Process for the production of solid, liquid and gaseous combustibles from organic materials.

The invention relates to a method for the production of solid, liquid and gaseous fuels from organic material in granular or powdered form using elevated temperature and under exclusion of air.

Solid and liquid fuels from fossil fuels such as coal and oil, obtained almost exclusively. The synthetic process for the production of hydrocarbons, including coal hydrogenation to Pier and Bergius or the so-called Fischer-Tropsch process to go from these fossil fuels, particularly coal, from.

Today it is assumed that coal originated primarily from plant material with a high cellulose content and oil from bacterial mass. Bacteria consist of 60 to 80% of proteins and lipids. These substances therefore must be eliminated on petroleum origin in the natural material originally present hetero functions, in particular nitrogen, sulfur and oxygen function. This should be done under conditions in which no carbon-carbon bonds were cleaved and oxidative or reductive processes were not necessary. The "natural reaction processes adopted could not nachgeahmtwerden previously. In particular, no method has been found which would have allowed the conversion of organic material, especially organic material of vegetable or animal origin, in solid or liquid fuels under normal pressure and without the involvement of reductive or oxidative processes.

The invention is therefore based on the object to provide a process for the recovery of solid, liquid and gaseous fuels, which does not rely on fossil fuels but the conversion of biomass microbial, plant or animal origin, of organic material sediments or garbage containing at normal pressure permits and without the intervention of reduction and oxidation processes.

Surprisingly now found a process which solves the previously indicated task.

The invention therefore relates to a process for the production of solid, liquid and gaseous fuels from organic material in granular or powdered form using elevated temperature and under exclusion of air, wherein passing the escaping when heated gases and vapors through suitable gas and liquid separator , the conversion temperature maintains until the gas and steam development is substantially complete and the solid conversion residue and the separated gases and liquids isolated, which is characterized in that, as organic material carbohydrates, lipids, proteins, plant, bacterial, algae masses raw sludge, sewage sludge or sludge from plants for waste water treatment or the organic components of municipal and industrial waste used and this material is heated in the presence of a conversion catalyst at a rate of 5 to 30 ° C per minute to a conversion temperature of 200 to 400 ° C.

It istvortei Ihaft, the organic starting material before heating admix a conversion catalyst. As the catalyst can be alumina, an aluminum salt, phosphoric acid, phosphate, borate, silica gel, silicates, aluminum silicate or an oxide of a transition metal, or use a mixture of these catalysts. As oxide of a transition metal used is preferably a Ti-, V-, Cr-, Mn-, Fe-, Co-, Ni-, Cu- or Zn-oxide, or a mixture of these oxides or a mixture of at least one of these oxides with at least one dervorhergenannten compounds. Have proved useful alumina, montmorillonite, mixed catalysts comprising aluminum oxide / copper oxide, aluminum / vanadium pentoxide and alumina / nickel.

The conversion temperature is preferably in the range of 250 to 350 ° C, even more preferred is the range from 280 to 330 ° C, a temperature of about 300 ° C is most preferred.

It istvorteilhaft heat the organic feedstock at a rate of 10 to 20 ° C per minute to convert temperature.

The proportion of catalyst is generally from 0.01 to 10 wt .-% preferably 0.1 to 6 wt .-%, based on the weight of the organic material used.

When the starting material mainly consists of cellulose and carbohydrates, such as vegetable origin, one obtains coal as the main product. If the starting material mainly composed of proteins and lipids, for example, of a biomass based on micro-organisms, the conversion product is mainly composed of oils and hydrocarbons. Overall, the materials used to 70 to 90% of the originally present carbon in coal and oil are converted by the inventive method. The remaining carbon occurs in gaseous form as a mixture of CO₂, CO, CH₄ and lower hydrocarbons from. The heat of combustion of oils obtained liegtje the starting material, reaction conditions and catalyst 29308-41868 kJ (7000-10000 kcal / kg). The heat of combustion is carbon dergebildeten 12560-33494 kJ (3000-8000 kcal / kg), depending on the amount present in the coal inorganic residues. The oils obtained are free of inorganic residues and relatively low sulfur content (0.05 to 1.0% S). They can be compared in this respect with the best petroleum oils having sulfur contents of 0.3 to 6%.

The inventive method is particularly suitable for processing and conversion of sewage sludge and sludge, as produced in plants for biological wastewater treatment. This sludge is usually dewatered mechanically in filter presses or centrifuges up to a water content of about 40 to 60%. This water content is still substantially reduced either by air drying or by heating, so as to obtain a dry solid bulk material in powder or granular form. This material is used in the inventive method. The mixture is heated slowly to the absence of air, it first evaporates the remaining water, which is condensed and collected. At about 180 to 200 ° C, the elimination of the hetero-features that sharply increases 250 ° C and from 320 ° C decreases slowly begins. This produces carbon dioxide, carbon monoxide, ammonia, hydrochloric acid, hydrogen sulfide and lower hydrocarbons from methane to hexane. Ammonia, hydrogen chloride, hydrogen sulfide and some carbon dioxide condense together with the water in the form of non-hazardous as ammonium salts and are thus removed from the gas phase. The escaping gases are free of basic substances and contain as main components CO₂, CO, CH₄ and lower hydrocarbons. One kg of sludge about 5 liters of gas is obtained with a calorific value of 18 600 people kJ /_m3,

Since those making according to low temperature shift - as opposed to pyrolysis - no CC bonds are cleaved substantially, the low gas content is understandable. During the conversion process this gas is used as inert gas, which prevents the ingress of atmospheric air.

The resulting when converting higher hydrocarbons or oils escape as gases or vapors from the reaction vessel. They are usually fused together and subsequently refined. Compared to petroleum, the conversion resulting oil has the advantage that it does not contain difficult to realize asphalts and tars. It is quantitatively vaporized, which is for further processing, particularly in cracking processes for fuel production, is advantageous. Analytical investigations of the conversion oil obtained according to the invention have also shown that the proportion of unbranched hydrocarbons and fatty acids can be up to 50%. The Fensäure Group can easily be removed from the oil, it is a valuable industrial raw material whose price currently is substantially higher than that of oil. The same is true for the unbranched hydrocarbons. If desired, the fatty acids can, however, also be converted in a known manner in hydrocarbons.

Since the conversion of sewage sludge, the carbon compounds contained therein are converted to a larger part in oil, the resulting end of the conversion process residue is relatively low carbon. It can be burned directly but nevertheless, if the usual security measures with respect to any existing heavy metals, especially mercury and cadmium, are complied with.

The sulfur and nitrogen content of the coal residue is relatively low, the coal can therefore be re-hydrated or be used for the production of water gas.

The novel process is advantageously carried out continuously by the dry starting material, for example, the dried sewage sludge, continuous granular or as a powder, for example by means of a Förderschnekke, conveyed through a heated reaction tube.

The conversion process is usually terminated after 2 to 3 hours.

If sewage sludge is used in the conversion, the addition of catalyst material is usually unnecessary because the existing sludge in inorganic components usually contain adequate amounts of silicates, aluminum compounds and transition metals. The large-scale conversion of this material is greatly facilitated.

The following examples serve to further illustrate the invention.

example 1

100 g albumin are heated for 3 hours under the exclusion of air to 230 ° C. It will obtain solid, carbon-like product 30 g of oil and 42 g.

Oil: C 70.5%; H 12.1%; Combustion heat 31 401 kJ / kg

Coal residue C 79%; Combustion heat 34332 kJ / kg.

example 2

100 g dried sludge (C 44%; H 6.66%; N 8.39%, 20% residue) are heated under the exclusion of air for 2.5 hours at 320 ° C. It will obtain solid, carbon-containing product 35 g of oil and 41 g.

Oil: C 66.1%; H 8.4%; N 7.5%; S 0.32% to. Combustion heat 29726 kJ / kg.

Carbon residue: 35.39% C; 1.7% H; 5.76% N.

Residue: 49.85%; Combustion heat 12980 kJ / kg.

example 3

100 g of dried sewage sludge are mixed with 5 g A1₂0₃ and 0.1 g CuO and heated for 3 hours at 300 ° C with air excluded. There are obtained 42 g of oil and 39 g carbonaceous solid product.

Oil: C 75.9%; H 10.2%; N 2:08%; S 0.05%; Combustion heat: 37 263 kJ / kg.

Residue containing: C 40.1%; H 1.8%; N 4.8%; S 1:26%;

Residue 42.5%; Combustion heat 15073 kJ / kg.

example 4

100 g of dried bacterial mass (Streptomyces species) are heated with 5 g of anhydrous montmorillonite 2 hours to 350 ° C with air excluded. There are obtained 47 g of oil and 34 g of solid residue containing carbon.

Oil: C 62%; H 12.5%; N 3.2%; S 0.3%; Combustion heat 32657 kJ / kg.

Residue containing: C 52%; H 1.5%; N 3.2%; S 0.5%;

Residue 30.7%, heat of combustion 21353 kJ / kg.

example 5

100 g dried sludge is mixed with 1 g A1₂0₃ and 0.01 g of V₂0₅ mixed and heated auf400 ° C for 3 hours under exclusion of air. There are obtained 33 g of oil and 59 g of residue.

Oil: C 75.2%; H 11.2%; N 5:06%; S of 0.15%.

Residue containing: C 37.2%; H 1.6%; Residue 47.2%.

Instead of V₂0₅ can also 0.1 g NiO are added.

example 6

100 g sewage sludge is mixed with 1 g A1₂0₃ mixed and heated to 280 ° C for 2 hours. It will obtain solid, carbon-containing product 29 g of oil and 51 g.

Oil: C 70.2%; H 10.1%; N 6.1%; S 0.4%; Combustion heat 29098 kJ / kg.

Residue containing: C 38.9%; H 3.3%; N 6.4%; S 1.4%.

Residue 42.1%.

example 7

100 g of cellulose are heated under the exclusion of air for 3 hours at 250 ° C. This gives 5 g of oil and 50 g residue containing carbon.

Residue containing: C 80.5%; H 2.4%; Combustion heat 29726 kJ / kg.

example 8

100 g starch are mixed with 5 g Al₂O₃ heated with exclusion of air for 3 hours at 210 ° C. Yield 52 g residue containing carbon and 4 g of oil.

Residue containing: C 78.8%; H 3.2%; Combustion heat 29308 kJ / kg.

example 9

100 g of finely ground, dried domestic waste are mixed with 1 g Al₂O₃ and 0.1 g CuO mixed and heated under the exclusion of air at 360 ° C for 4 hours. There are obtained 20 g of oil and 51 g residue containing carbon.

Oil: C 71.2%; H 11.3%; N 1.0%; S 0.3%.

Residue containing: C 43.4%; H 3.75%, N 1.5%; S 0.7%;

Residue 37.0%.