CH714685A2 - Processes and devices for the pyrolysis of carbon-containing organic compounds for the production of liquid fuels, coke or charcoal and fuel gases. - Google Patents

Abstract

Process and apparatus for pyrolysis of carbonaceous organic material as input material, dissolved in a liquid, hot suspension in the temperature range 260 to 560 ° C under an overpressure between 2.0 to 25 bar and with exclusion of oxygen to produce liquid fuels, coke or charcoal and fuel gases to cover the Process energy, wherein the melting and cracking process takes place together in a container which is designed as a fully mixed loop reactor, and bound with the admixture of alkali metals chloride and sulfur and eliminated as slag.

Description

Description [0001] Method and device for pyrolysis of carbon-containing organics.

From WO 2008/022 790 A2 a method and device is known for the treatment of plastic-containing waste for the oiling and extraction of diesel fuel and low boilers, the plastic mixtures are melted in the first reactor stage at 180 ° C to 250 ° C and in the second reactor stage is cracked at approx. 400 ° C. and the cracked gases are fed to a partial condenser, in which the long-chain polymers are returned to the cracking reactor and the short-chain polymers are separated into liquid fuels and fuel gases in a condenser. This complex procedure with a separate melting tank and a downstream cracking plant and condensers requires considerable outlay on equipment.

From CH 000 000 706 819 A2,000,000 706 818 A2 and 000,000 706 804 A2 a process for melting and oiling mixed plastics is known in which, under vacuum and admixing catalysts, a hot oil bath, with horizontally located screw pumps which are surrounded by a heating jacket, heated and mixed and a plastic melt is continuously added to the oil circuit.

The screw conveyor of the screw pump extends over the entire length of the high-temperature heat exchanger.

In practice, this arrangement has shown that the cracked gases have built up in the lying spiral and formed a gas spigot over the entire length of the screw pump, so that no more liquid could be pumped and circulated.

Even at an angle of 45 ° from the horizontal, no significant improvement could be found.

Another experimental setup with a vertically standing, short spiral pump (22) or a channel wheel pump (92), which sucks in the oil bath to be circulated freely and at the same time sweeps away the cracking gases that are formed, and also allows the rising gases to flow freely through the rotor even at a standstill, has led to a satisfactory result, the results of which are presented here in the combination of features of claim 1 and with respect to the device by the features of claims 14 and 15.

The presented oiling system is designed for the throughput of mechanically processed and dried substitute fuel from household waste collection or industrial and commercial waste, as well as renewable raw materials in the form of energy crops or residues such as fruit bundles from palm oil extraction or pomace from olive oil extraction, as well as algae from sea or lakes.

Up to 10% of the entry weight may also contain contaminants such as glass, sand, stones and metals, but these reduce the throughput while increasing the heat energy to be entered.

Fig. 1 shows by the dividing line (1) delimited the field with the scope of claim (3) and outside the prior art (2).

The entry material (5) is fed to the material processing system (4) and processed in the processing system (6) to a dry, calibrated and free of impurities (7) input material (8).

The input material (8) and the metered alkali metals (7) are fed to the pyrolysis reactor (11) via an entry and metering device, which takes place here as an example of a possible embodiment variant via an extruder.

The control and monitoring of the metering takes place via the fill level measurement (38) with which the fill level (36) in the pyrolysis reactor (11) is adjusted and held by the regulated metering quantity of the input material (8).

The reactor chamber (78) is filled with a start-up suspension (35) from a mixture of heavy oil and synthetic oils, the boiling point of which is above 600 ° C and also when waste oils or plastic mixtures are added, which contain low boilers and solvents, The chemical and thermal stability of the suspension (35) is maintained by simultaneously increasing the internal pressure in the reactor to + 12 to 15 bar when the process temperature is increased to> 370 ° C. This keeps the volatile components of the middle distillate and low boilers liquefied and react with the alkali metals to bind the chloride and sulfur to sulfide, which is discharged as a solid together with the slag (84) from the pyrolysis reactor (11).

This pressure regulation takes place via the gas pressure of the cracking gases (46) which accumulate in the gas space (34) in front of the pressure holding valve (81) and the pressure holding valve (81) is smoothly opened or closed by the control of the thermostat and pressostat (83), so that at a selected temperature in the suspension (35) of +260 ° C the holding point is 2.0 bar and at +560 ° C the holding pressure is 25 bar.

After the hot cracking gases (46) have left the pyrolysis reactor (11), they are cooled in the condenser (47) via the refrigeration (48) and the condensate obtained is collected and stored in the form of liquid fuels (50).

The non-condensable and combustible gases (51) are supplied to the heat generation system (53) for process energy generation.

CH 714 685 A2 [0018] If the process temperature is below +300 ° C, a thermal oil can be used as the heat transfer medium. At temperatures above +300 ° C it is advantageous to work with a hot and pressureless molten salt.

The entire reactor chamber (78) including the sink sludge discharge (27) and the gas and liquid dome (33) are filled and overlaid with the suspension (35) up to the fill level (36), and provided with a double jacket (15) and heated via a heating medium (18) and the entire contents of the reactor space (78) can be evacuated via a common emptying (76) provided at the lowest point (72).

With the increase in the operating level (36) by blowing nitrogen (36.12) into the shuttle tank (36.7) in the pyrolysis reactor (11), the accumulation level (36.1) is set and the floating substances (31.1) are pressed into the discharge spiral (37) and conveyed in the conveying direction (37.1) into the sink sludge discharge (27).

The discharge spiral (37) of the horizontally lying gas and liquid dome (33) promotes the suspended matter (31) rising from the reactor chamber (78) into the sloping discharge (27) arranged obliquely underneath, the inclination (39) thereof of the horizontal between 30 ° to 50 ° and with the discharge spiral (28) conveys the sediments (29) from the reactor chamber (78) together with the suspended matter (31) as a sludge mixture (30) via the dividing line (77) into the discharge chute (41) ,

The discharged sludge mixture (30) from the discharge chute (41) falls into the horizontally arranged dryer (42) below, the guide tube (14) of which is enclosed by a double jacket (15) in which a heating medium (18) flows and volatile constituents in the form of gases or cracking gas (46) are led through the gas space (40) into the gas outlet (85) by the heat input (82).

The dry residues (84) from the sludge mixture (30) consist of inert materials, coke or charcoal (29.1) and non-crackable hydrocarbon compounds and metals are with the scraper spiral (28) from the dryer (42) into the lock (44 ) promoted.

The lock (44) consists of two mutually interlocked gas-tight slides, which are flushed and inerted after each opening and closing process by injecting nitrogen (86).

Fig. 2 shows a cross section through the pyrolysis reactor (11) with which the functions and features described in Fig. 1 are shown in detail.

The arrangement of the inlet nozzle (13) for loading (10) with input material (8) and the alkali metals (7) depends on the nature of the input material (8).

If the input material (8) consists of liquids such as waste oils, fats and cooking oil as well as pre-melted and hot suspensions (35), these are entered via the melt nozzle (13.1) into the riser pipe (11.1) of the pyrolysis reactor (11), which immediately is arranged above the pressure side of the spiral pump (22) or channel wheel pump (92).

If the input material (8) consists of dry chopped organic substance mixtures such as substitute fuel mixtures from the processed household waste or agricultural waste materials, such as straw and olive or grape pomace, they will be cut over the solid (13.2) into the downpipe (11.2) of the pyrolysis reactor (11 ) entered.

The flow rate of the circuit flow (26) in the heated guide tubes (14) and the counterflow of the heating medium (18) in the double jacket (15) is between 0.5 to 2.0 m ¹ per second depending on the nature and specific heat content of the input material (35) with heat input from mixed plastics of 0.5 to 0.8 kW per one kilogram and with a residence time of 25 to 120 minutes until the complete transition to cracking gases (46) with an expansion of the cracking gases (46) in the reactor of 0.2 to 0.5m ³ per one kilogram is completed.

The drive (21) of the scraper spirals (23) takes place via a geared motor, which can change the direction of rotation (23.2) and also perform a lifting movement (23.1), the functions of which are explained in more detail in FIGS. 4 and 5.

The expansion of the cracking gases (46) at a suspension (35) temperature of +400 ° C takes up about 30% of the reactor space (78) volume and generates additional turbulence and turbulence (75) of the suspension (35) the heat exchanger surfaces of the guide tubes (14) and, in cooperation with the circulation flow (26), helps to accelerate the heat input into the suspension (35).

In order to carry out an exact level measurement (38) in the event of turbulence and turbulence (75), a measuring chamber (88) is created, which is hydraulically connected to the reactor chamber (78) via a labyrinth, consisting of a storage plate (87), and thus the gas flow is led past the measuring chamber.

Depending on the nature of the input material (8), suspended substances (31) are formed, which accumulate as floating substances (31.1) on the surface of the operating fill level (36) and, if necessary, raise the accumulation level (36.1.) To the accumulation level (36.2) ) pressed into the area of the discharge spiral (37) and through it through the gas and liquid dome (33) from the pyrolysis reactor (11) through the conveying direction (37.1) of the discharge spiral (37) and over the sink sludge discharge (27) and the discharge chute ( 41) are carried out.

After completion of this discharge process, the accumulation level (36.1) can be lowered to the operating level (36) by manual or automatic actuation of the three-way valve (36.8).

CH 714 685 A2 The function of the three-way valve (36.8) shown here can also be carried out by other control devices or devices and carried out by them.

The manual or automatic lifting of the fill level takes place via the pendulum container (36.7) which is connected via the connecting piece (36.5) as a communicating vessel with the reactor space (78) and the suspension (35) therein and both containers have the same operating fill level ( 36) and the gas space (34) of both containers are also connected to one another via the gas suspension line (36.11).

Fig. 3 shows a cross section through the pyrolysis reactor (11) similar to Fig. 2 with the difference that instead of the spiral pump (22), the suspension (35) with an open channel pump (92) from the lower deflection chamber ( 79) is sucked in and pressed into the riser pipe (11.1) by the impeller (94) in the pressure delivery direction (99).

This creates the circuit flow (26), which is adjusted by regulating the speed (100) of the impeller (94), the speed (69) in the riser pipe (11.1) and down pipe (11.2).

The form on the channel wheel pump (92) is exactly the head, which is given by the operating level (36) and the work to be performed by the channel wheel pump (92) is reduced to the displacement capacity of the suspension (35) to generate the circulating flow ,

Together with the adjustable flow rate of the heating medium (18) in the heat exchanger (11.3), the ideal heat input into the suspension (35) can thus take place.

4 shows a section through the riser pipe (11.1) with a vertical (70.1) built-in spiral pump (22) with which the suspension (35) is sucked out of the lower deflection chamber (79) and with the revolutions (73) the rotor (89) the suspension (35) is conveyed together with the gas bubbles (32) in the conveying direction (25) through the guide tube (14) into the upper deflection chamber (80).

The guide tubes (14) of the spiral pump (22) and the heat exchanger (11.3) arranged above them are encompassed by a double jacket (15) in which a heating medium (18) with the flow direction (19) in counterflow to the conveying direction (25) of the Suspension (35) flows and the suspension (35) is heated via the heat input (82).

With the slow-running scratch spiral (23) caking and residues (91), which are deposited on the hot surface of the guide tube (14), are removed by changing the direction of rotation (23.2) and the lifting movement (23.1).

Between the guide tube (14) and the outer diameter (23.3) of the scratch spiral (23), there is an annular gap (61.1) of approximately 3.0 millimeters, which limits the build-up of the carbon-containing residues (91) and at the same time protects the inner surface against wear the guide tube (14) and also as a sliding surface lubrication for the scratch spiral (23).

In the spiral pump (22) the passage (64) between the shaft (22.1) and the wall of the guide tube (14) is dimensioned after the ball passage (90) of the largest dimension of substances to be assumed, which as input material (8) the entry nozzle (13) are entered into the pyrolysis reactor (11).

The throughput of the spiral pump (22) and flow rate (69) in the guide tubes (14) are determined by the dimensions and revolutions (73) of the rotor (89) and the pitch (65) of the helix (61).

During a revolution (73) of the rotor (89) of the spiral pump (22) via the slope (65) of the helix (61), the displaced volume (67) in the spiral pump (22), the volume (68) in the guide tube of the heat exchanger (11.3) and the volume (68) has a length (66) of one meter.

4 and 5 shows a section through the heat exchanger (11.3) of the downpipe (11.2).

In the guide tube (14) build up on the inner wall by the heat input (82) in the suspension (35) buildup and caking of non-cracked carbonaceous residues (91) which by the slowly rotating spiral conveyor (23) from the wall of the guide tube (14) is scraped off and dropped in the conveying direction (25) as sediments (29) into the lower deflection chamber (79) and then disposed of via the sink sludge discharge (27) from the pyrolysis reactor (11) via the dryer (42).

At the same time, the coating of carbon-containing residues (91) on the heating surface walls of the guide tubes (14) forms an ideal armor and sliding surface for the conveyor spirals (23), discharge spiral (37) and clearing spirals (28), which together with the oil-containing suspension ( 35) ensure silent and low-wear operation even when throughput of a small proportion of wear and disruptive substances.

Via the passage (60) of the open scratch spiral (23) also called the eye, the hot ascending gas bubbles (32) together with the suspended matter (31) can rise into the upper deflection chamber (79).

At the same time, the descending circulation flow (26) and the oppositely rising gas bubbles (32) between the coils (61) of the conveyor spiral (23) generate a swirl (75) of the suspension (35) which on the heat exchanger surfaces of the guide tubes (14 ) lead to an increased mass transfer and thereby accelerate the heat input (82) into the suspension (35).

CH 714 685 A2

Reference symbol list [0053]

parting line

State of the art

Scope of the claim

Mineral processing

Eintragsgut

processing plant

alkali metals

7.1 Entry device

Inputgut

entry device

loading

pyrolysis reactor

11.1 Riser pipe

11.2 downpipe

11.3 Heat exchanger

11.4 Loop reactor

reactor shell

feed connection

13.1 Melt nozzle

13.2 Trim solid

guide tube

jacketed

Heizmediumeintrag

Heizmediumaustrag

heating medium

flow direction

Drive Through

drive

spiral pump

22.1 shaft

scratch spiral

23.1 stroke

23.2 Direction of rotation

23.3 outside diameter

CH 714 685 A2

direction of rotation

conveying direction

Circuit flow

Sinkschlammaustrag

Räumerspirale

conveying direction

sediments

Coke or charcoal

sludge mixture

suspended solids

floating matter

gas bubbles

gas flow

Gas and liquid dome gas space suspension operating level

storage level

accumulation height

Dynamic pressure level

Backpressure height

connecting pieces

pendulum liquid

pendulum container

Three-way valve

nitrogen Storage

nitrogen

Gas displacement line

nitrogen

Austragsspirale

conveying direction

level measurement

Tilt

gas vent

chute

dryer

CH 714 685 A2

dry material

lock

pusher

Crack gas

capacitor

refrigeration

Refrigeration circuit

Liquid fuel

fuel gases

gas storage

heat generation

gas burner

boiler

leader

returns

circulating pump

Outer diameter

passage

spiral

annular gap

Outer diameter

Inner diameter

passage

annular gap

pitch

length

volume

volume

speed

Horizontal

Vertical

angle

Lowest point

revolution

reserve position

turbulence

CH 714 685 A2

emptying

parting line

reactor chamber

Lower deflection chamber

Upper deflection chamber

Pressure holding valve

heat input

Thermostat and pressostat

slag

gas vent

nitrogen

baffle

measuring chamber

rotor

Ball passage

arrears

Kanalradpumpe

pump housing

impeller

clutch

drive motor

mounting plate

Suspensionsansaug

Pressure conveying direction

100 speed

Claims (29)

claims 1.Method and device for pyrolysis of carbon-containing organic matter as input material (8) dissolved in a liquid, hot suspension (35) in the temperature range between 260 to 560 ° C under an overpressure between 2.0 to 25 bar and with the exclusion of oxygen for the production of liquid fuels (5 ), Coke or charcoal (29.1) and fuel gases (51) to cover the process energy with the steps: - Loading (10) of the vertical (70.1) standing pyrolysis reactor (11) with the input material (8) which is free of impurities and oxygen. - Addition of alkali metals to bind chloride and sulfur. Melting the input material (8) in the circulating flow (26) of the hot suspension (35) until the input material (8) changes into a gaseous and solid state. - Discharge of the cracked gases (46) into the condensation (47) for the production of liquid fuel (50) and fuel gases (51). - Discharge of the dried sediments (29) consisting of inert substances, bound sulfur and chloride, coke or charcoal (29.1) from the dryer (42). 2. The method according to claim 1, wherein the reactor chamber (78) of the pyrolysis reactor (11) from the riser pipe (11.1), the down pipe (11.2) and an overhead deflection chamber (80) and a bottom deflection chamber (79) and the sink sludge discharge (27 ), the gas and liquid dome (33) and the dryer (42), CH 714 685 A2 which are spatially connected to one another and is designed as a loop reactor (11.4) with a circulating flow (26) and the manometric height is set by the operating fill level (36). 3. The method according to claims 1 and 2, wherein the circulation flow (26) of the hot suspension (35) is generated with the spiral pump (22) or channel wheel pump (92) arranged in the riser pipe (11.1). 4. The method according to claims 2 and 3, wherein with the slow-running scratch spirals (23) which has a change of direction (23.2) and stroke movement (23.1). Caking and residues on the hot inner wall of the guide tubes (14) are scraped off and removed. 5. The method according to claims 2 and 3, wherein the conveying direction (25) of the spiral pump (22) or channel wheel pump (92) and the delivery spirals (23) takes place in the direction of the circuit flow (26). 6. The method according to claims 2 and 3, wherein the vertical, standing spiral pump (22) and the horizontal, lying channel pump (92) is arranged above the lower deflection chamber (79) and the conveying direction (25) against the upper deflection chamber (80) is directed. 7. The method according to claims 2 and 6, wherein the loading (10) of the vertical (70) standing pyrolysis reactor (11) with the inoculum (8) in the riser pipe (11.1) above the spiral pump (22) or channel wheel pump (92) and the dropping of the sediments (29) and suspended matter (31) and the cracking gases (46) at the uppermost point above the dividing line (77). 8. The method according to claims 2, 3 and 7, wherein the following mutually spatially connected system parts such as the pyrolysis reactor (11), the sludge discharge (27) and the gas and liquid dome (33) as a communicating vessel with the hot suspension (35) superimposed and have a common fill level (36) and a common emptying (76) of the pyrolysis reactor (11) content located at the lowest point (72) and the cracked gases (46) are discharged via the common gas outlet (40). 9. The method according to claims 3, 6 and 8, wherein the heat input (82) into the suspension (35) via the heating surfaces of the guide tubes (14) and the flow direction (19) of the heating medium (18) in the double jacket (15) Flow direction of the circulating flow (26) takes place in the opposite direction. 10. The method according to claims 1, 8 and 9, wherein the chemical and thermal stability of the suspension (35) with increasing process temperature is maintained by increasing the system pressure in the pyrolysis reactor (11) and the pressure control valve (81) via the thermostat and pressostat (83 ) is controlled. 11. The method according to claims 7, 8 and 9, wherein in the parallel connection of several pyrolysis reactors (11) side by side, these a common lower deflection chamber (79) and upper deflection chamber (80), and a common sink sludge discharge (27) and one have common gas and liquid dome (33), and only the centrally arranged pyrolysis reactor (11) has a material inlet connection (13). 12. The method according to claims 7 and 8, wherein the weight ratio between the suspension (35) in the reactor space (78) and the input material (8) based on the throughput per hour for four parts in the reactor space (78) to one part of the input material (8) lies. 13. The method according to claim 1, wherein alkali metals are added to the chloride and sulfur binding. 14. The method according to claims 6 and 7, wherein the loading (10) with liquids as input material (8) via the melt nozzle (13.1). 15. The method according to claims 6, 7 and 13, wherein the loading (10) with dry mixtures of substances takes place via the solid nozzle (13.2). 16. The method according to claims 7 and 8, wherein by lifting the operating level (36) to the accumulation level (36.1) the floating substances (31.1) are pressed into the area of the discharge spiral (37). 17. The method according to claims 8 and 16, wherein the floating substances (31.1) are conveyed through the conveying direction (37.1) of the discharge spiral (37) into the sediment discharge (27). 18. The method according to claims 16 and 17, wherein the raising and lowering of the operating level (36) via the application or relief of the pendulum container (36.7) with nitrogen (36.10). 19. The method according to claims 16 to 18, wherein the shuttle tank (36.7) via the gas shuttle line (36.11) and the connecting piece (36.5) for the shuttle liquid (36.6) are spatially connected to the reactor space (78). 20. Apparatus for carrying out the method according to claims 3 and 6, wherein with one revolution (73) of the rotor of the spiral pump (22) via the slope (65) of the helix (61) the displaced volume (67) in the spiral pump (22 ) corresponds to the volume (68) in the guide tube (14) with a length (66) of one meter. 21. Device for performing the method according to claims 7 and 14, wherein the passage (64) between the shaft of the spiral pump (22) and the guide tube (14) or the impeller (94) of the channel pump (92) to the pump housing (93) corresponds to the ball passage (90) of the largest dimension to be assumed in the input material (8). CH 714 685 A2 22. Device for carrying out the method according to claims 20 and 21, wherein even when the spiral pump (22) and the channel wheel pump (92) stand still, the gas bubbles (32) rising from the lower deflection chamber (79) are unhindered by the annular gap (64.1) and the rotor (89) of the spiral pump (22) or the passage (64) in the channel wheel pump (92) can rise via the guide tube (14) into the upper deflection chamber (80). 23. Device for performing the method according to claims 7 and 12, wherein the feed of the input material (8) into the pyrolysis reactor (11) is controlled via the fill level (36) of the suspension (35) and the fill level measurement (38). 24. Device for carrying out the method according to claim 23, wherein the measuring chamber (88) for the level measurement (38) is hydraulically connected to the reactor space (78) and is protected from turbulence by a labyrinth of dust plates (87). 25. Device for carrying out the method according to claims 7 and 8, wherein the discharge of the sediments (29) via the sink sludge discharge (27) and the discharge of the suspended substances (31) via the discharge spiral (37) and both material flows via the dividing line ( 77) are guided together in the same chute (41). 26. Device for performing the method according to claims 8 and 25, wherein in the dryer (42) the two material flows from the discharge chute (41) with the scraper spiral (28) as a sludge mixture (30) pushed through the hot guide tube (14) and the adhering volatile fractions as crack gases (46) via the discharge chute (41) into the gas outlet (40) and the dry residues (84) are ejected via the lock (44). 27. The device for carrying out the method according to claims 16 to 19, wherein by the actuation of the three-way valve (36.8) the pendulum container (36.7) is charged with nitrogen (36.12) and is relieved with the counter-movement via the gas pendulum line (36.11). 28. Device for carrying out the method according to claims 4, 25 and 26, wherein all heating surfaces are equipped with scraper spirals (28) or scraping spirals (23). 29. Device for performing the method according to claims 4 and 28, wherein the scratching spirals (23) on the drive (21) changes the direction of rotation (23.2) and can also perform a lifting movement (23.1).