DE19941497B4 - Process and apparatus for the production of liquid fuels from re-chargeable substances - Google Patents

Abstract

A process and apparatus is described which produces liquid fuels using special fumable residue and wood catalysts. The energy production for this process is carried out by catalytically assisted combustion to a clean flue gas. The carbonization and the catalytic evaporation in the distillation unit is carried out with special aluminosilicate catalysts, which are used one behind the other in the distillation and carbonization.

Description

The The present invention relates to a method according to the preamble of claim 1 and a device according to the preamble of claim 9th

Such Methods and devices are used to remove residues, such as Wood, unusable animal feed, digested sludge and residual waste to liquid fuels and to refine gases. This is done by a thermal-catalytic Cleavage of oil and gaseous Hydrocarbons from residues with subsequent catalytic workup of these Products too liquid Fuels.

Known are the gasification or carbonization of such residues. Thereby arise Products for the Use as a liquid Fuel are not suitable because the products are so inferior quality are that they can not be used in engines and burners. So During the gasification also resin materials, which become a short-term Failure of the engines lead, and the carbonation gives rise to tars and acids that are predominantly in the form can not be used as fuels.

Wood is over available in the thermal market and in the form of a liquid fuel and coal better for suitable for storage and consumption. The transport problems and handling would partly considerably simplified by such a conversion.

It therefore becomes a possibility sought to split the residues so that the products in shape of oil, Gas and residual coal for the use in the heat and power engineering can be used. This is by pure heat treatment only in a few cases succeeded. Especially with wood has been only gas with high load for the Engines or tars and acids generated at the felling, which for the use in the engine also in the form are not usable. developments in the hydrogenation could not be economical because of the high cost being represented.

Out DE 3806365 C1 For example, a process for the further processing of liquid and solid products obtained by the carbonization of waste products by bottom or gas phase hydrogenation using a catalyst is known. In this process, the combustion process is very unstable. Stabilization by using honeycomb catalysts is not described.

Out EP 0872535 A1 is the workup of various distillation fractions known by redistillation, to which a catalyst for stabilization was added. The distillation step of the process does not take place in the presence of a catalyst. Only the workup / refinement of the fractions in a mixing tank is carried out in the presence of a catalyst. In addition, in this prior art process non-fusible, but fusible materials are processed.

Out EP 0276081 A2 For example, an aluminosilicate catalyst is described as Zeolioth ZSM-5. This zeolite catalyst is added to the starting material. A distillation step after the thermal decomposition is not described there. Also in the process of this prior art, fusible plastic material is used. Softenable substances should not be processed. Also, a reuse of the catalyst in the step of thermal decomposition is not disclosed.

Out EP 0555833 A1 Also, a process for the preparation of low-boiling liquid hydrocarbons from waste plastics is described. This method has the same disadvantages as the methods EP 0872535 A1 and EP 0276081 A2 ,

The Object of the present invention is therefore a method and to develop a device of the type mentioned, that this too for non-fusible materials can be used while keeping one Combustion is performed in a stable manner.

The The object is achieved by a Method with the characterized features of claim 1 and by a device having the characterized features of the claim 9 solved.

Surprisingly was now in the heat treatment with catalysts found that the desired changes in the residuals then arise when the carbonization coupled with the catalytic conversion catalytically active surfaces carried out becomes. Substance groups have been found which catalyze such transformations and are so economical that the product conversion pays off.

A embodiment The present invention will be explained in more detail below with reference to the drawings. It demonstrate:

1 a schematic representation of a part of the plant, in which the catalytic evaporation of the volatile components of the residues takes place, and

2 a schematic representation of a Part of the plant in which the catalytic processing of the liquid products formed in the evaporation takes place, wherein the spent catalysts are used as catalytic substance in the plant part in 1 be used.

1 shows the device of the catalytic evaporation of these residues. With 1 is the input of the residues and those in the 2 withdrawn catalytic substance characterized. The residues are added in a ground state and mixed with catalytic material. The catalytic substances are multi-layer minerals of aluminum silicate.

The mixing ratio is residual material to mineral 1000: 1 to 10: 1, depending on the type of residue, the first value substances with high water content, such as digested sludge, the last value low-water materials, such as milled plastics. With 2 is the entry lock, consisting of two flaps called. In a Schwelbehälter are with 3 called the Schwelböden. They are alternately provided with an internal passage opening, see top and bottom floor, and with an outer overflow edge.

In the bottom is a flue gas duct 4 arranged for the passage of in a combustion vessel 8th arising flue gas from bottom to top, separate from the interior of the Schwebebehälter worry. This countercurrent arrangement of the flue gas and the residue in the carbonization is by a screw conveyor 5 with counterpressure plate that allows the gas-tight seal of the carbonization tank to the combustion tank 8th forms.

Due to the gas-tight closure of the screw conveyor 5 is a catalyst layer 6 consisting of hot catalyst blocks, the only passage for the flue gases from the combustion vessel 8th , connected with flue gas pipes 4 passing through the Schwelböden 3 be directed and at the top into a circulation evaporator 13 open out. The circulation evaporator 13 has an upper connection line 18 and a lower connection line 17 to a distillation column 29 in 2 ,

On the Schwelböden 3 Material transport rails move through a drive shaft 16 are driven. This drive shaft 16 is with a stirrer 24 connected and ends in the screw conveyor 5 , At the bottom of the combustion tank 8th is a rust 7 arranged below with an oil burner 9 and above is connected to a secondary air line. This air line is via a heat-pipe heat exchanger 10 connected at the bottom with a flue pipe from the circulation evaporator 13 and with a combustion gas line 11 and at the top with a fresh air line 12 connected is.

2 shows the inventive device after an outlet opening 15 for the smoldering products. These pass through an opening 21 and a separator 22 in a mixing container 23 , In the mixing container 23 is the stirrer 24 for a catalyst / condensate mixture. The mixing container 23 is with two connections 25 and 26 to the circulation evaporator 13 connected. At the top of the mixing tank 23 is an entry lock with an input line 27 for hydrocarbons and an input line 28 for a catalyst and a distillation column 29 appropriate.

At the bottom of the mixing container 23 is a discharge lock 30 attached with the two mutual flaps. The discharge lock 30 is a sieve 31 downstream with a container for a residue catalyst 32 and a support group 33 and a return line 34 that with the mixing container 23 connected is.

At the distillation column 29 is a product line 35 and a capacitor 36 arranged, a compressor 37 and a product line 38 having. The openings of the system part are with a gas extraction 39 provided with the fresh air line 12 in 1 connected is.

The inventive method is also by the 1 and 2 explained. In the 1 is the entrance path of the residue with 1 designated. By alternately opening the flaps of the entry lock 2 The material is directed into the carbonization tank. It is necessary that a mixture between the residue and the spent catalyst from the catalytic distillation at the point of entry 1 the residues prepared and by the screw conveyor 5 is realized in the sump.

The material to be smoldered by the mixing and conveying on the Schwelboden 3 from outside to inside, on the next downpour 3 from inside to outside and immediately to the screw conveyor 5 transported. The residue discharged from the sump downwards and heated to at least 350 ° C passes over the screw conveyor 5 into the combustion tank 8th , This combustion container 8th is from the first smoldering ground 3 of the carbonization tank through the catalyst layer 6 separated from honeycomb.

These Honeycombs are combustion catalysts with the base material cordierite, TiO2 / WO3 or SiC in porous Form coated with active material of precious metals, lanthanum cerium cobaltite manganites are.

These honeycomb catalysts not only lead to a complete and clean combustion, but also act by their re-radiation from the glowing honeycomb stabilizing the combustion. The honeycombs have a bore in the middle, through which the supply of the swelled residue and the axis of rotation passes. At the bottom of the combustion tank 8th is the rotating grate 7 through which the catalyst / ash mixture passes. This is disposed of to a part and returned to another part as a dilute catalyst again in the Schwelbehälter.

Also get into the Schwelbehälter the slurried catalyst residues from the circulation evaporator 13 , These are homogeneously mixed before their entry with the remaining feedstock or residue. This ensures that the catalytic effect of these catalyst residues can develop during the evaporation of the volatile components of the residue used. The dried and vorwelten catalyst residues fall into the combustion vessel 8th and, in the case of low-ash residues, can be reused in the distillation tank as a regenerated catalyst since their catalytic inhibiting carbon deposits are oxidized away.

In countercurrent to it is in the Schwelböden 3 the hot flue gas from bottom to top in the flue gas duct 4 passed and finally pulled up and into the circulation evaporator 13 and from there into the heat-pipe heat exchanger 10 directed. At the same time, the flue gas is kept at a constant 1000 ° C via the cooling in the carbonized soils 3 to 650 ° C in the circulation evaporator 13 to 450 ° C and in the heat-pipe heat exchanger 10 cooled to 200 ° C.

The constant combustion temperature in the lower combustion vessel 8th is achieved by the regulated secondary air supply. It changes the lambda in such a way that the excess of air keeps the catalyst temperature at a constant 1000 ° C. This means an adjustment of the amount of air to the combustion conditions of the dried and smoldered residues.

These combustion conditions are with the preheated air of 250 to 350 ° C and under reflection of the catalyst layer 6 at the top of the combustion vessel 8th very cheap. As a result, substances that are difficult to burn with a high proportion of ash can be completely and quickly incinerated.

By the flue gases, the vaporizable fractions of the residues are evaporated twice. The first evaporation takes place on the smoke flames heated with flue gas 3 of the upper repository in 1 and the second evaporation takes place in the mixing vessel 23 above the circulation evaporator 13 ,

The evaporation is done while stirring with the stirrer 24 which is the catalyst in the mixture 28 , a multi-layer mineral, also of aluminum silicate, holds in suspension. The catalyst 28 causes the catalytic after-reaction of the swelled vapors from the carbonization tank. In this case, longer-chain hydrocarbons are catalytically cleaved and dehydration reactions, such as the reaction of tars and acids from the wood to oil and water, catalytically activated.

Through the distillation column 29 with the capacitor 36 that by the compressor 37 is exhausted, the substances from low boilers and water at the top of the distillation column 29 subtracted, the product in the form of light fuel oil is in the middle of the distillation column 29 withdrawn and the spent catalyst is at the bottom of the mixing vessel 23 deducted. The feed from the carbonization tank takes place in the lower half of the distillation column 29 , wherein the previously condensed out fractions directly into the mixing vessel 23 be directed.

The at the bottom of the mixing container 23 over the lock 30 discharged muddy liquids as a mixture between spent catalyst and oil from the mixing vessel 23 be via a screen belt separation 31 separated in oil and catalyst residue. The catalyst residue 32 is in the sump of the 1 brought in. The oil is returned to the mixing tank 23 pumped.

Claims (18)

Process for the production of liquid fuels from substances which can be liquefied by smoldering the smoldering substances, burning the smoldering residues and distilling the volatile smoldering products, characterized in that the distillation of the volatile smoldering products is carried out in admixture with catalysts of aluminum silicates such that the smoldering of the smoldering substances occurs with mixing with coming from the distillation residues and that the combustion of swelled, solid residues in a combustion vessel with honeycomb catalysts takes place at the upper end. A method according to claim 1, characterized in that the coming of the distillation residues are catalyst residues of aluminum silicates, which are a Schwelbehälter for the Schwe ment be supplied. Method according to claim 1 or 2, characterized that the mixing ratio from residue to catalyst is 1000: 1 to 10: 1. Method according to one of claims 1 to 3, characterized that as honeycomb catalysts, a base material selected from the group consisting of cordierite, TiO2 / WO3 and SiC in porous form and coated with active material selected from a material of the group consisting of precious metals, lanthanum cerium cobaltite manganites. Method according to one of claims 1 to 4, characterized that the honeycomb catalysts at a constant temperature of 1000 ° C held become. Method according to one of the preceding claims, characterized characterized in that vaporizable fractions of the residues are evaporated twice. Method according to one of the preceding claims, characterized characterized in that with a catalyst of aluminum silicate in the case of carbonization, a catalytic after-reaction of the vaporized vapors is achieved becomes. Method according to claim 7, characterized in that that the catalytic post-reaction longer-chain hydrocarbons catalytically cleaved and dehydration reactions are activated. Apparatus for the production of liquid fuels from re-chargeable substances, using a bunker tank, a combustion tank for the catalytic workup of carbonization residues to flue gases and a distillation unit, characterized in that the combustion tank ( 8th ) has a flue gas outlet which is gas permeable with a catalyst layer ( 6 ) is closed off from honeycomb catalysts whose heat radiation has a stabilizing effect on the combustion. Apparatus according to claim 9, characterized in that the Kataysatorschicht ( 6 ) in the middle of a hole for the supply of slaked residues and for the passage of a drive shaft ( 16 ) having. Device according to claim 9, characterized in that at a lower end of the combustion container ( 8th ) a rotating grate ( 7 ), through which a catalyst / ash mixture can pass. Device according to one of claims 9 to 10, characterized in that above the combustion container ( 8th ) a Schwelbehälter with several Schwelböden ( 3 ) is arranged. Apparatus according to claim 12, characterized in that the carboniferous soils ( 3 ) are formed alternately with an inner passage opening or with an outer overflow edge. Device according to claim 12 or 13, characterized in that on the carbonized soils ( 3 ) Moving material transport rails, which through the drive shaft ( 16 ) are driven. Device according to one of claims 12 to 14, characterized in that the catalyst layer ( 6 ) from honeycomb catalysts via a screw conveyor ( 5 ) with a flue gas duct ( 4 ) through the Schwelböden ( 3 ) a passage opening for flue gases from the combustion container ( 8th ) in a circulation evaporator ( 13 ) form. Device according to one of claims 12 to 15, characterized in that the Schwelbehälter a mixing container ( 23 ) is subordinate. Apparatus according to claim 16, characterized in that the mixing container ( 23 ) at an upper end an input line ( 27 ) for hydrocarbons and an input line ( 28 ) for a catalyst and at the top with the distillation unit ( 29 ) is connected to receive catalyst residues. Apparatus according to claim 16 or 17, characterized in that the mixing container ( 23 ) at a lower end of a discharge lock ( 30 ) having.