WO2014106650A2

WO2014106650A2 - Methods and apparatuses for the thermal depolymeriaztion of hydrocarbon-containing starting material

Info

Publication number: WO2014106650A2
Application number: PCT/EP2014/050064
Authority: WO
Inventors: Sayed Amir Karim
Original assignee: EZER, Argun
Priority date: 2013-01-03
Filing date: 2014-01-03
Publication date: 2014-07-10
Also published as: WO2014106650A3

Abstract

The present invention relates in principle to the technical field of thermal depolymerization, in particular of hydrocarbon-containing materials and/or plastics. The invention provides methods and apparatuses by which hydrocarbon-containing starting materials are mixed with the heat carrier during the thermal depolymerization by means of a centering flow. The invention relates particularly to methods and apparatuses in which liquid metal is used as the heat carrier for the thermal depolymerization of hydrocarbon-containing starting materials.

Description

Processes and devices for the leaching of

hydrocarbonaceous input material

The present invention basically relates to

technical field of the sale, in particular of

hydrocarbons and / or plastics. The invention provides methods and apparatus in which hydrocarbonaceous input materials are mixed during the heat treatment with the heat transfer medium by means of a centering flow. In particular, the invention relates

Processes and devices in which liquid metal as

Heat transfer medium is used for the treatment of hydrocarbonaceous input materials.

The known methods for the treatment of

hydrocarbon-containing substances and / or plastics in a crude oil fraction go, for example, from biomass,

Sewage sludge, plastics, tires or the like as

Input material.

Here are the liquefaction of the input material

Reactors are used in which the hydrocarbonaceous input material is melted and heated to a temperature of at least 150 degrees Celsius, typically between about

320 degrees Celsius and about 460 degrees Celsius is heated. Different types of heat transfer medium are used. When

Heat transfer medium is usually sand, a thermal oil or water used; Alternatively, procedures are known in which no heat carrier is used.

WO 2008/098036 Al relates to a process for the cleavage of lignocellulose comprising the mixture with an ionic solvent and heating with exclusion of oxygen to a temperature of preferably 150 to 300 degrees Celsius. DE 10 2005 017 715 A1 relates to a solution containing cellulose and an ionic liquid containing anions and cations as solvent, wherein the cations have at least one atom selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, which in

protonated form is present. Preferably, the solution has a temperature of at most 180 degrees Celsius.

DE 196 23 528 AI discloses high molecular weight polyolefinic plastics, plastic mixtures or plastic waste in a first stage via an extruder feed into a heated cracking tube and vorzuspalten there at a temperature of 380 to 400 degrees Celsius at the tube outlet and in a second process stage at temperatures of 400 to 420 degrees Celsius and pressures between 2 and 70 mbar in

direct coupling of the 2nd cracking stage with a distillation to further reduce.

In the process according to DE 43 11 034 AI old or

Waste plastic in the presence of a liquid auxiliary phase, a solvent or solvent mixture at

Temperatures from 150 to 470 degrees Celsius oiled. The resulting gaseous and condensable

Depolymerization products and the pumpable viscoses

Depolymerisationsprodukte containing bottom phase withdrawn in separate streams and worked up separately.

DE 44 23 394 C1 relates to a process for the treatment of polyethylene-polypropylene mixtures or high-melting

Degradation products of polyethylene-polypropylene mixtures at 350 to 400 degrees Celsius and the distillative separation of the resulting fission products directly in the formation process under atmospheric pressure.

According to DE 44 12 941 AI comminuted, dried waste plastic mixture is melted, dissolved in an originating from the process aromatic oil fraction and a Temperature of 250 to 300 degrees Celsius generates a pumpable mass. With the addition of hydrogen donors, the polymers are split in a liquid-phase pyrolysis reactor at a temperature of <500 degrees Celsius.

EP 0 599 795 B1 claims a process for the conversion of polymer waste at a temperature above 120 ° C with a solvent consisting of a predominantly

aromatic hydrocarbons existing fraction with a boiling temperature above 180 ° C consists. The

Decomposition gases are extracted and the recovered polymer solution in a thermal cracking process

further processed.

When using Thermoolen, strict adherence to the maximum temperature must be ensured because the thermal oils used have a maximum boiling temperature of approx

380 degrees Celsius. The resulting lower

Process temperature usually has a lower one

Efficiency during the oiling result. This lower efficiency is attempted to counteract in known methods by additional catalysts.

DE 199 41 497 B4 discloses a process wherein wood, residues and substances which can be smoldered by smoldering and then burning the smoldered residues in

The presence of catalysts of aluminum silicates reacted and the volatile carbon black products are distilled. This process operates under combustion conditions with 250 to 350 degrees hot air and under the back radiation of

Catalyst layer at the top of the reactor.

According to DE 100 49 377 AI hydrocarbon-containing waste in the presence of a catalyst of sodium aluminosilicate in a circulation evaporator and using a

high boiling point hydrocarbons such as thermal oil, base oil or Bunker C oil oiled at temperatures of 430 to 470 degrees Celsius.

A particular disadvantage is that reaction coke is formed on a large scale by the temperature difference between the heated wall and the reaction temperature in the reactor. In this case, the amount of coke formed increases when more heated, to a better efficiency of the treatment

to reach. The heating from the edges of the reactor and the poor thermal conductivity of the thermal oil leads to a rising temperature difference between the reactor wall and

Reaction mixture, i. to an over-temperature of the wall opposite the reaction mixture. The formed reaction coke then reacts with the sodium-doped aluminum silicate

Catalyst to a non-reactive residue, which pollutes the system and stops the reaction. The

Reaction mixture of catalyst and the reaction coke connects to the wall of the plant or the reactor to a hard residue and requires a high

Cleaning effort. This can only be done through intensive

Heating the wall to be diminished, as the low

Heat conduction of the reaction oil in circulation a high temperature difference between the heater located on the outside of the wall and that taking place in the oil

Depolymerization conditioned.

In order to overcome this disadvantage, in the process disclosed in EP 1 538 191 A1, the heat is released directly in the reaction system. In the process according to EP 1 538 191 A1, carbonaceous residues are oiled by means of special catalysts at temperatures of 300-400 degrees Celsius. The energy input takes place in the system of pump and

counter-rotating agitator system in that the

Residuals are introduced tangentially into the stirred tank and ground in the agitator with an opposite direction of rotation. The flow energy of the pump is through the counter-rotating agitator braked and converted into heat. Here, for the catalytic conversion, a catalyst in the form of fully crystallized mineralized Y molecules with sodium dopants for mineral hydrocarbons, oils and plastics, a catalyst with calcium dopants for biological feedstocks, a catalyst with

Magnesium dopants for wood and a catalyst with

Potassium dopants used for high-halogen substances.

With this mechanical heat generation can

Reaction temperatures of a maximum of 400 degrees Celsius can be achieved. Another disadvantage is that the expensive catalyst and the heat transfer oil are consumed during the reaction. The resulting high refusal and

Cleaning costs are contrary to the broad economic use of this method.

DE 196 31 201 AI relates to the heating of organic

Material of biological origin by means of microwave radiation to 150 to 800 degrees Celsius and conversion of the input materials under pressure increase and non-oxidative conditions in

Fuels. Further, DE 196 31 201 AI discloses a reactor for carrying out the method, which is a generator for

Generation of microwaves includes.

DE 195 16 379 AI relates to a process for the processing of waste or waste plastics by depolymerization under turbulent flow conditions to a pumpable and a volatile phase and separating the volatile phase in a gas phase in a condensate and condensable

Depolymerisate. Condensate and condensable Depolymerisat be heated in the presence of hydrogen under pressure and after removal of non-constituents a

Hydrotreating to obtain a Syncrude subjected. The Depolymersiation is carried out at a temperature of 250 to 450 degrees Celsius. DE 197 27 565 A1 relates to a process for working up mixtures of substances which contain heavy metals or halogenated

Hydrocarbons contained by thermal evaporation in vacuo, suction of the evaporation products and after cooling are separated after phase condensed. This is the

Reaction space, a reaction gas, preferably oxygen, fed and heated the reaction space to a temperature of up to 1050 degrees Celsius.

DE 10 2008 029 927 B4 discloses a flash pyrolysis process for biomass and organic wastes using a suitable ionic liquid to make a

Pyrolysis gas for use in gas CHP s or a slurry (oil-containing intermediate) or a pyrolysis oil fraction comprising the work-up by a unit consisting of shredder, conveyor, warm mixer, colloid pump and intermediate container with degassing / deaeration and mixing of ionic liquid with a temperature in the range of approx 200-250 degrees Celsius and subsequent pyrolysis in a plant combination comprising hot mixers, main process pump, expansion and separation vessel and cyclone, preferably sand or steel balls are used as heat transfer.

To thermally depolymerize used and waste plastics, a high amount of energy at a high temperature level of about 400 degrees Celsius must be entered into the reactor. In addition, plastics are very sensitive to overheating, as overheating leads to uncontrolled decomposition with undesirable side reactions. In order to protect against overheating, the reactor contents in DE 44 17 721 A1 and DE 44 28 355 A1 were driven via a circulatory system connected to the reactor, which comprises an external furnace / heat exchanger and a high-performance pump in order to achieve a high circulating flow in the reactor. To protect the circulatory system from erosion, the reactor includes a riser to separate coarser

Solid particles. The depolymerization can in the presence of Catalysts such as Lewis acids or heavy metal salt solutions and a liquid auxiliary phase, preferably at temperatures between 150 and 470 degrees Celsius, are performed. The reactors used have an adding device for waste and waste plastics in the head region of the reactor and a depolymerizer for removal of material in the bottom region of the reactor.

DE 101 36 619 AI relates to a device for the treatment of high temperature resistant components, in particular of high temperature resistant metal parts, the organic

Contain waste materials. The apparatus comprises a reactor having a high-temperature region, a depolymerization bath arranged therein for the thermal depolymerization of the organic constituents of the waste materials and an imide

High temperature region of the reactor arranged

Depositing means for depositing at least a portion of the high temperature resistant components from the

Discharge stream of the depolymerization bath. in the

High temperature range of the reactor is a magnetic device, in particular a solenoid device, arranged, which allows magnetic components of waste materials, such as the steel reinforcements of used tires, which are usually the majority of the tendency to block or clogging of the discharge paths and devices components of the

Waste materials are very early to separate from the other solid reaction products. As Depolymerisationsbad is a melt of the heat carrier, such as a

Lead melt or a melt of other metals or metal alloys or a molten salt used.

US 3,770,419 relates to a process for the pyrolysis of

organic and inorganic wastes in a closed reactor with a molten metal bath, preferably a lead bath at temperatures between 350 and 620 degrees Celsius and mixing the waste with the metal bath. The usage of lead is opposite to the use of others

molten metal baths, for example, molten tin, because lead has a higher specific gravity. Rollers with paddles for mixing waste and molten lead bath and separating the pyrolysis products can be located in the reactor.

After the Formex process scrap tires are thermally decomposed at just under 500 ° C in a tin bath melt.

DE 102 12 104 AI relates to methods for pyrolysis of fiber composites containing waste in a metal bath at a metal bath temperature between 550 to 700 degrees Celsius and methods for recycling waste from the

Animal body utilization in a metal bath at a metal bath temperature between 250 and 450 degrees Celsius. The metal bath preferably contains tin, zinc and / or aluminum,

preferably at least 99%, in particular at least 99, 99% pure tin. DE 102 12 104 AI also discloses an apparatus for carrying out the method with a reactor and a metal bath arranged therein, which is in heat-conducting contact with a heating device and a

Temperature control unit, which is connected to the heater, but without mixing of the components.

DE 493 475 relates to a process for the degassing and gasification of fuels in molten salt baths as a heat carrier, wherein the fuels are heated in the molten salt bath so far that their volatile constituents are driven off.

For use in solar power plants, the use of

Liquid metal discussed as a heat transfer medium.

Due to the large amounts of waste and the need for

However, there is still a need for cost effective fuels for the commercialization of plastics and other carbonaceous materials, in particular for the oilification of plastic waste and biomass used as carbonaceous input material and oiled.

All previously known processes for REALIZATION have considerable problems with the coking in the reactor, whereby a

continuous process - if any - only with

considerable technical effort is possible. A regular comprehensive cleaning of the reactor due to the

Coking residue is obligatory, costly and time consuming.

In addition, the possible reaction temperatures are limited by the heat transfer medium used in the known methods to temperatures of up to 400 degrees Celsius, resulting in low efficiencies in the VERÖlung. This lower efficiency is tried in known methods by additional catalysts, such as zeolite or the like, to counteract. Naturally, in this case, the catalyst must also be discharged from the system and reactivated, including an additional technical

Setup is required. This is associated with high costs and additional technical effort.

Another problem is the mixture or the

Mixing of the input material with the heat carrier and the catalyst in the reactor, which is currently possible only with stirrers or other mechanical couplings.

Based on the disadvantages set out above and

Inadequacies and in appreciation of the outlined

Prior art, the present invention is the

Task, means such as a device and a corresponding method with the highest possible

Provide efficiency for the sale of hydrocarbon-containing input materials without this being a significant technical effort to make.

This object is achieved by the use of Heat transfer medium with a high density achieved in the treatment of hydrocarbonaceous input material. Due to the high density of the heat carrier, the carbonaceous input material introduced into the reactor floats on the

Heat carrier on and thus does not come into contact with the actual reactor, whereby a coking can be excluded or largely excluded.

According to the invention, heat carriers which are chemically inert, have a high thermal conductivity and a high density in comparison with the carbonaceous input material

exhibit.

As a heat carrier according to the invention preferably

Liquid metal, preferably tin, silver, tin alloys or silver alloys used. In particular, the liquid metals tin or silver or the corresponding

Mixtures or alloys used because they have a high

Have thermal conductivity and are chemically inert, whereby they comprise as heat transfer medium or heat transfer bath for the oiling of carbonaceous input materials, the mixtures of different origin and composition and are not pre-sorted or otherwise processed,

are particularly suitable. In addition, the

According to the invention heat transfer liquid metals a high density and can be easily separated from the products of the oil, which also float on the liquid metal heat transfer medium. As a result, a continuous operation of the Verkölungsverfahrens is possible, for example in one

Continuous flow reactor.

The invention relates to a method for the oiling of carbonaceous input material, wherein

hydrocarbon-containing input material is introduced into a reactor comprising a heat carrier made of liquid metal, and the heat carrier is heated from liquid metal. The invention relates to a process for the treatment of carbonaceous input material, wherein

hydrocarbon-containing input material is introduced into a reactor which comprises a heat carrier made of liquid metal, and the heat carrier is heated from liquid metal, characterized in that the liquid metal either a. Silver, b. at least 1% silver, preferably 2 to 10% silver, c. Silver and tin, d. at most 90% tin, preferably 50 to 95% tin or e. 99% tin and at least 1% silver.

The invention relates to a process for the treatment of carbonaceous input material, wherein

hydrocarbon input material is introduced into a reactor comprising a heat carrier of liquid metal, and the heat carrier is heated from liquid metal, characterized in that the liquid metal with the hydrocarbonaceous input material during the

The mixture is mixed.

Hydrocarbon input material is introduced into a reactor comprising a heat carrier of liquid metal, is introduced and the heat carrier is heated from liquid metal, characterized in that the heat carrier from

Liquid metal a. Silver, b. at least 1% silver, preferably 2 to 10% silver, c. Silver and tin, d. Max. 90% tin, preferably 50 to 95% tin, or e. 99% tin and at least 1% silver and the heat transfer medium with the

hydrocarbonaceous input material during the

The mixture is mixed.

In particularly preferred embodiments of the above method, the heat carrier of liquid metal to a temperature of at least 380 degrees Celsius, preferably 400 heated to 550 degrees Celsius.

In addition to a suitable heat transfer medium is the possible

uniform temperature distribution throughout the reactor during the oiling necessary to achieve efficient oiling while avoiding undesirable side reactions in the oilation of the hydrocarbonaceous input materials

to reach. This is inventively by the formation of an artificially generated centering flow, the

centripetal acts on the carbonaceous input material achieved. The carbonaceous input material has a lower density than the heat transfer medium and therefore floats on the heat transfer bath. The oil is by definition carried out at elevated temperature, wherein the heat transfer medium is chosen so that it at this temperature in liquid

Condition exists, ie in the form of a heat carrier bath during oiling. The centering flow according to the invention, which acts centripetally on the carbonaceous input material and thereby pulls it downwards, causes thorough mixing of the carbonaceous input material with the heat carrier during the oiling. Through this type of mixing is an optimal heat transfer from the heat carrier to the

reached carbonaceous input material. This is further promoted by the fact that in the inventive

Method to be used heat transfer medium, which is preferably a liquid metal, has a high thermal conductivity.

A centering flow centripetal to the

carbonaceous input material acts, can be generated for example by rotation of the heat carrier or heat carrier bath. A rotation of the heat carrier can be achieved for example by the addition of geometrically shaped particles such as balls, the

Reaction mixture added and rotated. For example, geometrically formed particles of paramagnetic or ferromagnetic material in the Reactor or the heat transfer medium or the heat carrier bath introduced and rotated by means of an applied from outside the reactor electromagnetic or magnetic field in rotation, whereby the centering flow can be generated in the heat carrier.

For example, the geometrically formed particles may have a density which approximates the density of the

Heat carrier corresponds, so that the geometrically shaped particles during the heat in the heat transfer bath swim. If the geometrically formed particles are set in rotation, the centering flow is generated in the heat carrier bath. This flow has a suction effect on the carbon-containing input material floating on the heat carrier or heat carrier bath and pulls the input material under the heat carrier.

The carbonaceous input material has a significantly lower density than the heat transfer medium and floats on the heat transfer bath. For example, the density difference between the heat transfer medium and the carbonaceous input material is 2 kg / m ³ , 2.5 kg / m ³ , 3 kg / m ³ , 3.5 kg / m ³ or more, for example 4 kg / m ³ , 5 kg / m ³ , 10 kg / m ³ or more. The artificially generated centripetal suction flow conveys this

hydrocarbonaceous input material despite the high density difference to the heat transfer medium under the heat transfer medium and thus leads to an optimal mixing.

The inventive centering flow in the reactor causes the hydrocarbonaceous input material is repeatedly transported under the heat transfer medium, thereby ensuring a complete and continuous mixing and an optimal Verkölungsprozess.

Geometrically formed particles in the heat transfer bath can also act like a grinder and with each other with each other or with the wall of the reactor one Crushing of the carbonaceous input material cause. As a result of the resulting increase in surface area, the oiling can be further accelerated.

The invention relates to a process for the treatment of hydrocarbonaceous input material comprising the steps

a. Filling hydrocarbonaceous input material into a reactor comprising a heat transfer medium, and wherein the hydrocarbonaceous input material floats on the heat transfer medium,

b. Mixing the hydrocarbon

Input material with the heat carrier by means of a flow, which pulls the carbonaceous input material under the heat carrier.

a. Filling with hydrocarbon

Input material into a reactor, the one

Includes heat transfer and wherein the

hydrocarbonaceous input material floats on the heat transfer medium,

b. Generation of a centering flow in the heat transfer medium, c. Obtaining the products of the REAL from the reactor.

In preferred embodiments of the method, the heat carrier comprises geometrically formed particles, for example balls. In a preferred embodiment of the method, the geometrically formed particles, for example balls, are set in rotation. In the invention

Processes can be geometrically formed particles,

For example, balls of paramagnetic or

ferromagnetic material can be used. By doing

Methods can be the geometrically formed particles, For example, spheres are set in rotation by an electromagnetic field or a magnetic field.

The invention also provides a process for the oilation of hydrocarbonaceous input material comprising the steps

a. Filling hydrocarbonaceous input material into a reactor comprising a heat transfer medium and geometrically formed particles, preferably spheres, and b. Extraction of the products of the sale.

a. Filling hydrocarbonaceous input material into a reactor comprising a heat transfer medium and geometrically formed particles, preferably spheres, and b. Generation of a centering flow in the heat transfer medium, c. Extraction of the products of the sale.

Preferably, in the inventive method as

Heat transfer medium is a liquid metal used, particularly preferably a liquid metal comprising or consisting of tin and silver or tin or silver.

a. Introducing hydrocarbonaceous input material into a reactor comprising a heat transfer medium and wherein the heat transfer medium is a liquid metal, for example a liquid metal comprising or consisting of tin and silver or tin or silver,

b. Thorough mixing of the hydrocarbon

Input material with the heat carrier,

c. Extraction of the products of the sale. The invention also provides a process for the oilation of hydrocarbonaceous input material comprising the steps

a. Filling of hydrocarbon-containing input material in a reactor comprising a heat carrier of liquid metal, for example, a heat carrier

Liquid metal comprising or consisting of tin and silver or tin or silver, preferably one

Heat transfer medium made of liquid metal, the a. Silver, b. at least 1

% Silver, preferably 2 to 10% silver, c. Silver and tin, d. Max. 90% tin, preferably 50 to 95% tin, or e. 99% tin and at least 1% silver, b. Generation of a centering flow in the heat transfer medium, c. Extraction of the products of the sale.

a. Filling of hydrocarbon-containing input material into a reactor, the geometrically formed particles, such as balls and a heat carrier

Liquid metal comprises, for example, a heat carrier made of liquid metal, which comprises or consists of tin and silver or tin or silver, preferably a heat carrier made of liquid metal, the a. Silver, b. at least 1% silver, preferably 2 to 10% silver, c. Silver and tin, d. Max. 90% tin, preferably 50 to 95% tin, or e. 99% tin and at least 1% silver, b. Generation of a centering flow in the heat transfer medium, c. Extraction of the products of the sale.

Of course, the above methods include the step of raising the temperature or heating the

Heat carrier, since the definition is carried out by definition at elevated temperature. The corresponding Tanning temperature can be easily determined by the expert. In a preferred embodiment of the method, the heat transfer medium, for example made of liquid metal, onto a

Temperature of 380 degrees Celsius or more heated. In a further embodiment of the method, the heat transfer medium, for example made of liquid metal, is heated to a temperature of 400 to 550 degrees Celsius. The step of

Temperature increase may be carried out before or after the introduction of the hydrocarbonaceous input material into the reactor. This depends on the configuration of the reactor and also on whether the oiling process is continuous

is carried out.

For example, the subject matter of the invention is a process for the oiling of hydrocarbon-containing starting material comprising the steps

a. Introducing hydrocarbon-containing input material into a reactor comprising a heat carrier of liquid metal and geometrically formed particles, for example spheres,

b. Heating the heat carrier of liquid metal to 410 to 445 degrees Celsius,

c. Mixing the hydrocarbon

Input material with the heat transfer medium of liquid metal by means of the geometrically formed particles and

d. Obtaining the products of the Verölung from the reactor.

Optionally, the oiling in the presence of a

Catalyst can be performed.

The methods may include measuring the temperature during the oiling at at least two different measuring points in the reactor.

The invention also relates to devices for

Implementation of the procedures, in particular appropriate Reactors. The invention relates to a device, for example, reactor for the oilification of

hydrocarbonaceous input material comprising

a. a heat transfer medium with a density greater than the density of the hydrocarbon

Input material is, so that the input material floats on the heat carrier and

b. Means for generating a centering flow in the heat carrier, the centripetal on the

hydrocarbonaceous input material acts and pulls it under the heat transfer medium.

For example, the density difference is between

Heat transfer medium of the reactor and to be oiled

carbonaceous input material 2 kg / m ³ , 2.5 kg / m ³ , 3 kg / m ³ , 3.5 kg / m ³ or more, for example 4 kg / m ³ , 5 kg / m ³ , 10 kg / m ³ or more. In one embodiment of the device, for example of the reactor, the means for generating a centering flow geometrically formed particles of paramagnetic or ferromagnetic material, for example by means of an electromagnetic or

magnetic field are set in rotation. The

Apparatus may further comprise means for electrical induction with a suitable geometric arrangement.

Preferably, means for electrical induction, for

Generation of an electromagnetic field or a

magnetic field arranged outside the reactor. But it is also a localization within the device or the reactor possible.

The invention is also the use of a

inventive method or apparatus according to the invention, for example for the production of fuels or raw materials for the chemical industry or for Purification of carbonaceous substances

Input material are contaminated.

Below are the individual features of

inventive method and devices explained in more detail.

In principle, the invention, i. the

inventive method the use of additives that promote the formation of the centering flow during the VERÖlung. With the aid of these additives, a suitable centripetal flow, i. a flow centered concentrically to the center of the reactor and acting centripetally on the carbonaceous feedstock, which thereby draws the carbonaceous feedstock downwardly beneath the heat transfer media. These accessories are

preferably geometrically formed particles, in particular spheres.

Depending on the configuration of the geometrically formed particles, the dimensions and shape of the reactor becomes a

centripetal or centering flow in the reactor

formed, which may have different flow velocities. By centripetal or centering

Flow in the reactor becomes the hydrocarbon

Input material, which floats due to the lower density without the flow on the liquid metal heat transfer medium, pulled under the liquid metal and achieved in this way optimum mixing and uniform temperature distribution, which can be detected or checked by measuring the temperature at least two different measuring points.

The geometrically formed particles are set in motion, for example, para- or ferromagnetic spheres are set in rotation by application of an (electro) magnetic field. By the locally different

Flow rates in the reactor, pressure differences generated, suck the carbonaceous input material under the liquid metal heat carrier or press and thus lead to a thorough mixing. Here, another, for example, mechanical method can be used to form the flow according to the invention in the heat transfer bath.

The geometrically formed particles, in particular spheres are preferably made of paramagnetic material and / or of ferromagnetic material. For example, the geometrically formed particles, in particular spheres, comprise a material selected from permaloy, supermalloy, nickel-iron alloy, nickel-cobalt-iron alloy, nickel-molybdenum alloy or the geometrically formed particles consist of one of the materials Permaloy, Supermalloy , Nickel-iron alloy, nickel-cobalt-iron alloy, nickel-molybdenum alloy or a mixture of these materials.

Preferably, in the method according to the invention

geometrically formed particles with a specific

Sizing used. Particularly preferred is a

Dimensioning of the geometrically formed particles

between 1 x 10 ^{~ 5} m to 1 x 10 ^{~ 10} m, for example 1 x 10 ^{~ 6} m to 1 x 10 ^{~ 9} m, 1 x 10 ^{~ 7} m to 1 x 10 ^{~ 8} m, their mathematical

For example, the description may correspond to the equation K / (x ² + y ² + z ² ) = r ² .

The sizing and / or the amount of geometric

formed particles are / are suitably dependent on the geometry of the reactor and / or on the nature of the carbonaceous input or input material. In a preferred embodiment, the geometrically formed particles may have a density which is approximately equal to the density of the heat carrier used, for example the

Liquid metal, preferably that of tin, a tin alloy, a silver alloy or a tin-silver Alloy, whereby a floating of the geometrically formed particles in the heat carrier or the

Heat transfer bath can be achieved.

Preferably, the heat transfer medium is a liquid metal.

According to the invention, however, other heat transfer media, which have a corresponding density, thermal conductivity and

Have inertness to the carbonaceous input material.

According to the invention is used as heat transfer in the case of the sale

preferably at least one low-melting metal, and / or at least one metal alloy, and / or at least one mixture of metals, preferably a mixture

and / or at least one metal powder dispersion and / or at least one thermal paste with a melting temperature of less than about 400 degrees Celsius used.

A liquid metal is a metal, an alloy, a

Mixture of metals, a metal powder dispersion or a thermal paste with a melting temperature of less than 970 degrees Celsius, preferably a melting temperature of less than 380 degrees Celsius, more preferably less than 250 degrees Celsius. In a further preferred embodiment of the method, the liquid metal with respect to the

Carbonaceous input material at a temperature of 380 degrees Celsius, a heat transfer coefficient of greater than 87 W / mK or more. In a further preferred

Embodiment of the method has the liquid metal with respect to the carbonaceous input material at a

Temperature of 380 degrees Celsius a specific

Heat capacity greater than 250 J / (kg x K) or more. In a further preferred embodiment of the method, the liquid metal has a density of at least 7 kg / m ³ at a temperature of 380 degrees Celsius. In a particularly preferred embodiment of the method, the liquid metal comprises tin, preferably 95% tin, particularly preferably 98% tin. In a further particularly preferred embodiment of the

Procedure, the liquid metal is tin with a

Purity of 99.998%.

In a particularly preferred embodiment of the method, the liquid metal comprises silver, for example 50% or less silver, for example 25% silver or less, preferably 10% to 6% silver, particularly preferably 5%, 4%, 3%, 2% or 1%. Silver. In a further particularly preferred embodiment of the method that consists

Liquid metal of silver, preferably at least 75% or more silver, more preferably 90% silver.

In a further particularly preferred embodiment of the method, the liquid metal comprises tin and silver,

for example, a tin-silver alloy. For example, the liquid metal comprises at least 90% tin and at least 1% silver, preferably at least 95% tin and at least 1% silver, more preferably at least 98% tin and

at least 1% silver or max. 99% tin and at least 1%

Silver.

The term liquid metal is used according to the invention for the designation of metals in the liquid state. These are metals whose melting point is below 400 degrees Celsius, preferably below 380 degrees Celsius,

particularly preferably below 350 degrees Celsius. The term liquid metal preferably comprises metals that are in the desired temperature range of 380 to 550 degrees Celsius in the liquid state.

Liquid metals also include alloys whose melting point is below 400 degrees Celsius, preferably below 380 degrees Celsius, more preferably below 350 degrees

Celsius is. The term liquid metal preferably includes alloys that are in the desired temperature range of 380 to 550 degrees Celsius in the liquid state, such as gunsmoke, bronze, brass, bismuth alloys such as Roses Metal, Cerrosafe, Wood's Metal, Field's Metal, Cerrolow 136, Cerrolow 117, Bi-Pb-Sn-Gd-In-Tl, NaK, gallium compounds such as gallinstane, preferably

Tin alloys, silver alloys or tin-silver alloys.

Liquid metals also include processed mixtures of

Metals whose melting point is below 400 degrees Celsius, preferably below 380 degrees Celsius, more preferably below 350 degrees Celsius. The term liquid metal preferably includes processed mixtures of metals in the desired temperature range of 380 to 550 degrees Celsius in the liquid state, such as mixtures of aluminum, iron, copper, tin and silver.

Liquid metals also include metal powder dispersions or thermal pastes whose melting point is below 400 degrees Celsius, preferably below 380 degrees Celsius,

particularly preferably below 350 degrees Celsius. The term liquid metal preferably includes metal powder dispersions or thermal pastes which are in the liquid state in the desired temperature range of 380 to 550 degrees Celsius, such as metal powder dispersions or thermal pastes comprising or consisting of tin, silver or tin and silver.

Particularly preferred is the use of tin as

Liquid metal in the above-mentioned inventive method. A preferred embodiment of the invention relates to heat carriers which consist of tin or tin

include, particularly preferred are heat transfer medium with at least 50 (mass)% tin or more, for example 99, 998% tin based on the total weight of the heat carrier.

Heat transfer media preferred according to the invention have one

Heat transfer coefficients of 60 W / mK or more, for example 67.3 W / mK or 68.3 W / mK, preferably 87.6 W / mK, particularly preferably 102.6 W / mK at room temperature. Tin has a heat transfer coefficient of 67.3 W / mK at a temperature of 380 degrees Celsius. The heat transfer coefficient can be determined, for example, by the laser flash method. The heat transfer coefficient (also

Heat transfer coefficient or heat transfer coefficient) is the intensity of the heat transfer at the interface between the heat carrier according to the invention and to be oiled

carbonaceous input material.

Heat transfer media preferred according to the invention have, for example, a specific heat capacity of> 0.5 kJ / (kg K), preferably of> 0.4 kJ / (kg K), particularly preferably> 0.3 kJ / (kg K). The heat transfer medium has for example a specific heat capacity between 0.25 and 0.15 kJ / (kg K), preferably between 0.24 and 0.2 kJ / (kg K), for example of 0.228 or 0.230 kJ / (kg K), which corresponds to the specific heat capacity of tin. These values refer to the specific heat capacity under standard conditions (according to IUPAC 1982).

According to preferred heat transfer medium has at 380 degrees

Celsius, for example, a density of 6.54 kg / m.

As oiling processes are referred to, with which oils which are similar in composition to petroleum, can be produced. Corresponding oils are the products of

Veröllung, which are obtained by the method according to the invention. The oilification is a technical one

Depolymerization process. This carbon-containing input materials in the absence of oxygen at

Normal pressure thermocatalytically converted into short-chain aliphatic hydrocarbons. Oil depletion is also referred to as Low Pressure Thermal Conversion (NTK). A special method of oiling is the catalytic

unpressurized oil reduction (KDV), in which the thermocatalytic Conversion process is carried out in the presence of catalysts. Also included according to the invention is the KDV.

The oil is always carried out at elevated temperature. The particular suitable Verölungstemperatur can be easily determined by the skilled person. Among other things, it depends on the carbonaceous input material to be oiled

Heat transfer medium, the dimensioning and design of the

Reactor, the heating, the type of centering flow, for example, the flow rate, the size and shape of the geometric particles and the material from which the geometrically configured particles consist of.

By using liquid metal as the heat carrier, reactor temperatures of more than about 380 degrees Celsius can be achieved, preferably from well over 380 degrees Celsius, more preferably from 380 to 1100 degrees Celsius, unlike the prior art. When using liquid metal as the heat transfer medium, temperatures in the range of, for example, 380 to 550 degrees Celsius, preferably in the range of 400 to 500 degrees Celsius, particularly preferably in the range of 410 to 450 degrees Celsius, can be used during the oiling. At these temperatures or in this temperature range, the tiling process is ideal, the temperatures are high enough for the tying process to be correspondingly accelerated and a medium to high depolmerization efficiency to be achieved. On the other hand, the temperatures are not so high that pyrolysis or cracking occurs on a large scale. Ideally, the temperatures are chosen so that pyrolysis is avoided depending on the carbonaceous input material. The pyrolysis starts in the temperature range between 500 - 900 degrees Celsius or takes place in this temperature range.

In the process according to the invention, the oiling

for example, at a temperature of about 410 degrees Celsius to about 445 degrees Celsius, more preferably about 420 degrees Celsius, about 430 degrees Celsius, about 440 degrees Celsius or more are performed. In the case of a suitable flow guidance, such as the centering flow in the heat carrier and a suitable flow rate in the reactor, the temperature distribution is almost identical to 1 + n different measuring points, where n is a natural number of 1 to 100, preferably n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more,

For example, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95. In a preferred embodiment of the invention, the temperature at 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 or more different measuring points in the reactor is almost identical. An almost identical

Temperature distribution "means that the deviation of the

Temperature at two different measuring points in the reactor less than 3%, preferably less than 2%, more preferably less than 1%.

As carbonaceous input material are all substances suitable, the artificial and / or natural

Hydrocarbon polymers include, i. everything that includes or consists of organic substances. Carbonaceous

Input materials may include, for example, plastics of all kinds, oils, waste oils, waxes, fats of all kinds such as animal, vegetable or mineral fats, for example

Kitchen fats, lipids, proteins of all kinds, wood, biomass, microbial biomass such as e.g. Sewage sludge, animal biomass such as animal meal, meat bone meal, animal fat, vegetable

Biomass such as renewable resources, plant residues, whole plants or parts of plants, wood, straw, grass,

Crop residues, cereals, maize, oilseed rape, soybean, sugar cane,

Sugar beets, agricultural and forestry residues and waste, in particular undemanding plants such as jatropha, sand peaches, miscanthus, glaucophyta, haptophyta,

Fiend Geyser, Cryptista, Euglenozoa, Chlorarachniophyta, Xanthophyceae, Chrysophyta, Bacillariophyta, Phaeophyta,

Rhodophyta, Castor, any type of waste products and waste, such as household waste, spoiled food, consumer goods, industrial residues and waste products of all kinds

For example, refinery residues such as bitumen, tars, residual, mixed or pure fractions from the plastics processing industry, elastomers, (technical) rubber articles, scrap tires, thermoplastics, thermosets, polyadducts, semi-finished products such

For example, panels and plates (printed circuit boards) or

Laminate sheets, which may contain metal coatings, parts, components, packaging, storage and transport containers.

The waste products can be plastics of all kinds such as

For example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, chloroprene rubber, polystyrene,

Polymer blends such as ABS, polycondensates, polysulfones, with

Sulfur bridges crosslinked rubber,

Include polyolefin waste, polyolefin waste.

The carbonaceous input material can

Minor components that can not be oiled contain. Secondary constituents are, for example, pigments, metals,

Glass fibers, flame retardants, pigment-containing printing inks, sand, carbon black and / or fillers. The starting material contains in preferred embodiments up to 50 vol.%,

preferably up to 40% by volume, more preferably up to 30% by volume or less of secondary constituents. But it is also the oilification of carbonaceous input materials possible, which consist almost exclusively of minor constituents such as 95 vol.% By-component, in which case, however, the yield of short-chain aliphatic hydrocarbons is correspondingly lower.

The hydrocarbonaceous input material may be sorted and / or pre-cleaned prior to oiling. The carbonaceous input material is preferably shredded, thinned, pulverized or otherwise broken down into smaller pieces or liquid.

In addition, carbonaceous input or

Input material come into use, which is only very coarse or not crushed, which again cost and process steps can be saved in the overall system.

By the depletion of the carbonaceous input material in the presence of the heat carrier according to the invention, low molecular weight hydrocarbons are used as product

(Starting material). The resulting low molecular weight hydrocarbons or Kohlenwassertoffgemische can be used as starting materials in the processing industry, for example as raw materials for the chemical industry. Products may be crude oil, crude oil fractions, diesel or other fuels, fuel components or liquid fuels. The products obtained can be further purified, separated, worked up or optionally used directly.

The crude oil fraction produced by the inventive process of the REO may be passed directly into at least one distillation column or else for direct utilization in at least one tank system.

In particular embodiments of the invention, the carbonaceous input material consists predominantly of

Nebenbestandteilen, for example, if the minor constituents are contaminated with hydrocarbons, these can

Impurities are removed by dissolution. In this way, for example, the cleaning of oil-contaminated sand or water is possible, for example from tanker or refinery accidents. The invention also encompasses the use of liquid metal heat carriers for cleaning carbon contaminated material. The invention also provides a process for the purification of carbonaceous material contaminated material, wherein the contaminated material is brought into contact with a heat transfer medium of liquid metal and the heat transfer medium is heated from liquid metal.

The invention also provides a process for purifying carbonaceous input material, for example sand or water from refinery accidents, comprising the steps of: a. Filling in the hydrocarbon

Input material into a reactor, the one

Includes heat transfer medium, for example, a liquid metal such as tin or a tin alloy,

b. Optionally generating a suitable mixing of the carbonaceous input material with the heat transfer medium, for example by a centering flow in the heat transfer medium,

c. Extraction of the purified input material,

for example, the purified sand or water from the reactor.

Basically, the heat transfer medium according to the invention together with the centering flow according to the invention in

Heat transfer medium can be used in all processes for the treatment.

The processes according to the invention are in principle applicable for use in all devices suitable for the improvement in the already existing reactors and oiling plants. The heat transfer medium according to the invention and the geometrically formed particles according to the invention are in principle suitable for use in all devices suitable for the purpose of REALIZATION, also in the already existing reactors and oiling plants. Existing reactors and oiling plants can either directly with the heat carrier according to the invention and optionally the geometrically formed particles

be recharged or simply converted become. Existing reactors and oiling plants can also directly or after appropriate conversion so

be designed that a centering flow in the

Heat transfer medium can be formed. The inventive methods can also be carried out in continuously operated reactors or flow reactors, wherein

basically any reactor size is possible, operation in large-scale systems and in small portable reactors.

The invention also provides a device for

Implementation of the method according to the invention. The invention also provides a reactor for carrying out the

inventive method.

The device according to the invention, for example the reactor, is designed in such a way that a centering flow is formed by its geometric design, which forms the

Mixing of the heat carrier with the to be oiled

carbonaceous input material causes. A particular embodiment of the reactor relates to a reactor which

Includes additives that promote or facilitate the formation of the centering flow. The invention relates in particular to a reactor which has a geometric design

Particles, in particular balls, for example

paramagnetic material and / or of ferromagnetic material, in particular of μ-metal or Mu-metal,

For example, one of the materials permaloy, supermalloy, nickel-iron alloy, nickel-cobalt-iron, nickel-molybdenum alloy or a mixture of these materials.

Furthermore, the device according to the invention, in particular the reactor, may comprise means for the kinetic excitation of the geometrically formed particles, for example outside the reactor. The device may comprise means with which the geometrically designed para- or ferromagnetic

Particles of the reactor by means of electrical induction with suitable geometric arrangement, for example, by an applied electromagnetic field or magnetic field are set in rotation, whereby the flow in the heat carrier or in the reactor can be generated. Here, another, for example, mechanical means can be used to form the flow in the reactor.

With optimally designed arrangement of the (electromagnetic field and suitable material selection of the reactor can advantageously also the process temperature through the

Eddy current fields are generated. This eliminates the

Need for an external heat supply. Any other type of heat generation can also be used.

The invention also provides a process for the oilation of hydrocarbonaceous input materials without external supply of heat for heating the heat carrier comprising the steps

a. Introduction of hydrocarbonaceous input materials into a reactor comprising a heat carrier and balls of para or ferromagnetic material,

b. Apply an electrical or electromagnetic

Field for generating eddy current fields in the reactor.

Another advantage results from the mechanical

Decoupling of the reactor. As a result, a continuous operation can be ensured.

The residual substances which may possibly arise in the case of the oiling, such as bitumen, paraffin, etc., can be replaced by at least one suitable structural arrangement, in particular by

at least one residue flow, for example, in the upper part of the reactor in a process step are easily discharged.

The invention relates to a device, in particular reactor comprising a heat transfer bath, geometrically formed Particles which may consist, for example wholly or partly of paramagnetic or ferromagnetic material, at least one residue discharge, for example in the upper part of the reactor and means for generating an electromagnetic or magnetic field, for example on the outer wall of the reactor or other suitable

Location of the device, possibly a heater,

optionally a tank system, optionally at least one distillation column.

The subject of the invention is also a device

preferably a reactor comprising a heat carrier

Liquid metal, wherein the liquid metal comprises at least 1% silver and optionally tin.

Figure 1 shows schematically a suitable reactor with

Heat transfer bath, paramagnetic and / or ferromagnetic particles and residue sequence.

example 1

According to Example 1, the oil is in a reactor in

Presence of paramagnetic and / or ferromagnetic particles carried out. As a heat carrier tin is used. The heat transfer bath made of tin is located in the lower part of the reactor. The carbonaceous input material to be oiled floats on top of the heat carrier bath. The heat transfer bath made of tin is heated to a temperature of at least 380 degrees Celsius. The paramagnetic and / or ferromagnetic particles are due to their density in the

Wärmeträgerbad. By the electromagnetic or magnetic field, the particles are set in rotation and thereby ensure optimum mixing and

Heat transfer. The obtained during the oiling

Starting material (product) can be drained or pumped out through the outlet opening in the upper part of the reactor. in the lower part of the reactor remains the heat transfer bath with the paramagnetic and / or ferromagnetic particles and can be used directly for the next oiling.

A corresponding reactor is shown in FIG.

Claims

claims

1. A process for the treatment of hydrocarbons

Input material comprising the steps

a. Filling with hydrocarbon

Input material into a reactor, the one

Includes heat transfer medium on which the

hydrocarbonaceous input material floats, b. Generation of a centering flow in the heat transfer medium, c. Obtaining the products of the REAL from the reactor.

2. A process for the treatment of hydrocarbons

Input material comprising the steps

a. Filling with hydrocarbon

Input material into a reactor, the one

Includes heat transfer medium on which the

flocculates hydrocarbonaceous input material, and wherein the heat transfer medium comprises geometrically formed particles,

3. The method of claim 1 or 2, wherein the heat carrier comprises geometrically formed particles, preferably balls.

4. The method according to any one of the preceding claims, wherein the geometrically shaped particles for generating the centering flow are set in rotation.

5. The method according to any one of the preceding claims, wherein the geometrically formed particles wholly or partly made of paramagnetic or ferromagnetic material.

A method according to any one of the preceding claims, wherein the centering flow is generated by an electromagnetic field or a magnetic field applied externally to the reactor.

7. The method according to any one of the preceding claims, wherein the heat transfer medium is a liquid metal.

8th . Method according to one of the preceding claims, wherein the heat carrier is a metal, an alloy, a mixture of metals, a metal powder dispersion or a

Thermal paste with a melting temperature of less than 400 degrees Celsius.

9. Method according to one of the preceding claims, wherein the heat carrier comprises tin or consists of tin with a purity of at least 99, 998%.

10. Method according to one of the preceding claims, wherein the heat carrier comprises tin and silver or comprises silver, but no tin.

11. Method according to one of the preceding claims, wherein the heat carrier is heated to a temperature of 380 degrees Celsius or more.

12. Method according to one of the preceding claims, wherein the heat carrier is heated to a temperature of 400 to 500 degrees Celsius, preferably a temperature of 410 to 445 degrees Celsius.

13. A process for the purification of hydrocarbonaceous input material, wherein the hydrocarbonaceous input material is introduced into a reactor comprising a heat carrier of liquid metal, characterized in that the heat transfer medium of liquid metal is mixed with the hydrocarbonaceous input material during the oiling.

14. A process for the treatment of hydrocarbons

Input material, wherein the hydrocarbonaceous input material is introduced into a reactor comprising a liquid metal heat transfer medium, characterized in that the liquid metal heat transfer medium comprises 50 to 95% tin and the heat transfer medium is mixed with the input material containing hydrocarbons during the oiling.

15. A process for the oilification of hydrocarbons

Input material, wherein the hydrocarbonaceous input material is introduced into a reactor comprising a liquid metal heat transfer medium, characterized in that the liquid metal heat transfer medium comprises 1 to 10% silver and the heat transfer medium is mixed with the input material containing hydrocarbons during the oiling.

16. Method Veröllung von hydrocarbonhaltigem

Input material, wherein the hydrocarbonaceous input material is introduced into a reactor comprising a liquid metal heat transfer medium, characterized in that the liquid metal heat transfer medium comprises tin and at least 1% silver, and the

Heat carrier with the hydrocarbon

Input material is mixed during the oiling.

17. The method according to any one of claims 13 to 16, wherein the heat carrier is heated to a temperature of 380 degrees Celsius or more.

18. The method according to any one of claims 13 to 17, wherein the heat carrier is heated to a temperature of 400 to 500 degrees Celsius, preferably a temperature of 410 to 445 degrees Celsius.

19. The method according to any one of claims 13 to 18, wherein the mixing takes place by means of a centering flow, which is generated in the heat transfer medium.

20. The method according to any one of claims 13 to 19, wherein the heat carrier geometrically formed particles,

preferably comprises balls.

21. The method according to any one of claims 13 to 20, wherein the geometrically shaped particles are set in rotation.

22. The method according to any one of claims 13 to 21, wherein the geometrically formed particles are wholly or partly of paramagnetic or ferromagnetic material.

A method according to any one of claims 13 to 22, wherein the centering flow is generated by an electromagnetic field or a magnetic field applied externally to the reactor. A process according to any one of the preceding claims, wherein the oiling is carried out in the presence of a catalyst. Method according to one of the preceding claims, wherein the temperature during the oiling at least 2

different measuring points in the reactor is measured. Apparatus, for example a reactor for the oilation of hydrocarbonaceous input material, comprising a. a heat carrier having a density which is greater than the density of the hydrocarbonaceous input material, so that the hydrocarbon-containing

Input material floats on the heat transfer medium and b. Means for generating a centering flow in the heat carrier, the centripetal on the

hydrocarbonaceous input material acts and pulls it under the heat transfer medium. Apparatus according to claim 26, wherein the heat transfer medium is a liquid metal. A device according to any one of claims 26 to 27, wherein the liquid metal comprises tin or silver or tin and silver. Apparatus according to any one of claims 26 to 28, wherein the means for generating a centering flow

geometrically formed particles of paramagnetic or ferromagnetic material are, for example, by means of an electromagnetic or magnetic

Field are set in rotation. Use of a method according to one of claims 1 to 25 or a device according to one of claims 26 or 29 for the production of fuels or

Starting materials for the chemical industry or for the purification of substances containing carbon

Input material contaminated, for example, for cleaning substances such as sand or water that are contaminated by oil.