WO2006092306A1 - Method for depolymerising residues containing hydrocarbons and device for carrying out said method - Google Patents
Method for depolymerising residues containing hydrocarbons and device for carrying out said method Download PDFInfo
- Publication number
- WO2006092306A1 WO2006092306A1 PCT/EP2006/001919 EP2006001919W WO2006092306A1 WO 2006092306 A1 WO2006092306 A1 WO 2006092306A1 EP 2006001919 W EP2006001919 W EP 2006001919W WO 2006092306 A1 WO2006092306 A1 WO 2006092306A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- scraper
- raw material
- wall
- cleaning
- Prior art date
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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
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
Definitions
- the invention relates to a process for the depolymerization of carbonaceous residues, in particular for the production of diesel and heating oil, according to the preamble of claim 1 and an apparatus for carrying out this process according to the preamble of claim 15.
- the depolymerization process ie the molecular shortening of long-chain hydrocarbon compounds, takes place relatively rapidly owing to the catalytic cleavage.
- the hydrocarbon molecules attach themselves to the catalysts until they have reached the - depending on the type of residue - reaction temperature and vaporize the cleavage products.
- a sequential heater such as a tube heat exchanger, the vaporization temperature of the desired and lower boiling fractions is regained. The remaining liquid components are returned to the raw material feed.
- the forming in this cycle process agglomerations of catalyst material and higher boiling components of the raw material are discharged and further processed.
- the leaving the circuit vaporous fraction is in a distillation unit to obtain z.
- Gaseous components are burned to produce hot combustion exhaust gases that provide the amount of heat and process temperature (gap temperature) required for evaporation in the fluid circuit.
- the raw material contains chlorine, sulfur, phosphorus and / or other components which are undesirable in the product (diesel or heating oil)
- these are removed in the cycle process. This is done, for example, by using calcium aluminum silicate or sodium aluminum silicate as the ion-exchangeable catalyst and adding z.
- lime in order to bind the chlorine, sulfur or phosphorus components to be removed from the raw material.
- the catalytic depolymerization plant according to DE 103 16 969 A1 likewise circulates a catalyst suspended in a cycle oil.
- the latter is formed by the depolymerization reactor, a hydrocyclone and a separation vessel.
- the heating takes place in the specially constructed reactor by electric wall heating.
- This reactor has a central supply pipe for raw material, fresh catalyst, lime and circulating oil, which is guided with a screw conveyor down and mixed there with the recirculation liquid flowing back from the separation vessel.
- the central tube is surrounded within the reactor by several riser tubes, which allow an increase in the reactor sump resulting mixture via augers.
- An electrical wall heating of the riser pipes ensures that the gap temperature is reached so that a liquid vapor mixture is withdrawn at the upper end of the reactor.
- a method with the features of claim 1 and a device having the features of claim 15 is proposed in a generic depolymerization to improve the raw material and heat input.
- the invention is based on the idea, the raw material in one - A - inject heated to nip temperature reactor in liquid or pasty consistency in a preheated state under pressure.
- the invention makes it possible to produce, in particular, diesel / heating oil in a simple manner and with high yield from various organic substances; on the other hand, the generation of by-products such as dioxin, methane and others can be avoided in this method of waste and residual material utilization.
- the gas production is extremely low and can e.g. be reduced to about 4.5% of the raw material. For underfiring this gas is anyway reusable in the process.
- the use of catalysts is possible, but advantageously the process allows the avoidance of catalysts and the associated procedural difficulties and costs.
- residues hydrocarbon-containing raw materials
- liquid products such as, in particular, diesel oil.
- raw material are mainly old, residual and waste materials into consideration, such as plastics, oils (also used and flushing oils), fats, dried garbage, electric cables, wood, paper, digested sludge, agricultural residues, natural fibers and many other waste or waste materials, but also renewable raw materials and rubbers.
- plastics and waste oils are particularly advantageous.
- the process of cracking or depolymerization can thus be used to produce a high quality asset, namely fuel oil or diesel fuel from waste oil and plastics again.
- a pre-heating of a mixture of plastics and waste oils which, particularly preferably, is carried out at temperatures above 200 0 C, in particular to temperatures between about 250 0 C and 300 0 C.
- a significant advantage here is that water components of the feed mixture evaporate and do not enter the reactor. In addition, all other low-boiling substances are expelled, which therefore do not have to be channeled through the system.
- the waste heat of the cleavage reactor can be used.
- the introduced plastics are thus, for example, recuperative, regenerative or by friction, preheated, conveyed to an injection nozzle such as an extruder and injected there under a certain or adjusting pressure in the reactor.
- an injection nozzle such as an extruder and injected there under a certain or adjusting pressure in the reactor.
- the pressure build-up and / or the injection nozzle which can also be formed by the mouth of a pipeline, it can be achieved that this process is carried out continuously, ie that the raw material feed into the reactor is continuous and approximately constant .
- keeping the level in the reactor constant also requires that the removal of gases and of solid and liquid constituents and the feed-in of raw materials be adapted to each other. This leads to constant process conditions, which ensure a consistent product quality. Waste oil can be introduced in the same way in the reactor.
- the raw material is further heated, whereby the long-chain hydrocarbons are broken down into shorter-chain molecules. These have the energy at this temperature to leave the melt as gas and ascend into a distillation column. Depending on their length they are collected in different stages of the column. If the process parameters of the column are set correctly in a manner known per se, then in a condenser, with z. B. water cooling, the product - this oil or fuel oil - won. So far, the feedstock without special measures in finely divided state was fed into the reactor. The injection is carried out for the purpose of careful further heating in a centrally located area of the reactor.
- the reactor As a particularly rotationally symmetrical pot, e.g. with a parabolic or hygrobular inner contour in which a multi-bladed mixer rotates. It is advantageous if the ends of the mixing arm made of temperature-resistant ceramic or graphite material and / or the inner contour of the reactor are modeled substantially and provided with, in particular very little game, so as to prevent or eliminate deposits. As a result, the interfering carbon is deposited on the bituminous sludges forming as a waste product and is removed with these instead of being baked on the heated walls of the reactor.
- the surface cleaning on the inner wall of the reactor can, if appropriate, also be carried out without a targeted mixing action by means of a cyclically operating scraping device, which is of independent inventive significance and is preferably guided cyclically along the contour of the inner wall of the reactor with minimal or no lateral play.
- Rotationally symmetric reactor inner wall contours are preferred for this purpose.
- a scraper head of the scraper device in this case carries at least two rotationally driven contour-matched scraper elements. These may be equipped with a replaceable wear pad, with the exceeding of a permitted wear clearance, for example, can be detected electrically measured. If the scraping head with its own weight or under the action of a force introduced by its rotational force to the reactor inner wall is applied or pressed, even small agglomerations can be removed from the reactor inner wall and fed to a reactor sump for discharging.
- the scraping device can be protected by a self-cleaning element, which can be activated from time to time for, in particular, scraping cleaning of the scraper elements via the scraping head.
- Typical cleaning cycles of a rotating scraper with two blades are about 1 to 1000 cleaning cycles per hour, preferably the rotational speed of a scraper head is from 1 to 20, preferably from 5 to 10 revolutions per minute.
- the weight of the scraping device which generates a certain contact pressure, may be a few grams to a few thousand kilograms. With a reactor capacity of about one cubic meter, typical self-weights of the scraping head are on the order of 10 kg to 1000 kg, preferably between 50 kg and 200 kg.
- the temperature differences between the mean desired temperature in the liquid to be depolymerized within the reactor and on the outer wall of the reactor can be kept advantageously low and can, for example, in the order of 20 ° and 8O 0 C are kept.
- a further aspect of the invention is the improvement of a scraping device for demopolymerisationsreaktoren and the like as such.
- a self-cleaning element of the scraper head is proposed for occasionally cleaning the scraper element during the ongoing depolymerization operation.
- the actuation preferably takes place via the rotational shaft, in particular by a telescoping movement.
- Self-cleaning scraping elements are of independent inventive importance.
- Another aspect of the invention is a reactor construction which promotes the long-term availability of the depolymerization plant.
- the reactor together with its heating separately from a reactor lid with the distillation column can be separated by lowering and exchanged for a new or overhauled reactor.
- the reactor may be e.g. be quickly replaced for overhaul purposes.
- Flow guiding elements on its outer surface allow effective heat guidance both during heating, during temperature maintenance and during cooling. This aspect of the invention is also of independent inventive significance.
- Fig. 1 is a block diagram of a Depolymerisationsstrom
- Fig. 2 is an overview view of the practical construction of a depolymerization plant
- FIG 3 is a schematic representation of the reactor of a depolymerization plant including the reactor heating as a schematic representation in vertical section through the reactor center.
- FIG. 4 shows a detail view of the coupling of a scraping head to a rotating shaft for a reactor according to FIG. 3;
- Fig. 5 of the same reactor is a sectional view (section along the line
- FIG. 3 shows a scraper element held and moved by a receptacle
- Fig. 6 of the reactor of Figure 3 is a perspective view of the outside view
- FIG. 7A shows a scraping head in the scraping position for a depolymerization reactor
- FIG. 8A shows an alternative embodiment of a scraping head in the scraping position
- Fig. 8B of the same scraper head an enlarged sectional view in a position during the self-cleaning of the scraper head
- FIG. 8C from the same scraper head (in the position corresponding to Fig. 8B) a further enlarged detail.
- the block diagram of Figure 1 shows that an existing made of plastics and waste oil raw material 1 is heated in a preheater 2 to 250 0 C and subsequently a device for pressure injection, such as for injection molding of plastic known pressure and delivery pump (injection 3) is fed ,
- This pump allows the direct injection of the raw material into a cleavage reactor (reactor 4), the liquid content by heating 5 (with eg oil or gas and an exhaust gas temperature of about 800 ° C) at a gap temperature between about 300 ° and 46O 0 C, preferably between 340 ° C and 440 0 C and in particular between 390 ° C and 42O 0 C is maintained and its waste heat in part in the preheating stage 2, z.
- a recuperator is recovered. From the reactor 4, a vapor fraction is withdrawn, which is obtained after appropriate treatment, such as a fractional distillation, as product 6. Likewise, in a conventional manner from the reactor 4 of the resulting solid material is removed, usually de-oiled and recovered as residue 7 and optionally further processed.
- the reactor 4 can be constructed in many different ways, as well as for the heating 5 no very narrow limits.
- FIG. 2 gives a basic idea of the possible structure of a depolymerization plant according to the invention.
- the preheating of the raw material 1 takes place in a conveyor and compressor screw by external heating and / or friction.
- Various raw materials are supplied at various points, such as plastics, oils, in particular old / flushing oils and optionally additives.
- After at least partial preheating is a pressure release.
- water vapor and other gases can be supplied via an exhaust duct, for example a filter.
- the now almost or already completely liquid or pasty raw material is conveyed further by means of the outer end of the screw conveyor under possibly further heating and generation of internal pressure and injected into the interior of a pot-shaped, externally heated Depolymerisationsreaktors 4.
- the reactor lid 4D carries a distillation column 9, which has a top condenser and a product tank, eg downstream of fuel oil / diesel. Swamp products are discharged at 4B for further processing / use.
- the vaporous cleavage products are preferably passed through a high-speed cylinder with a large safety container. This cleans the vapors of aerosols entrained particles via so-called demistors. From there, the desired cleavage products reach the distillation column.
- the level in the reactor 4 is preferably measured and regulated to a desired setpoint. This is done with known measuring probes, leaving a gas space 4A (see FIG. 3).
- the reactor inner wall 4C is permanently cleaned, solid constituents being fed down the reactor sump in a preferably helical movement.
- the filling state of the reactor sump with solid constituents is monitored, preferably without contact.
- the sump product receiving reservoir 4B allows the accumulation of solids in a flow-calm zone.
- Fig. 3 shows in the form of a schematic representation (in central vertical sectional view) by way of example a pot-shaped, rotationally symmetrical reactor 4 with a stirrer 8 with a plurality of stirrer arms 8A and wing-like mixing elements 8B, which may consist at least partially of ceramic or graphite material.
- the mixer elements 8B are adapted to the dome-shaped inner contour, ie, the inner wall 4C of the reactor 4, wherein a comparatively small gap distance S can be maintained.
- the inner contour of the reactor 4 which is preferably heated externally, is constantly freed from caking deposits that form.
- the mixing of the contents of the reactor prevents overheating of the contents of the reactor near the heat-carrying walls.
- the reactor outer wall 4E forms part of a windbox of heating 5.
- the reactor pot 4G is mounted with its peripheral mouth flange 4G 'on a flange 5A' of a box-shaped heating jacket 5A.
- a break-through intermediate bottom 5B which is supplied via a flexible line 5C from a mixer 5D with eg 560 ° C hot gas. This is created by mixing the exhaust gases of a gas-heated flame, which is mixed via a blower 5E air, for example, to room temperature (RT).
- the hot exhaust gases leave the heating jacket via a trigger 5F.
- the reactor 4 is tightly closed by a reactor lid 4D lying on the mouth bottle 4G '.
- This lid carries a distillation column 9 and receives the raw material feed 4H. He is kept stationary on a suitable rack.
- the reactor pot 4G together with the heating mantle 5A can be detached from the reactor lid 4D and lowered as shown by double arrows A and subsequently moved out of the position below the reactor lid 4D, eg by pivoting (double arrows R).
- the stirrer or doctoring head to be described can be removed at the same time (FIG. 4).
- the outlet for residues is correspondingly flexible or detachable connected to a residue line.
- the outlet consists of a reactor sump 4B 1 provided with a thermally insulated wall 4B 1 through the heating jacket or windbox out and intermittently closed with a discharge lock 4J.
- the decoupling of the rotation shaft 4E of a scraper or mixing head represented in FIGS. 7 and 8 can be effected by a pluggable rotary drive connection, so that a vertical play is permitted for the head while the drive motor M with its drive shaft is stationary on the shaft Reactor cover 4D remains.
- FIGS. 7A / 7B show a first embodiment of a scraping head 10D, which can be used as a stirrer in the exemplary embodiment according to FIG.
- a scraping head 10D which can be used as a stirrer in the exemplary embodiment according to FIG.
- two side representations with a) and c) and the view from above with b) are designated.
- the two approximately quarter-round wings 10B which together form approximately a crescent shape, can be seen, which act or are formed on their radially outer side as scraper elements 10C.
- the scraping elements 10C can be attached to the Inner wall 4C of the reactor 4 abut under the weight of the scraping head 10D.
- the scraping head 10D which also acts as a mixer, is rotated slowly, for example at 5 to 10 revolutions per minute.
- the reactor walls are kept free from deposits.
- the scraping head 10D is cleaned by continuous rotation or during interruption of the rotation by a self-cleaning element 10G.
- This is simulated in the embodiment of the sickle shape of the wings 10B and is during the normal scraping operation in a position spaced from the reactor wall position, as shown in Figure 7B.
- the self-cleaning element 10G is connected to a drive element 10H, which is telescopically guided in or on the rotation shaft 10E.
- the self-cleaning member 10D By a telescoping movement of the driving member 10H, the self-cleaning member 10D is vertically displaced. In this case, his scraping edge 10G 1 is applied to the wings 10B and removes any caking schabend from the front in the direction of rotation wing surfaces close to or up to the scraping edge of the scraper element 10C zoom.
- This scraping self-cleaning step can also be done by multiple up and down movement. - Alternatively, it is also possible to perform for self-cleaning, the relative movement between self-cleaning element and cocking element so that the self-cleaning element remains in its original position and the cocking element is pulled up by a suitable amount and then lowered again.
- the scraper elements 10C are provided with cross-sectionally C-shaped profiles which adjoin the lower end of a rotary shaft 10E and each receive a driving element 10H in a guiding manner.
- a self-cleaning head 10G "is also routed and abutted against the scraper 10C.
- This self-cleaning head is connected to one end of the associated driver 10A and thereby travels along the scraper edge as the driver 10H is telescopically moved relative to the rotary shaft 10E.
- the figures show different intermediate positions of the self-cleaning head. This knows in the illustrated embodiment, for example, a U-shape, wherein the U-legs do not project beyond the scraping edge of the scraper element 10C to the outside.
- the possibilities of use correspond to the exemplary embodiment according to FIGS. 7A to 7C.
- the scraper elements can be designed in very different ways.
- the scraper element 10C consists of a material profile held by a receptacle 10F with the interposition of a separating layer 12A, wherein the material can be selected according to the desired wear resistance or / or reactor wall protection.
- the wear is already well advanced, so that the receptacle 10F almost touches the reactor wall. If the wear has progressed so far that such a contact occurs, the receptacle 10F and the scraping element 10C are electrically conductively bridged by the reactor wall 4C.
- An evaluation circuit determines the permissible limit wear and states that the cocking element 10C is to be replaced.
- the reactor pot 4G is provided on its outer wall 4E with flow guide elements 4F which promote efficient heating or cooling.
- flow guide elements 4F which promote efficient heating or cooling.
- a circulation flow of the heating air can be achieved.
- the heating jacket 5A of the heating 5 can be shaped accordingly to further promote this purpose.
- the flow guide can be adapted to the inner contour of the heating jacket 5A.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
- Accessories For Mixers (AREA)
- Mixers Of The Rotary Stirring Type (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2006220013A AU2006220013A1 (en) | 2005-03-02 | 2006-03-02 | Method for depolymerising residues containing hydrocarbons and device for carrying out said method |
JP2007557430A JP2008531799A (en) | 2005-03-02 | 2006-03-02 | Method for depolymerization of hydrocarbon-containing residues and apparatus for carrying out this method |
EP06723171A EP1859009A1 (en) | 2005-03-02 | 2006-03-02 | Method for depolymerising residues containing hydrocarbons and device for carrying out said method |
US11/886,164 US20090050525A1 (en) | 2005-03-02 | 2006-03-02 | Method for deploymerising residues containing hydrocarbons and device for carrying out said method |
CA002599841A CA2599841A1 (en) | 2005-03-02 | 2006-03-02 | Method for the deploymerization of hydrocarbon-containing residues and device for performing this method |
PCT/EP2007/001771 WO2007098949A1 (en) | 2006-03-02 | 2007-03-01 | Depolymerisation installation and method for the depolymerisation of raw materials containing hydrocarbon |
PCT/EP2007/001770 WO2007098948A1 (en) | 2006-03-02 | 2007-03-01 | Depolymerisation installation and method for the operation and maintenance thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005010151A DE102005010151B3 (en) | 2005-03-02 | 2005-03-02 | Process for the catalytic depolymerization of hydrocarbon-containing residues and apparatus for carrying out this process |
DE102005010151.8 | 2005-03-02 |
Publications (1)
Publication Number | Publication Date |
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WO2006092306A1 true WO2006092306A1 (en) | 2006-09-08 |
Family
ID=36590239
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/001919 WO2006092306A1 (en) | 2005-03-02 | 2006-03-02 | Method for depolymerising residues containing hydrocarbons and device for carrying out said method |
Country Status (7)
Country | Link |
---|---|
US (1) | US20090050525A1 (en) |
EP (1) | EP1859009A1 (en) |
JP (1) | JP2008531799A (en) |
AU (1) | AU2006220013A1 (en) |
CA (1) | CA2599841A1 (en) |
DE (1) | DE102005010151B3 (en) |
WO (1) | WO2006092306A1 (en) |
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WO2007098949A1 (en) * | 2006-03-02 | 2007-09-07 | Clyvia Technology Gmbh | Depolymerisation installation and method for the depolymerisation of raw materials containing hydrocarbon |
WO2007098948A1 (en) * | 2006-03-02 | 2007-09-07 | Clyvia Technology Gmbh | Depolymerisation installation and method for the operation and maintenance thereof |
DE102007051373A1 (en) | 2007-10-26 | 2009-04-30 | Hii-Gmbh - Industrianlagen - Bau Und Beratung | Process and apparatus for recovering diesel or fuel oil from hydrocarbonaceous residues |
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US8895796B2 (en) | 2009-06-19 | 2014-11-25 | Innovative Energy Solutions, Inc. | Thermo-catalytic cracking for conversion of higher hydrocarbons into lower hydrocarbons |
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Also Published As
Publication number | Publication date |
---|---|
EP1859009A1 (en) | 2007-11-28 |
DE102005010151B3 (en) | 2006-09-14 |
JP2008531799A (en) | 2008-08-14 |
CA2599841A1 (en) | 2006-09-08 |
US20090050525A1 (en) | 2009-02-26 |
AU2006220013A1 (en) | 2006-09-08 |
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