AU613784B2 - Transformation of organic/inorganic waste material into useful products - Google Patents

Description

6i3784 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION NAME ADDRESS OF APPLICANT: Hans Weber-Anneler Vorstadt 6 Brugg CH-5200 Switzerland NAME(S) OF INVENTOR(S): Hans WEBER-ANNELER ADDRESS FOR SERVICE: DAVIES COLLISON Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: "Transformation of organic/inorganic waste material into useful products".

The following statement is a full description of performing it known to me/us:of this invention, including the best method A$ 12- la The present invention is directed to a process for the production of useful components, elements or compounds from mixtures or organic/inorganic waste materials and may be used for reduction of huge amounts of waste by chemical transformation of waste, as well as for the diminution or the avoidance of wastes by production processes and consumption processes.

It is an object of the inventive process to use the waste materials as raw materials for the production of useful components, elements or compounds. When there is objects are reached: The production needs less of raw materials and thus becomes more economical, and, more importantly, the undesired detrimental compounds have disappeared. The use of the undesired compounds Go according to the inventive process is attractive for the economy and it serves to relieve both ecology and economy.

This object of the inventive process is reached by ensuring that all cycles of compounds and energy are regarded and are closed completely, comparable with an electric circuit in which never waste electricity may S. 25 arise. Thereby two elements will have to be considered: the couple production and the use of reaction partners which are present anyhow in the process as products.

This become possible in the so-called hydrokrit process.

Hydrokrit means "separation of water" or more 30 precise separation of chemical bondings with the aid of water. As in the wash cycle the water separates the dirt from the tissue (physical wash cycle), in the hydrokrit process the undesired chemical bondings are cleaved (chemical wash cycle), preferably all those of the undesired compounds of the waste materials. The separation (cleaving) with 910220,dbdatO53,db39782.spec,1 L -2water is practically complete at temperatures of about 1000'C when the contact time between the overheated water vapor and the molecules to be cleaved is sufficiently long. It is to be noted that all organic gaseous molecules which contain besides carbon, hydrogen and oxygen also chlorine, fluorine, nitrogen or sulphur, are always cleaved in the same small fragments. Here this is a mixture of carbon monoxide, hydrogen withX-OM tloe bit of.

nitrogen, as well as the simple compounds of chlorine, fluorine, sulphur or phosphorus with hydrogen.

The mixture of carbon monoxide and hydrogen, occasionally mixed with a little bit of nitrogen, is denoted as synthesis gas or water gas and is used as feed gas in the production of pure hydrocarbons or alcohols in a chemical synthesis. The undesired compounds, such as hydrogen chloride, hydrogen fluoride, hydrogen sulphide and phosphorous hydride, are separated before the synthesis in a gas washer with the help of Redox processes.

Whereas the cleaving of the undesired molecules at a temperature of ca. 1000'C needs heat of the corresponding temperature, in the subsequent synthesis of the cleaving gas for the preparation of liquid combustable materials or raw materials in about the same heat is set free at a temperature of ca. 200'C. This heat is used for the preheating of the feed water for the water vapor generator, whereas the sensible heat of the produced hot cleaving gases is used to distill the wash water and to transform the undesired compounds, such as sulphur and occasionally present volatile heavy metals or their salts, into a concentrated nontoxic and difficultly soluble form. About half of the energy contained in the used materials is used up for the entire process. The other half remains stored in the form of obtained pure organic raw materials or energy carriers.

0 0 00 0 o o 0 0 00 0 o e 0000 0 0« 00 0 0 0 0 o 0 a0 O 0 *0 0 0 *o 0 00* 00 o o -3- Beside these liquid organic products, the hydrokrit process produces also solid or dissolved compounds as products or intermediate products for the further processing.

Shortly summarized the hydrokrit process consists of -the following 4 partial processes: 1. Cleaving of the materials to be processed with water vapor and carbon dioxide in the flame of a combustible gas at a temperature between 350 and 1050 0

C.

2. Cleaving of all produced gases at a temperature between 950 and 1050°C during a time of direct contact of at least one second into low-molecular compounds and/or elements.

15 3. Washing of the cleaving gas by feeding the hot gases into water and separating the synthesis gas (mixture of CO and H 2 from the other low-molecular compounds or elements contained in the water. Recovering of the wash water by evaporation and sedimentation of the difficultly soluble parts in the produced salt water.

4. Synthesis of liquid organic compounds from the cleaving gas and admixing of the gaseous hydrocarbons, obtained during the synthesis, and carbon dioxide to the combustible gas.

In the hydrokrit process are obtained the inorganic product mixtures, produced in the first step, the concentrated wash water, produced in the third step, and the hydrocarbons and/or alcohols produced in the fourth step. There remain no undesired residues, detectable with today's detection methods.

Thus, according to the present invention there is provided a process for the production of useful components, elements or compounds from mixtures of organic/inorganic waste materials, characterized in that in a first step said mixture of organic/inorganic waste material is heated to a temperature between I 350°C and 1050°C and is reacted with a mixture, r3 910220,dbdat053,db39782.spec,3 ^y L i; S *5 8S

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*6 3a containing water vapor, and at least one combustible gas, oxygen and carbon dioxide until the organic portion in the mixture of organic/inorganic waste material is degraded to a value below 100 ppm, corresponding to 100 gram or organic portion per 1000 kg of mixture of waste material, whereby a solid inorganic product mixture as well as a gas mixture are produced; in a second step said produced gas mixture is cleaved at a temperature between 950'C and 1050°C into low-molecular compounds and/or elements; in a third step the obtained low-molecular compounds and/or elements are introduced into water at a temperature from 2000 to 800'C in order to separate 15 the produced mixture of carbon monoxide and hydrogen, abbreviated as synthesis gas, and in order to retain the remaining low-molecular compounds and/or elements in the water, abbreviated as wash water; in a fourth step the synthesis gas, mixed with water vapor, is transformed catalytically according to common processes into liquid hydrocarbons and/or alcohols, whereby the gaseous hydrocarbons and carbon dioxide, obtained as by-products, are added 25 to the combustible gas required in the first step; and obtaining the solid inorganic product mixture, produced in the first step, the wash water, produced in the third step, and the hydrocarbons and/or alcohols, produced in the fourth step.

The waste materials may either be homogeneous or heterogeneous, they may also be either of organic or inorganic origin and they may be present in any of the three states of aggregation (solid, liquid or gaseous).

For example such materials may be wastes from households, sewage sludges, residues of the waste combustion, such as slag or filter dusts, rubble, wastes from agriculture, industry or hospitals or wastes of foodstuffs. A further category of such materials is mineral containing sands, 910220,dbdat053,db3782spec,4 -4salts, oil or carbon containing rocks. Usually mixtures of such material are used.

The mixture of material is composed in such a way that under the conditions, chosen In any single case a chemical transformation affords the desired solid product in the converter, and that the separation into synthesis gas, difficultly soluble residues and salt water in the gas washer occurs simultaneously.

Besides water vapor the converter is fed with at least one combustible gas, oxygen as well as carbon dioxide during such a long time until the desired transformation in the used material is obtained. The gases to be fed are replaced whenever possible by gases which are obtained in the other steps of the running process or by an additional process simultaneously run.

In the first step, the reaction time is preferably between 0.5 and 3 seconds for liquid iixtures of o materials and preferably between 20 minutes and 2 hours for solid mixtures of materials.

The inventive process shall be explained in more detail with the help of the flow sheet (figure The desired mixture of materials is taken from the three material silos 2 or the sludge silo 3 with the help of S-conveyor screws 1 and fed into the converter 4. To this q 25 is Ld through the supply line 5 a mixture of carbon "dioxide with about 10 vol.-% oxygen and through the controlling valve 6 the needed combustible gas mixture.

With the steam generator 7 is fed additional water vapor into the converter 4. The gas mixture produced in the converter 4 is released from particles in the cyclone 8, some particles are recycled into the material flow. The gas mixture, released from particles, is fed through the supply line 9 and the inlet ring 10 into the gas washer 11. The washed gas mixture passes the condenser 12, wherein the water vapor is cn-idensed and is separated in the feed water tank 13. The pump 14 presses a small amount of feed water through the sprinkler 15 into the S gas washer for cooling and to improve the wash effect.

7 91022,dbdatO53,db3978sec ,4 The main part of the feed water is used for cooling the wave reactor 16 and thus is fed prewarmed into the steam generator 7. The gas compressor 17 compresses the washed synthesis gas to a pressure between 5 and 20 bar and feeds it into the wave reactor 16. Herein takes place the exothermic synthesis reaction which produces water vapor, carbon dioxide, gaseous hydrocarbons, containing among others propane or butane. In zhe first instance, gaseous mixture is fed into the distillation container 18, and thereby is condensed by means of cooling the water and the propane or butane. The water is fed into the electrolysis cells 19 and finally into the feed water container 13 and the propane or butane is stored in the S 15tank 20. The gaseous products are fed through the line S 15 21, together with the electrolysis hydrogen, into the steam generator 7 and the converter 4. The steam generator 7 is controlled by regulation of the gas oxygen fed by means of the controlling valves 22 and 23 in such a way that the vapor pressure is in the desired interval between 8 and 10 bar and that in its outlet for exhaust gas remains a sufficient amount of excess oxygen for the maintenance of the temperature in the converter 4.

The drainage water of the distillation container 18 is fed through the electrolysis cells 19 into the feed 25 water tank 13. The cooling of the cooler 12, the distillation container 18 and the converter 4 is realized by means of a separate cooling water circuit with a cooling water inlet KE and outlet KA which trans- 910220,dbdaL53,db3978 I -6 ports forward the heat with an external water-water or water-air heat exchanger to a user.

The solid product produced in the converter 4 is stored according to its quality, through the conveyor screws in one of the three different product silos 26 until distribution. The produced salt water is stored in the tank 27 until its further processing. The difficult.

-ay. soluble sludges collected in the washer are separated in the sludge tank 28 from the salt water and are recycled with or without a further treatment into the sludge silo 3 The following examples of operation shall illustrate the inventive process.

Example 1: In the filter dust process a mixture of 65% by weight of sewage sludge having a dry content of 40% by weight and by weight of filter dust from wet cleaning plants of the waste combustion is fed into the converter and is exposed at a temperature from 850-1000°C for a duration of a half an hour to a srrean of 30 vol.-% of steam, vol.-% of methane, 10 vol.-% of hydrogen, 45 vol.-% of deo de, carbon di~cad" (and 5 vol.-% of oxygen. The electrolysis cells afford 160 standard m of hydrogen and 80 standard 3 m of oxygen per 1000 kg of used mixture of materials at an electricity consumption of 720 kilowatt/hours. The 3 steam generator affords 480 standard m of saturated steam of 10 bar at a gas consumption corresponding to ca. standard m 3 of synthesis gas or hydrogen. Overall there where obtained 460 standard m 3 of synthesis gas, and therefrom 80 kg of butane. In the filter dust process 650 kg of sewage sludge have been gasefied and 350 kg of filter dust have been decontaminated, together with an electricity consumption of 720 kilowatt/hours at a yield -v of 80 kg of butane (960 kilowatt/hours of stored energy).

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^J -L 7 Example 2 For the gasefication of oils, especially halogenated hydrocarbons (figure the converter 24 is constructed as a gas burner and is operated with synthesis gas from the washer 29 which is branched off in front of the cooler 30 Through a compressor 31 air is fed into the converter,/same air is prewarmed to ca. 400°C by the hot synthesis supply line 32 which concentrically surrounds the air inlet. From the oil tank 33 with stirrer 34 oil is fed into the burner through the valve 35 ,4 same oil evaporates in the prewarmed air stream and the resulting vapor is sucked in by the gas flame. Because the synthesis gas from the washer 29 contains about the same volume portion of water vapor, this mixture is well prewarmed in the heat exchanger 36 by means of the cracked gas in the outlet of the converter 24 there results an effective evaporization of the oil. The synthesis gas may directly be used for heating or for motor fuel or it may be fed into a unit power station. In the case of chlorinated or fluorinated oils chalk, soda or metal hydroxide must be added to the feed water in the feed water tank 37 for the neutralization of the hydrochloric acid to be formed. Depending on the quality of the used oils and the controlling of the process the hydrochloric acid to be produced may also be obtained directly in the salt water tank 38 In the case of a chlorinated oil having a chlorine content of ca. 30% by weight are obtained per megawatt hour of 3 F heating value ca. 300 standard m of synthesis gas at a requirement of about 170 standard m 3 of air. The synthesis gas mixed with nitrogen has a portion of about 70 vol.-% and a heating value of about 2 kilowatt/hours per standard m The residual sludges obtained by the processing of oils either in the tank 33 or in the sludge tank 39 may be processed in analogy to the sewage sludges.

8 During the production of coffee or spice extracts residues will be obtained which might not be used completely as feed or furtilizer. These materials may be transformed with the inventive process into synthesis gas or methane or butane.

The hydrokrit process distinguishes from conventional production or regeneration processes in that a radical degradation of undesired compounds or components takes place through the thermo chemical reaction with water vapor or equivalent reagents. Whereas in most production processes either selective synthesis steps are coupled without or with just unimportant degradation reactions, in the hydrokrit process the degradation is radical. The undesired bondings are completely degraded in the first two process steps to single elements or compounds containing two different elements at most. Therefore, in production processes without a sufficient degradation many undesired components are obtained as waste, or during the regeneration of waste only a partial regeneration may be obtained with reasonable costs. Dumps or the high temperature combustion, both of which are Loday connected with high costs, are the only alternatives forx the undesired products. Contrary to this the hydrokrit process makes possible the reorganisation or the avoidance of dumps and high temperature combustion by the complete utilization of the used materials and energies.

The hydrokrit process has some similarities with the pyrolysis process which presently has been developed for the utilization of plastic wastes. Istead of air or water vapor only combustion air e-MAi(oxygen is fed. As in the ypd tolir s also here a gas mixture is formed which may be processed to chemical raw materials. But in the pyrolysis a very broad spectrum of products is formed, and the solid residues are no more usable. In addition a big amount of heavy metals containing carbon black is formed which will have to be stored in dumps.

i l 1 -^Jr ii 9- The prior art is contained in the following publications: Hans Grfitter A.M. Egger Kldrschl ammentsorgung SIA-Zeitung, January 14, 38-41 (1988) Die Integrierung der Sondermtillverbrennung in das Entsorgungskonzept eines Chemiewerkes SIA-Zeitung, January 14, 41-45 (1988) B. Milani Dr. A. Sticheli Abfallwirtschaft zwischen Ideologie und Wissen, SIA-Zeitung, January 28, 105-107 (1988) Abgasreinigung bei Kehrrichtverbrennungs ani agen, SIA-Zeitung, January 28, 116-124 (1988) Kunststoffpyrolyse: Rohstoffquelle ftir die Chemie, Techn.

Rundsch. 23/88, 78-81.

G. Hilscher

I

Claims (17)

1. A process for the production of useful components, elements or compounds from mixtures of organic/inorganic waste materials, characterized in that in a first step said mixture of organic/inorganic wast material is heated to a temperature between 350°C and 1050°C and is reacted with a mixture, containing water vapor, and at least one combustible gas, oxygen and carbon dioxide until the organic portion in the mixture of organic/inorganic waste material is degraded to a value below 100 ppm, corresponding to 100 gram or organic portion per 1000 kg of mixture of waste material, whereby a solid inorganic product mixture as well as a gas mixture are produced; in a second step said produced gas mixture is cleaved at a temperature between 950 0 °C and 1050°C into low-molecular compounds and/or elements; in a third step the obtained low-molecular compounds and/or elements are introduced into water at a temperature from 2000 to 800 0 C in order to separate the produced mixture of carbon monoxide and hydrogen, abbreviated as synthesis gas, and in order to retain the remaining low-molecular compounds and/or elements in the water, abbreviated as wash water; in a fourth step the synthesis gas, mixed with water vapor, is transformed catalytically according to common processes into liquid hydrocarbons and/or alcohols, whereby the gaseous hydrocarbons and carbon dioxide, obtained as by-products, are added to the combustible gas required in the first step; 0 ^7 910220,dbdat.053,db39782.spec,10 4 0 I~J -11 and obtaining the solid inorganic product mixti j produced in the first step, the wash water, pr in the third step, and the hydrocarbons and/or I alcohols, produced in the fourth step. 1 2. A process according to claim 1, characterized I that the mixture of waste materials contains at lea; starting material selected from the group consistin earth, coal, slag, dust, sludge, foodstuff, chemica organs, rubber and plastic material. ure, oduced in st one g of Ls,

3. A process according to claim 2, characterized in that said mixture of waste materials contains two starting materials.

4. A process according to claim 2 or claim 3, characterized in that the earth is earth contaminated with solvents, oil, tar or heavy metals, components of earth contaminated with organic and inorganic materials or sand contaminated with heavy metals and/or precious metals. A process according to claim 4, characterized in that the components of earth contaminated with organic and inorganic materials is rubble.

6. A process according to any one of claims 2 to characterized in that the coal is coal containing sulphur and lignin, or activated charcoal contaminated with vapors of solvents.

7. A process according to any one of claims 2 to 6, characterized in that the slag is slag of industrial firing equipments, blast furnaces, thermic power stations or waste combustion plants.

8. A process according to any one of claims 2 to 7, characterized in that the dust is filter dust of electric 910220,dbdat053,db39782.spec.l -12- separators, or dry residues of the wet, semiwet or dry cleaning of flue gas of waste combustion plants or industrial firing equipments.

9. A process according to any one of claims 2 to 8, characterized in that the sludge is sewage sludge produced in excess during the purification of sewage, sewage sludge contaminated with heavy metals, sludge from galvanization, sludge from the production of ammunition or explosives, residues from the distillation of solvents, or residues from the production of dyestuffs or lacquers. A process according to any one of claims 2 to 9, o 15 characterized in that the foodstuff is residues, excess or by-products of production or consumption of foodstuffs, coffee-grounds, or waste from slaughter- houses.

11. A process according to any one of claims 2 to characterized in that the chemicals are by-products of :chemical or bio-chemical analysis or processes, :0 filtration residues, tainted non-liquid chemicals, or slightly radioactive wastes from laboratories.

12. A process according to any one of claims 2 to 11, characterized in that the organs are carcasses, tissue and blood materials from surgery or other solid residues from hospitals, or tainted medicines.

13. A process according to any one of claims 2 to 12, characterized in that the rubber and plastic material is residues of production and consumption, tyres, elastomers mixed or combined with metallic or other inorganic materials, thermoplastics, or thermosetting plastics.

14. A process according to any one of the preceding claims, characterized in that the mixture of waste 0 910220,dbdat053,db39782.spec,12 -13- materials is selected from a mixture of filter dust and sewage sludge, a mixture of filter dust and coal, and a mixture of sand, sewage sludge and coal.

15. A process according to any one of the preceding claims, characterized in that the mixture of waste materials contains at least one starting material selected from the group consisting of oils and paraffins, alcohols and ketones, halogenated hydrocarbons and inorganic liquids.

16. A process according to claim 15, characterized in that said mixture of waste materials contains two Sstarting materials.

17. A process according to claims 15 or claim 16, characterized in that the oils and paraffins are heavy oils or paraffins, or heavy oils or paraffins from crude oil refinement or waste oil regeneration.

18. A process according to any one of claims 15 to 17, characterized in that the alcohols and ketones are methanol, ethanol, industrial alcohols or ketones, or acetone.

19. A process according to any one of claims 15 to 18, characterized in that the halogenated hydrocarbons are trichloroethane, trichloroethylene, chloroform, chlorinated aromatic compounds, chloro benzenes, polychloro-biphenyls, -furans, -dioxins, freon or freon

113. A process according to any one of claims 15 to 19, characterized in that the inorganic liquids are mineral acids and bases with or without heavy metals, hydrochloric acid, dissolved iron chloride, chromium containing sulphuric acid, dissolved cyanides, nitrites, ni nitrates, or phosphates. O3 910220,dbdat.053,db39782.spec13 (A V I 14- 0 a 0 '0* 0 0 00 0 *00 0 0 0 S 0500 S 0 0 0 00 0 000* 0* 0 21. A process according to any one of the preceding claims, characterized in that the mixture of waste materials is selected from a mixture of waste oil and chlorinated hydrocarbons, and a mixture of sand, sewage sludges and halogenated hydrocarbons. 22. A process according to any one of the preceding claims characterized in that the gas mixture, as mentioned in the first step, contains 10-40 vol.-% of water vapor, 10-40 vol.-% combustible gas, 5-20 vol.-% of 10 oxygen and 30-70 vol.-% of carbon dioxide. 23. A process according to claim 22 characterized in that the combustible gas is methane. 24. A process according to any one of the preceding claims, characterized in that in the first step the 15 reaction time is between 0.5 and 3 seconds for liquid mixtures of materials, and between 20 minutes and 2 hours for solid mixtures of materials. A process according to any one of the preceding claims, characterized in that to the gas mixture, as mentioned in the first step, are admixed noxious gases, burnt gas from firings, waste gas from internal combustion engines or exhaust air from ventilation shafts. 26. A process according to any one of the preceding claims, characterized in that the reaction, as mentioned in the first step, is carried out in the case of liquid mixtures of materials in a gas burner which is run by the mixture of synthesis gas and water vapor obtained in the third step. 27. A process according to any one of the preceding claims, characterized in that the second step is carried out in a secondary combustion chamber. 910529,dbdatG06Z39782.res,14 I^ 28. A process according to any one of the preceding claims, characterized in that the reaction, as mentioned in the first step, is carried out in a solid matter firing equipment in the case of solid and muddy mixtures of materials, whereby said firing equipment is run by the mixture of synthesis gas and water vapor obtained in the third step. 29. A process according to any one of the preceding claims, characterized in that the oxygen, as needed in the first step, is residual oxygen which is contained in the exhaust air from combustion accessories, combustion engines or in the exhaust air from ventilating systems. 0f 15 30. A process according to any one of the preceding claims, characterized in that the water, as needed in the third step is waste water, percolating water from dumps, infested water, or sea water. 31. A process for the production of useful components, elements or compounds substantially as hereinbefore described with reference to the drawings. I' 0 e c DATED this 20th day of February, Hans Wever-Anneler By Its Patent Attorneys DAVIES COLLISON p 910220,dbdat053,db39782.spec,15 I M