall. The reactor is thus designed as a static mixer, with no active stirring devices are required. This contributes to a cost-effective construction of the reactor. The reactor may have an inwardly curved container bottom, so that a sedimentation cone is formed in the lower region of the reactor, which prevents the discharge of spent catalyst. material, aggregates and unreacted energy from the reactor.

In a further embodiment of the method according to the invention it can be provided that a further process oil mixture stream from the reactor is passed into a pre-reactor with mixing devices, the input material is fed to the prereactor and mixed with the further process oil mixture stream in the prereactor and wherein the hydrocarbon-rich Process oil mixture stream from the pre-reactor is returned to the reactor. In the prereactor there is a pre-dewatering and pre-degassing and only a small part of a catalytic reaction. In the pre-reactor, the input material is of about 350 ⁰ C hot Prozeßölge- mixed, originating from the reactor (main), mixed with the liquefaction process of the energy source used. However, the cracking of hydrocarbon compounds is preferably largely prevented due to short residence times in the prereactor and then takes place only in the (main) reactor. The pre-reactor, preferably designed as a screw conveyor, has at least one feed screw, preferably a twin screw, as input unit for the input material and a mixing container connected to the feed screw, wherein, more preferably, the feed screw engages into the lower region of the mixing container and has mixing vanes at the lower end , This ensures on the one hand intensive mixing of the input material with the process oil mixture originating from the (main) reactor and on the other hand ensures good self-cleaning of the feed screw.

In principle, the feed screw is cooled by incoming input material, but cooling of the feed screw may be necessary, in particular when the process is shut down for reasons of material resistance. In principle, it is also possible that a heating of the feed screw is provided to ensure a sufficiently high temperature in the prereactor.

For intensive mixing, the mixing vessel of the pre-reactor may at least have a lower inlet for the further process oil mixture stream from

(Main) reactor and at least one upper outlet for the hydrocarbon have rich process oil mixed stream. The mixing container is thus designed as a static mixer in which, however, essentially no cracking processes of the energy carrier take place. Corresponding internals can be provided in addition to intensify the mixing. For the same purpose, a tangential supply of the further process oil mixture stream into the mixing container can be provided.

Finally, via the prereactor, in particular via the mixing vessel, a carrier oil can also be fed to the (main) reactor, which forms a constituent of the process oil mixture in the reactor.

In order to ensure a high process stability and a high yield of the calorific value of the input material, the volume ratio of the process oil mixture in the (main) reactor to the further process oil mixture in the pre-reactor should be adjusted to 5: 1 to 8: 1. This requires a corresponding structural design of the reactor vessel and the mixing chamber of the pre-reactor.

The hydrocarbon-rich process oil mixture stream recycled from the prereactor is mixed with the process oil mixture contained in the reactor and the process oil mixture stream from the degasser which is relieved of the vaporous middle distillate. The feed of the hydrocarbon-rich process oil mixture stream into the reactor takes place below the internals provided in the upper region of the reactor for the flow deflection of the relieved process oil mixture returned from the degasser to the reactor. The hydrocarbon-rich process oil mixture stream recirculated from the prereactor is preferably introduced tangentially into a mixing zone of the reactor, so that a rotational flow of the entire process oil mixture is formed in the reactor. The targeted entry of the recirculated from the pre-reactor hydrocarbon-rich process oil mixture stream, the process oil mixture in the reactor is rotated. The direction of rotation of the discharged from the degasser discharged process oil mixture stream after entering the reactor may correspond to the direction of rotation of the tangentially introduced hydrocarbon-rich process oil mixture stream from the prereactor. According to the device, the reactor may have a lower part with a conically tapering upper wall section and a conically tapered lower wall section, the upper and lower wall sections being connected to one another by a cylindrical wall section. The process oil mixture stream, which is supplied to the static mixer for heating and mixing, can be removed in the upper region of the conically tapering upper wall section, wherein at least one outlet is provided there. As a result of this design of the reactor, it is possible to discharge the process oil mixture stream to be heated from an upper first sedimentation zone of the reactor and to pass it to the static mixer with integrated heat transfer device.

At least one further outlet may be provided in the upper region of the conically tapering lower wall section of the lower part. This outlet is provided for discharging a process oil mixture stream enriched with at least one catalyst and optionally with at least one aggregate from a lower second sedimentation zone of the reactor.

For multiple use of the catalyst, it is possible to mix the process oil mixture stream to be heated from the upper first Sedimendationszone with an enriched with catalyst and optionally additive process oil mixture stream from a lower second sedimentation zone of the reactor and thus set a certain catalyst concentration in the process oil mixture. The mixing of the two streams takes place before entering the static mixer, so that both streams are intensively mixed and heated in the mixer. Otherwise, a control or regulating device for controlling or regulating the volume flow ratio of the process oil mixture stream to be heated to the enriched process oil mixture stream can be provided.

A partial flow of the process oil mixture stream to be heated and, if appropriate, a further partial stream of the process oil mixture stream enriched with catalyst and optionally neutralizer form the further process oil mixture stream conducted to the prereactor. Shortly before conveying the process oil mixture stream to be heated and, if appropriate, the catalyst-enriched process oil mixture stream into the static mixer, an admixture of at least one unconsumed catalyst and / or optionally at least one additive from corresponding feed containers may be provided. In this case, the catalyst and / or additive is preferably mixed before admixture with a carrier oil or emulsified in a carrier oil, which simplifies the mixing.

According to the invention, it is further provided that the energy carrier, the catalyst and optionally the aggregate, which together can form the input material for the process, are mixed together before being fed into the prereactor and heated to a temperature of less than 120 ^° C., preferably up to about 80 to 100 ⁰ C, to be heated. This leads on the one hand to drying and on the other to aggregate formation before the addition of the input material into the prereactor. The energy carrier is dry mixed with preferably powdered catalyst and / or neutralizer and heated, wherein the resulting aggregate has a high reaction surface and segregation does not take place. Moreover, the unit has a longer residence time in the process oil mixture. This further increases the yield level.

The invention allows individual ideas of the invention to be combined with each other, even if this is not described in detail. Incidentally, the static mixture and surface enlargement of the process oil mixture in the degasser and in the reactor and the premixing of the input material with the process oil mixture in the prereactor are of inherent relevance, whereby the inventive concepts associated therewith can also independently substantiate an inventive performance.

The invention will now be described by way of example with reference to the drawing. In the drawing shows

1 is a schematic process flow diagram of the entry of a hydrocarbon-rich energy carrier together with a catalyst and a neutralizer into an oil circuit for the production of vaporous middle distillate and FIG. 2 is a schematic flowchart of the reaction cycle in the production of middle distillate from hydrocarbon-containing energy sources. FIG.

FIG. 1 shows a process flow diagram representing the entry of a hydrocarbon-containing energy carrier 1 into an oil circuit for producing middle distillate 2. The energy carrier 1 in the present case is dried and comminuted biomass which is stored in a storage container 3. Due to gravity, the energy carrier 1 falls from the storage tank 3 into a first conveyor screw 4. By rotation of the spindle, the mixture is pushed into the lower hopper of a Rohrkettenförde- rers 5. The tube chain conveyor 5 transports the energy source 1 to a height of about 12 m in an upper funnel. From there, the energy source 1 falls due to gravity in a feed screw 6. The feed screw 6 promotes the energy source 1 with a quantity of 5 m ³ / h in a first rotary valve 7 or in a second rotary valve 8. The rotary valves 7, 8 serve the periodic metering of cone mixers 9, 10 with the starting material, wherein each rotary valve 7, 8 is designed with a delivery capacity of 5 m ³ / h. The rotary valves 7, 8 represent dynamic barriers, since material can be transported through and at the same time a slight negative pressure, generated by a vacuum system, in the conical mixers 9, 10 is made possible.

The conical mixers 9, 10 are degassed in order to reduce the proportion of oxygen and to minimize the risk of ignition of the oil vapor produced in the further process. The cone mixers 9, 10 have a net volume of about 2.4 m ³ . The cone mixers 9, 10 are operated alternately periodically. While the first cone mixer 9 is being filled with the energy carrier 1, the second cone mixer 10 can be mixed with the aid of the integrated screw.

In addition to the energy carrier 1, at least one catalyst Ia and / or one additive Ib, such as a neutralizer, may periodically be added to the cone mixers 9, 10, where the catalyst Ia and the additive Ib may be present as a pulverulent mixture. The time of mixing, heating, dehumidification and degassing in the Konusmi- 9, 10 is about half an hour, the time of filling is also half an hour. Since both cone mixers 9, 10 have a double jacket, the heating of the mixture in the cone mixers 9, 10 to about 100 ⁰ C is possible. The cone mixers 9, 10 are with a heating medium, preferably heating a thermal oil so that the input material 12 preferably reaches into the cone mixers 9, 10, a temperature of about 80 ⁰ C. This leads to the drying of the input material 12 in agglomerate formation, which has an advantageous effect on the yield in the production of middle distillate 2 from the energy carrier 1. The temperature increase is necessary in order to reduce the proportion of water in the mixture, since it evaporates at this temperature and can be discharged via degassing lines of the cone mixers 9, 10. Excessive water content could lead to a steam explosion in the further process. In addition, at a high water content, the effective separation efficiency would be reduced in the production of middle distillate from hydrocarbon-containing energy sources 1.

The two conical mixers 9, 10 allow a continuous loading of a four-zone reactor 11 shown in FIG. 2, whereby the cone mixers 9, 10 are emptied periodically via gas-tight slides. From the cone mixers 9, 10, the input material 12 is discharged, which is composed of the energy source 1, possibly the catalyst and optionally at least one additive. The input material 12 passes into a connecting screw 13 and then into a compacting screw 14, in which the input material 12 is compressed to half the original size. The connecting screw 13 and the compression screw 14 each have a double jacket, through which a heating medium, preferably thermal oil, with a temperature of about 100 to 120 ⁰ C is passed. This ensures that the temperature of the input material 12 is kept constant at about 100 ⁰ C.

Moreover, the compression screw 14 suction points to more water, u.a. To remove adhesive water from the dried input material 12. In addition, the proportion of oxygen is further reduced.

From the compression screw 14, the input material 12 passes into two ATEX Räumradschleusen 15, 16. The Räumradschleusen 15, 16 promote the Input material 12 into the hopper 17 of a screw feed mixer 18. The screw feed mixer 18 is a pre-reactor with mixing device and has an oval connecting tube 19, a twin screw 20 and a mixing container 21 containing about 800 1.

The input material 12 is pushed from the hopper 17 through the connecting pipe 19 in the mixing vessel 21 by means of the twin screw 20 and mixed with a circa 350 ⁰ C hot process oil mixture stream 22, which is removed from the reactor 11 and from a carrier oil with already dissolved energy source. 1 exists, which is partly in cracked form. The screw ends of the twin screw 20 have mixing vanes 23, which contribute to the mixing of the input material 12 with the process oil mixture stream 22. The mixing function is assisted by metered tangential pumping in of the process oil mixture stream 22 from the reactor 11 into the mixing tank 21 by means of the volute casing pump 24, namely at two feed points 25, 26 of the mixing tank 21. This ensures double mixing. Furthermore, the twin screw 20 acts as a baffle, since it is located in the region between the center of the mixing container 21 and its wall. The twin screw 20 causes additional turbulence of the flow. The use of a twin screw 20 is characterized, moreover, at relatively high temperatures in the mixing container 21 by a high reliability.

In the mixing vessel 21, the process oil mixture 22 flows upwards with a rotational movement and mixes with the fed-in input material 12. After a short time, a hydrocarbon-rich process oil mixture stream 26 obtained in the upper region of the mixing vessel 21 is withdrawn and returned to the reactor 11.

When the input material 12 enters the screw feed mixer 18, the liquefaction process begins. The cracking process, namely the cleavage of the carbon chains, starts due to a very short residence time of the process oil mixture in the screw feed mixer 18 not or only to a small extent, but exclusively or predominantly only in the main process in the reactor 11. Should on the surface of the reaction mixture in the mixing vessel 21st the not yet completely dissolved energy sources 1 swim is this retained by appropriate installations in the mixing tank 21 and returned to the mixture. If the input material 12 dissolves in the screw feed mixer 18, residual water fractions released from the screw feed mixer 18 are released. The water vapor passes into a demister 27, which contains fillers, which adhere to the oil droplets transported by the steam and then flow back into the screw feed mixer 18. The water vapor is discharged via a vacuum system and the residual water is liquefied in a condenser 28.

Both spindles 29, 30 of the twin screw 20 work self-cleaning. The spindles 29, 30 are rotatably mounted at the lower end to the conical bottom of the mixing container 21 and at the upper end by shaft passages of the hopper 17. The connecting tube 19 is likewise equipped with a double jacket, since temperatures of up to 350 ^° C. can prevail in the mixing container 21. The temperature in the hopper 17 may not exceed 100 ⁰ C, since the Räumradschleusen 15, 16 are designed with ATEX protection only up to 100 ⁰ C. Should too much heat flow upwards via the connecting pipe 19, this can be discharged via the double jacket, whereby a corresponding cooling medium is passed through the double jacket.

For the entry of carrier oil 31, such as dewatered waste oil, in the oil circuit a heatable container 32 is provided as a reservoir. Also, such liquid residues can be introduced as an energy source in the oil circuit. With the pump 33, the carrier oil 31 is introduced into the mixing container 21. The filling of the container 32 via a pump from an oil storage. As a result, via the screw feed mixer 18, the carrier oil 31 can be fed to the reactor 11, for example to compensate for evaporation losses. In addition, a carrier oil stream 34 for producing a catalyst / additive emulsion can be conducted from the container 32 into containers 35, 36 shown in FIG. 2. The containers 35, 36 have feed hoppers to facilitate filling with the catalyst Ia and the additive Ib.

The structure of the entry system shown in Fig. 1 allows sufficient drying, mixing and deaeration of the input material 12. Die Danger of steam explosion in the reactor 11 is therefore not. Likewise, the ignition of released oil vapor need not be feared. Finally, a high separation efficiency is ensured by a small proportion of water in the reactor 11.

FIG. 2 shows the main circulation system in the production of middle distillate 2 from the hydrocarbon-containing energy carrier 1. The components of the main circulation or reaction system are the four-zone reactor 11, a degasser 37 and three Mischwärmetauscherpaare 38, 39, 40 and a plurality of pumps and the associated piping.

In the production of middle distillate 2 from hydrocarbon-containing energy source 1, a molecular dehydration, a molecular polymerization and a molecular shortening (depolymerization / de-oiling) take place at a lower temperature in relation to the pyrolysis without pressurization. The process control is carried out in the main stream at temperatures between 300 to 400 ⁰ C and a slight negative pressure of - 30 to - 100 mbar compared to the ambient pressure. The method described is characterized by a high degree of yield of the calorific value of the energy carrier 1. If polymer waste is used as the energy carrier, more than 70 to 80% of the hydrocarbons present can be obtained. Incidentally, there is a detoxification of environmentally relevant halogens by binding in the liquid state as immobilizable salts.

The hydrocarbon-enriched process oil mixture stream 26 originating from the screw feed mixer 18 as prereactor is introduced into the reactor 11. The process oil mixture 54 contained in the reactor 11, comprising the dissolved energy carrier 1, optionally the catalyst Ia, optionally the additive Ib and carrier oil, is circulated, wherein each circulation a resulting amount of vaporous middle distillate in a above the degasser 37th provided processing system 41 is transferred. The work-up system 41 is shown only schematically in FIG. The main constituents of the work-up system 41 are a steam release pre-distillation unit or pre-rectification unit, a rectification column, as well as condensers and water separators. In the work-up system 41, the vaporous middle distillate is divided into four groups by distillation. separates, namely low boilers (hydrocarbon in the boiling range of kerosene and gasoline), intermediate product (gas oil, namely hydrocarbon mixture in the boiling range of diesel), high boilers (process oil or carrier oil) and bottom product (distillation residues).

The reactor 11 is structurally equipped with a double cone shape in the lower region. The reactor 11 has an upper cylindrical wall section 43 with a lower part 44, wherein the lower part 44 has a tapered upper wall section 45, a conically tapered lower wall section 46 and a cylindrical central wall section 47. In the region of the lower part 44 outlet port 50, 51 are welded, and an outlet 52 for filter bed material 42, which is part of the sump circuit.

A double jacket in the region of the upper cylindrical wall section 43 serves for additional heat transfer / cooling with a liquid heat carrier, namely thermal oil. The double jacket is made so that the introduced through the upper inlet port 48 thermal oil flows through a helically mounted on the reactor outer wall guide around the reactor 11 and the double jacket leaves at an outlet 49. Otherwise, the reactor 11 has internals for the flow deflection in the region of its lid.

The reactor 11 can be divided into four zones I-IV. The uppermost zone I is a gas / steam zone. Here, a small amount of middle distillate steam flows from the mixing zone II underneath into the degasser 37. In the uppermost zone I, the internals for flow diversion are also arranged.

In the upper section of the mixing zone II, the hydrocarbon-rich process oil mixture stream 26 is introduced tangentially into the mixing zone II in the region of an inlet connection 53 and mixes with the process oil mixture 54 present there. In addition, mixing takes place in the mixing zone II with a discharge of vaporous middle distillate 2 Process oil mixture stream 55 from the degasser 37. Due to the tangential introduction process, the entire liquid in the reactor 11 rotates. The rotational movement is additionally caused by the deflected liquid medium from the degasser 37 Kept moving. The direction of movement of the rotating process oil mixture 54 and the relieved process oil mixture stream 55 correspond to each other.

A sedimentation zone III represents a third section of the reactor 11 and is located in the upper cone segment. Here, part of the process oil mixture 54 is required by the nozzles 50 as the process oil mixture stream 56 to be heated by means of the pumps 57, 58, 59 from the reactor 11 to the three mixed heat exchangers 38, 39, 40.

In a lowermost zone IV of the reactor 11, i. in the lower cone segment, the enrichment of the process oil mixture 54 with catalyst and additive takes place in high-boiling hydrocarbon matrix. The lowermost zone IV represents a second sedimentation zone. From the lowermost zone IV, a process oil mixed stream 60 enriched with catalyst Ia and the additive Ib is mixed with the process oil mixture stream 56 to be heated by means of the pumps 61, 62, 63 as required. A partial flow 56a of the process oil mixture stream 56 to be heated and a partial stream 60a of the enriched process oil mixture stream 60 form the process oil mixture stream 22 conducted to the screw feed mixer 18, in which the energy carrier 1 is dissolved before it enters the reactor 11.

The mixing heat exchangers 38, 39, 40 each consist of two flange-mounted mixed heat exchanger units, wherein mixed heat exchanger units with the trade name "CSE-XR" from Fluitec can be used. Between the tube bundles of the mixed heat exchanger units mixing elements are welded, which lead to a turbulent mixing of the process oil mixture.

Shortly before the process oil mixture stream 56 and possibly the enriched process oil mixture stream 60 are conveyed into the three mixing heat exchangers 38, 39, 40, an admixture of catalyst Ia and, if necessary, of additive Ib may take place. In the mixing heat exchangers 38, 39, 40, the components are then turbulently mixed and heated to about 380 ⁰ C. The heating takes place via a liquid heat carrier, namely thermal oil, which is supplied via inlet connection 64 and discharged via outlet connection 65. Furthermore have the mixing heat exchanger 38, 39, 40 inlet and outlet nozzle for a cleaning oil and nozzle for introducing nitrogen.

The process oil mixture stream 56 and optionally the enriched process oil mixture Ström 60 and optionally the attached catalyst Ia and possibly the added additive Ib arrive as a heated process oil mixture stream 67 from the mixed heat exchangers 38, 39, 40 in the upper portion 66 of the degas 37 In the region 66, the degasser 37 has a dicing space with flow-conducting and surface-enlarging internals for dicing and surface enlargement of the heated process oil mixture stream 67. The process oil mixture stream 67 is partly applied, preferably in the middle, into the dicing space from above onto the internals in the upper region 66 of the degas 37.

In addition, the degasser 37 has at least one inlet port for a partial stream 68 of the heated process oil mixture stream 67, wherein the partial stream 68 is conveyed tangentially into the degasser 37 in the upper region 66 of the degas below the internals and flows downwardly on the container inner wall of the degas 37 ,

Of the internals of the degas 37, the process oil mixture 67 flows down as a falling film, whereby a large surface is created by the fine division, which facilitates the escape of cracked carbon chains from the process oil mixture 67. These go into the vapor phase and flow off as vaporous middle distillate 2 to the work-up system 41. The thin streams flow together with the partial flow 68 flowing downwards in the direction of the inner wall of the container and reach the four-phase reactor 11. Shortly after entry, they encounter the internals in the gas-vapor zone I of the reactor 11 diverted and the cycle begins again.

The method for producing vaporous middle distillate 2 described with reference to FIGS. 1 and 2 is characterized by a statically enforced, absolutely turbulent mixture of the process oil mixture in the mixed heat exchangers 38, 39 and 40. This will the heat transfer gradients minimized and the system self-cleaning for the process oil solid mixture (catalysts, mineral aggregates) out.

As additives Ib hydrated lime, soda, clay and bentonites can be used. As catalyst Ia preferably mineral zeolitic solids are used. The preferably continuous solid addition of catalyst Ia and / or additive Ib is in the range of 0.5 to 20 wt .-% with respect to the process oil mixture 54 in the reactor 11. Catalysts Ia and aggregates Ib such as soda and hydrated lime, are usually with a proportion of 1 to 10 wt .-%, preferably from 1 to 5 wt .-%, promoted to the substance entry of the energy carrier 1 in the reactor 1.

In the sedimentation zone III of the reactor 11, partially undissolved residues sediment, the catalyst Ia and additives Ib. The catalyst bed thus formed in the lowermost zone IV is fed to the mixed catalyst fluidized bed by means of at least one volumetric pump 69 by recirculation over the upper part of the lowermost zone IV. Thus, if appropriate, the catalyst Ia and the additive Ib can be used several times for the material conversion. The mixed fluidized bed is kept constant in height by partial discharge of filter bed material 42 by means of the pump 69. To shut down the process, a drain tank 70 is provided.

Claims

claims:

1. A process for the production of middle distillate (2) from hydrocarbon-containing energy sources (1), wherein at least one hydrocarbon-containing energy carrier (1), optionally at least one catalyst (Ia) and optionally at least one additive (Ib) as input material (12) a Process oil mixture (54) containing reactor (11) are supplied, wherein a process oil mixture stream (56) discharged from the reactor (11) and to a process temperature between 150 ⁰ C to 400 ⁰ C, preferably between 350 ⁰ C to 380 ⁰ C. wherein the heated process oil mixture stream (67, 68) is fed to a degasser (37), wherein in the degasser (37) vapor middle distillate (2) is separated from the heated process oil mixture stream (67, 68) and wherein one of the vaporous middle distillate (2 ) Relieved process oil mixture stream (55) from the degasser (37) to the in the reactor (11) existing process oil mixture (54) is returned.

2. The method according to claim 1, characterized in that the heated process oil mixture stream (67) at least partially abandoned from above into the degasser (37) and divided at internals of the degasifier (37) into a plurality of sub-streams, wherein the partial streams in drain a trickle film flow to the reactor (11).

3. The method according to claim 1 or 2, characterized in that a partial stream (68) of the heated process oil mixture stream (67) is introduced tangentially into the degasser (37) and as a rotational flow on a container inner wall of the degaser (37) down in the direction flows to the reactor (11).

4. The method according to any one of the preceding claims, characterized in that the main energy input in the heating of the Prozeßölge- mixed stream (56) to process temperature by indirect heat transfer from a preferably liquid heat carrier to the process oil mixture stream (56) takes place in at least one static mixer with integrated heat transfer device ,

5. The method according to any one of the preceding claims, characterized in that in the static mixer, a turbulent flow of the process oil mixture stream (56) is formed.

6. The method according to any one of the preceding claims, characterized in that an indirect heat transfer in the reactor (11) contained process oil mixture (54) is provided, wherein a heat transfer from a heat transfer medium to the process oil mixture (54) through an outer wall of the reactor (11 ) he follows.

7. The method according to any one of the preceding claims, characterized in that the relieved process oil mixture stream (55) is deflected upon entry into the reactor (11), wherein a tangential rotational flow is generated on the reactor wall.

8. The method according to any one of the preceding claims, characterized in that a further process oil mixture stream (22) from the reactor (11) is passed into a pre-reactor with mixing device, that the input material (12) fed to the pre-reactor and with the further process oil mixture stream (22). is mixed in the prereactor and that the hydrocarbon-rich process oil mixture stream (26) thus obtained from the pre-reactor in the reactor (11) is recycled.

9. The method according to any one of the preceding claims, characterized in that the recycled from the pre-reactor hydrocarbon-rich

Process oil mixture stream (26) with the process oil mixture contained in the reactor (11) (54) and the vapor of the middle middle distillate (2) relieved process oil mixture stream (55) from the degasser (37) is mixed.

10. The method according to any one of the preceding claims, characterized in that the recycled from the prereactor hydrocarbon-rich process oil mixture stream (26) tangentially into a process oil mixture (54) containing mixing zone (II) of the reactor (11) is introduced so that a rotational flow of the entire process oil mixture (54) in the reactor training.

1 1. A method according to any one of the preceding claims, characterized in that the direction of rotation of the relieved process oil mixture stream (55) after entering the reactor (1 1) corresponds to the direction of rotation of the hydrocarbon-rich process oil mixture stream (55).

12. The method according to any one of the preceding claims, characterized in that the volume ratio of process oil mixture (54) in the reactor (11) and further process oil mixture in the prereactor to 1: 5 to 1: 8 is set.

13. The method according to any one of the preceding claims, characterized in that the to be heated process oil mixture stream (56) from an upper first sedimentation zone (III) of the reactor (11) dissipated and passed to the static mixer with integrated heat transfer device.

14. The method according to any one of the preceding claims, characterized in that from a lower second sedimentation zone (IV) of the reactor (11) enriched with at least one catalyst (Ia) and optionally with at least one additive (Ib) enriched process oil mixture stream (60) off guided and possibly mixed with the process oil mixture stream (56) to be heated.

15. The method according to any one of the preceding claims, characterized in that a partial stream (56a) of the process oil mixture stream to be heated (56) and, optionally, a further partial stream (60a) of the enriched with catalyst and optionally neutralizer process oil mixture stream (60) the Form pre-reactor led further process oil mixture stream (22).

16. The method according to any one of the preceding claims, characterized in that shortly before conveying the process oil mixture stream to be heated (56) and optionally the enriched process oil mixture stream (60) in the static mixer with integrated heat transfer device, an admixture of at least one catalyst (Ia) and or optionally at least one additive (Ib) is provided.

17. The method according to claim 16, characterized in that the catalyst (Ia) and / or aggregate (16) before the admixture in a carrier oil (34) are emulsified.

18. The method according to any one of the preceding claims, characterized in that the energy carrier (1), the catalyst (Ia) and the additive (Ib) mixed before being fed into the prereactor and to a temperature of less than 120 ⁰ C, preferably about 80 to 100 ⁰ C, to be heated.

19. The method according to any one of the preceding claims, characterized in that the reactor (11) continuously with the energy carrier (1), the catalyst (Ia) and the additive (Ib) is charged

20. An apparatus for carrying out a process for producing middle distillate (2) from hydrocarbonaceous energy sources (1) according to one of the preceding claims, comprising at least one degasser (37), wherein the degasser (37) has an upper dewatering space and a lower degassing space. space, wherein in the dicing space flow-conducting and surface enlarging internals for the division of a process oil mixture stream (67) and surface enlargement of the process oil mixture stream (67) are provided, wherein, preferably, the process oil mixture stream (67) is aufgebar centrally in the dicing space from above on the internals.

21. The apparatus according to claim 20, characterized in that the Dega- sungsraum at least one inlet for a partial stream (68) of the process oil mixture stream (67) such that the partial stream (68) tangentially into the Degaser (37) can be introduced and as a rotational flow flows down at a container inner wall of the degassing space in the direction of the reactor (11).

22. An apparatus for carrying out a method for producing middle distillate (2) from hydrocarbon-containing energy carriers (1) according to any one of the preceding claims, in particular according to claim 20 or 21, with at least one static mixer with integrated heat transfer device, wherein the static mixer as a mixed heat exchanger (38 , 39, 40) is formed with a plurality of tube bundles for a heat transfer medium and mixing elements between the tube bundles for turbulent mixing of a process oil mixture.

23. Apparatus for carrying out a process for producing middle distillate (2) from hydrocarbonaceous energy sources (1) according to one of the preceding claims, in particular apparatus according to one of the preceding claims 20 to 22, with at least one reactor (11) for a process oil mixture ( 54), wherein the reactor (11) has an upper cylindrical wall section (43), wherein, preferably, the upper wall section (43) is designed as a double-walled cylinder with a reactor inner wall and a reactor outer wall and wherein, more preferably, in the double jacket spirally mounted on at least one reactor wall guide is provided for a heat transfer medium.

24. The device according to claim 23, characterized in that in an upper inlet region into the reactor (11) internals for Strömungsumlen- kung of a process oil mixture are provided, wherein the internals are formed to produce a tangential wall flow along the reactor wall.

25. The apparatus of claim 23 or 24, characterized in that the reactor (11) has a lower part (44) with a tapered upper wall portion (45) and a tapered lower wall portion (46), wherein the upper and the lower wall portion (45, 46) are interconnected by a cylindrical wall portion (47)

26. Device according to one of claims 23 to 25, characterized in that at least one outlet is provided in the upper region of the conically tapering upper wall portion (45)

27. Device according to one of claims 23 to 26, characterized in that at least one further outlet is provided in the upper region of the conically tapered lower wall portion (46).

28. Device according to one of claims 23 to 27, characterized in that a control or regulating device for controlling or regulating the Volume flow ratio of at least two process oil mixture streams (56, 60) is provided.

29. An apparatus for carrying out a process for producing middle distillate (2) from hydrocarbonaceous energy sources (1) according to one of the preceding claims, in particular apparatus according to one of claims 20 to 28, with at least one prereactor, wherein the prereactor comprises at least one feed screw, preferably a twin screw (20) as an entry unit, for the energy carrier (1), the catalyst (Ia) and the aggregate (Ib) and a mixing bowl connected to the feed screw (21), wherein, preferably, the feed screw into the lower region of the mixing container (21) engages and has mixing vanes (23) at the lower end.

30. The device according to claim 29, characterized in that the entry screw is heated and / or cooled.

31. The apparatus of claim 29 or 30, characterized in that the mixing container (21) has at least one lower inlet and at least one upper outlet for a process oil mixture stream (22, 26).

32. Device according to one of claims 29 to 31, characterized in that the inlet for the tangential supply of the process oil mixture stream (22) in the mixing container (21) is formed.

33. Device according to one of claims 29 to 32, characterized in that via the mixing container (21) a carrier oil (31) in the reactor (11) can be fed.