DD283960A5 - METHOD FOR OBTAINING COMPONENTS, ELEMENTS OR COMPOUNDS FROM MATERIAL MIXTURES - Google Patents

Abstract

The invention relates to a method for obtaining components, elements or compounds from material mixtures. It is a thermochemical process which, in addition to the material mixtures used, does not require any additional reagents, but only those which, in the process itself, are produced in sufficient quantity and at the same time can take over the functions of the heat transfer agent and release agent. One such reagent is water vapor. The process according to the invention is carried out in such a way that only those products are obtained which are either the desired end products or can be returned to one of the cycle runs. The inventive method is particularly suitable for the processing of organic materials, coal or oelhaltigen earths, sands or slates in suitable mixtures of high-energy and low-energy material. With the method according to the invention, no waste is produced, but waste is thus processed into useful products. Waste utilization, thermochemical}

Description

For this 2 pages drawings

Field of application of the invention

The present invention relates to a process for recovering components, elements or compounds from mixtures of materials and can be used to reduce waste streams by chemically converting Ab.Wen and to reduce or avoid waste in production and consumption processes.

Characteristic of the known state of the art

Pyrolysis processes for recycling plastic waste are known. However, pyrolysis produces a very broad spectrum of products and the solid residues are not reusable. In addition, a large amount of soot interspersed with soot, woheher must be deposited

 The state of Tecimik has been recorded by the following publications:

HansGrütt & r Sewage Sludge Disposal SIA-Zeitung, 14.Jan.33-41 (1988)

A. M. Egger The integration of special waste incineration into the disposal concept of a chemical plant

SIA Newspaper, 14.Jan.41-45 {1988)

B.Milani Waste Management between Ideology and Knowledge SIA-Zeitung, Jan. 28, 105-107 (1988)

Dr.A.Stücheli Exhaust gas cleaning in waste incineration plants SIA-Zeitung, Jan. 28, 116-124 (1988) G. Hilscher Plastic pyrolysis: raw material source for the chemical industry, Techn. 23 / 88.78 to 81

Object of the invention

The invention provides a process for obtaining components, elements or compounds, wherein undesirable substances are used as raw materials.

The utilization of undesirable substances according to the method according to the invention is economically attractive and relieves both the ecology and the economy.

Λ Presentation of the essence of the invention

The present invention has for its object to provide a method for obtaining components, elements or compounds that uses undesirable pollutants as raw materials available.

According to the invention, this object is achieved in that in the planned process all material and energy cycles are observed and completely closed, similar to a circuit in which the waste electricity can arise. Two elements must be taken into consideration here: the co-production and the use of reaction partners, which in any case occur as products in the process. This is made possible in the so-called hydrocritical process.

Hydrocritic means "separation of water" or, more precisely, separation of chemical bonds with the aid of water. Just as the water separates the dirt from the fabric during the washing process (physical washing process), the undesirable chemical bonds, especially those of the unwanted constituents, are used in the hydrocrystallization process Materials separated (chemical washing process) The separation with water (cleavage) is practically complete at temperatures around 10GO ⁰ C, if the contact time between the superheated steam and the molecules to be cleaved enough long.

It is noteworthy that all organic gaseous molecules, which in addition to carbon, hydrogen and oxygen still contain chlorine, fluorine, nitrogen or sulfur, are always converted into the same, small cleavage products. This is a mixture of carbon monoxide, hydrogen with little nitrogen and the simple compounds of chlorine, fluorine, sulfur or phosphorus with hydrogen.

The mixture of carbon monoxide and hydrogen, optionally mixed with a small amount of nitrogen, is called synthesis gas or water gas and serves as a feed gas in the production of pure hydrocarbon or alcohols in a chemical synthesis.

The undesirable substances such as chlorine, fluorine, sulfur and hydrogen phosphide are separated before the synthesis in a gas scrubber by means of redox processes.

While the cleavage of the unwanted molecules at a temperature of about 1000 ⁰ C requires heat of the corresponding temperature, in the subsequent synthesis of the cracking gas for the production of liquid fuels or raw materials about the same heat at a temperature of about 200 ° C again. It is used to preheat the feed water to the steam generator while using the sensible heat of the generated hot cracking gases to distill the wash water and the undesirable substances such as sulfur and any volatile heavy metals or salts thereof into a concentrated, non-toxic and sparingly soluble form to convict. Overall, about half of the energy contained in the materials used for the process is consumed. The other half remains stored in the form of recovered, pure organic raw materials or energy sources.

In addition to these volatile organic products, the hydrocritical process provides solids or solutes as products or intermediates for further processing.

In summary, the hydrocritical process consists of the following four toileting processes:

1. The said material mixture is called Ruf a temperature between 35O ⁰ C and 1050 ⁰ C heated and reacted with a mixture containing water vapor, at least one combustible gas, oxygen and carbon dioxide, until the organic content in the material mixture used a value of below 100 ppm, corresponding to 100 g of organic content per ton of material mixture, is degraded, resulting in a solid inorganic product mixture and a gas mixture.

2. The resulting gas mixture is split at a temperature between 950 and 1050 ⁰ C for at least one second in low molecular weight compounds and / or elements.

3. The resulting low molecular weight compounds and / or elements are introduced at a temperature of 200 to 800 ⁰ C in water, on the one hand, the resulting mixture of carbon monoxide and hydrogen, called synthesis gas briefly separate and on the other hand, the remaining low molecular weight compounds and / or the elements in the water, briefly referred to as wash water, retain, recovery of the wash water by evaporation and sedimentation of the brine.

4. The synthesis gas mixed with water vapor is catalytically converted into liquid hydrocarbons and / or alcohols by conventional methods and ciie thereby added as by-products gaseous hydrocarbons and carbon dioxide added to the combustible gas required in the first step.

In the hydrocrystallization process, the inorganic product mixtures formed in the first step, the concentrated washings obtained in the third step and the hydrocarbons and / or alcohols obtained in the fourth step are recovered. There are no undesirable residues detectable with today's detection methods.

The materials used may be homogeneous or heterogeneous as well as organic or inorganic in nature and in any of the three states of matter (solid, liquid or gaseous). Such materials may for example consist of:

Earth: earth contaminated with solvents, oil, tar or heavy metals, or 'organise', and

Inorganically contaminated earth components, such as rubble, or sand contaminated with heavy metals and / or precious metals,

Coal: in particular coal containing high sulfur and hyin content or activated carbon loaded with solvent vapors

Slag: in particular slag from industrial furnaces, blast furnaces, thermal power plants or

Waste incineration plants, dust: in particular filter dust from electrostatic precipitators or dry residues of wet, semi-wet or dry

Flue gas cleaning in waste incineration plants or industrial furnaces, sludges: especially in wastewater treatment in excess accumulating or with heavy metals

contaminated sewage sludge, galvanic sludge, sludge from the Mur itions- and Explosengabrikation

and residues of solvent distillation and dye and varnish production, foodstuffs: in particular residues, surpluses or by-products of food production or of food

Food consumption, in particular coffee grounds, waste from slaughterhouses, chemicals: in particular by-products in chemical or biochemical analyzes or processes, in particular

Filter residues, spoiled non-liquid chemicals or low-level radioactive waste from laboratories, organs: in particular carcasses, surgical tissue and blood materials and other solid residues

Hospitals, in particular spoiled drugs, rubber and in particular residues of production and

of consumption, eg. B. Pneu, with metallic or anderon plastics: inorganic materials bonded or blended elastomers, thermoplastics and thermosets.

Normally mixtures of such materials are used. The material mixture is composed so that among those chosen in each individual case. Conditions leads to a chemical reaction in the desired solid product in the converter and at the same time the separation into synthesis gas, poorly soluble residues and sols in the gas scrubber takes place.

Selected material mixtures can consist of:

a filter dust slurry, a filter rod-coal mixture and a sand-sludge-coal mixture or a spent oil-chlorinated hydrocarbon mixture and a sand-sludge-halogenated hydrocarbon mixture

said material mixture contains at least one, in particular two, starting materials selected from the group consisting of:

Oils and paraffins: such as heavy oil or paraffins, in particular from petroleum refining or waste oil treatment, alcohols and ketones: such as methanol, ethanol or industrial alcohols, or ketones, in particular acetone, halogenated hydrocarbons: such as trichloroethane, trichlorethylene, chloroform and chlorinated aromatic compounds, especially chlorobenzenes or polychlorinated biphenyls, furans or dioxins, or a freon, in particular Froon 113, inorganic liquids: such as mineral acids and bases with or without heavy metals, in particular hydrochloric acid, dissolved iron chloride, chromium-containing sulfuric acid, as well as dissolved cyanides, nitrites, nitrates and phosphates.

In addition to water vapor to the converter at least a combustible gas, oxygen and carbon dioxide is supplied until the desired conversion is achieved in the material used. The gases to be supplied are replaced as far as possible by gases which are produced in the other stages of the ongoing process or a simultaneous additional process.

The gas mixture mentioned in the first step contains 10 to 40% by volume of water vapor, 10 to 40% by volume of combustible gas, in particular methane, 5 to 20% by volume of oxygen and 30 to 70% by volume of carbon dioxide.

For liquid material mixtures, the reaction time in the first step is between 0.5 and 3 seconds and for solid material mixtures between 10 minutes and two hours.

The gas mixture mentioned in the first step, harmful gases, such as flue gases from furnaces, exhaust gases from internal combustion engines or exhaust air from ventilation ducts, be mixed.

The reaction mentioned in the first step is carried out with liquid material mixtures in a gas burner, which is operated with the synthesis gas / steam mixture obtained in the third step.

The second step of the method according to the invention is carried out in a secondary combustion chamber.

The reaction mentioned in the first step is carried out with solid and muddy material mixtures in a solidification system which is operated with the synthesis gas / steam mixture obtained in the third step.

The oxygen required in the first step is residual oxygen, which is contained in the exhaust air from fires, internal combustion engines or in the exhaust air from ventilation systems.

The water needed in the third step is sewage, landfill leachate, contaminated water or seawater.

The method according to the invention will be explained in more detail with the aid of the block diagram (FIG. 1).

The desired material mixture is removed by means of screw conveyors 1 the three material silos 2 or the sludge silo 3 and fed to the converter 4. This is fed via the supply line 5 a mixture of carbon dioxide with about 10 vol .-% SauerstoN and via the control valve 6, the required combustible gas mixture. With the steam generator 7 4 additional steam is supplied to the converter. The gas mixture formed in the converter 4 is freed of particles in the cyclone 8, which are recycled to the material flow. The liberated from particles gas mixture is supplied via the line 9 and the inflow ring 10 to the scrubber 11. The leached gas mixture passes through the cooler 12, which brings the water vapor condensation and deposits in the feedwater tank 13. The pump 14 presses a little feed water through the shower head 15 in the gas scrubber for cooling and improving the leaching effect. The main part of the feedwater is used to cool the wave reactor 16 and thereby preheated fed to the steam generator 7. The gas compressor 17 compresses the washed synthesis gas to a pressure between 5 and 20 bar and supplies it to the wave reactor 16. Here, the exothermic synthesis reaction takes place, which produces water vapor, carbon dioxide, gaseous hydrocarbons, among other propane or butane. The initially gaseous mixture is supplied to the distillation vessel 18, and thereby the water and the propane or butane is condensed by means of cooling. The water is supplied to the electrolysis cells 19 and finally to the feedwater tank 13, which stores propane or butane in the tank 20. The gaseous products are fed via the line 21 together with the electrolysis hydrogen to the steam generator 7 and the converter 4. The Damper generator 7 is regulated by gas and oxygen supply

controlled via the valves 22 and 23 so that the vapor pressure is in the desired interval between 8 and 10 bar and in its output for delivery sufficient excess oxygen for maintaining the temperature in the converter 41st Oibi. The dewatering water of the distillation vessel 18 is passed through the electrolysis cells 19 in the feedwater tank 13. The cooling of the cooler 12, the distillation vessel 18 and the converter 4 via a separate cooling water circuit with cooling water inlet (KE) and outlet (KA), which passes the heat with an external water-water or water-air heat exchanger to a consumer.

The solid product produced in the converter 4 is stored depending on the quality of the screw conveyors 25 in one of the three different product silos 26 until distribution. The generated brine is stored in the tank 27 until further processing. The resulting in the scrubber sparingly soluble sludge are separated in the sludge tank 28 from the brine and returned with or without Zwischenverai boitung in the mud silo 3.

embodiments

The following exemplary embodiments illustrate the process according to the invention.

Example 1:

In the filter dust method, a mixture of 65Gew .-% sewage sludge with 40Gew .-% dry content and 35Gew .-% filter dust from wet cleaning the waste incineration fed to the converter and at a temperature of 850 to 1000 ⁰ C with a residence time of half an hour a stream of 30Vol % Of steam, 10% by volume of methane, 10% by volume of hydrogen, 45% by volume of carbon dioxide and 5% by volume of oxygen. The Eloktrolysezellan deliver 160 standard cubic meters of hydrogen and 80 standard cubic meters of oxygen per ton of mixed material with an electricity consumption of 720 kilowatt hours. The steam generator delivers 480 standard cubic meters of saturated steam of 10 bar with a gas consumption, which corresponds to about 30 standard cubic meters of synthesis gas or hydrogen. A total of 460 standard cubic motor synthesis gas and from it 80 kilograms of butane are obtained. A total of 650 kilograms of sewage sludge were gasified in the filter dust process and 350 kilograms of filter dust were detoxified with an electricity input of 720 kilowatt hours with a butane yield of 80 kg (960 kilowatt hours of stored energy).

Example 2:

For the gasification of oils, in particular halogenated hydrocarbons (Figure 2), the converter 24 is formed as a gas burner and with synthesis gas a.js the scrubber 29, which abgr is before the cooler 30, operated. Via a compressor 31 air 24 is supplied to the Konveiter which is preheated by the hot synthesis gas line 32, which surrounds the air supply concentrically around 400 ⁰ C. From the Öltank33, with stirrer 34 is supplied to the burner via the valve 35, which is evaporated in the preheated air stream and its vapor is sucked by the gas flame. Because the synthesis gas from the scrubber 29 contains approximately the same volume of water vapor, which mixture is strongly preheated in the heat exchanger 36 by the cracked gas in the outlet of the converter 24, an efficient gasification of the oil results. The synthesis gas can be used directly for heating or motor purposes or fed to a combined heat and power plant. For chlorinated or fluorinated oils 37 lime, soda or metal hydroxide must be supplied to the feed water in the feedwater tank to neutralize the resulting hydrochloric acid. Depending on the quality of the oils used and the process, the resulting hydrochloric acid can also be obtained directly from brine tank 38. In the case of a chlorinated oil with a chlorine content of around 30% by weight, around 300 standard cubic meters of synthesis gas are recovered per megawatt hour of calorific value, with about 170 standard cubic meters of air required. The synthesis gas mixed with nitrogen has a proportion of about 70% by volume and a calorific value of about 2 kilowatt hours per no. r.ikubikmeter. The remaining in the processing of oils in the oil tank 33 or in the sludge tank 39 sludge can be processed analogously as sewage sludge.

The production of coffee and spice extracts produces residues that can not be fully reused as feed or fertilizer. These materials can be converted to synthesis gas, or methane or butane using the process of the invention.

The hydrotrope process differs from conventional production or regeneration processes in that there is a radical degradation of undesired compounds or components by the thermochemical reaction with steam or equivalent reagents While in most production processes either selective synthetic steps are coupled with no or only minor degradation reactions The unwanted bonds are radically decomposed in the first two process steps down to individual elements or compounds of at most two different elements.Therefore, in production processes without sufficient degradation, many unwanted components are produced as waste or can be used in the treatment of waste only a partial regeneration can be achieved with reasonable costs, leaving only the landfill or the high tempee associated with high costs combustion as alternatives. In contrast, the hydrocritical process allows the remediation or avoidance of landfills and high-temperature combustion by the full utilization of the materials and energies used.

The Hydrokritverfahren has some similarities with the pyrolysis, which are currently developed for the recovery of plastic waste. Instead of air or water vapor only oxygen-free combustion air is supplied. As in the case of hydrolysis, a gas mixture is formed here, which can be further processed into chemical raw materials. However, pyrolysis produces a very broad spectrum of products and the solid residues are not reusable. In addition, a large amount of soot metal interspersed soot, which must be landfilled.

Claims (13)

1. A process for the production of components, elements or compounds from material mixtures, characterized in that in a first step, said material mixture is heated to a temperature between 35O ⁰ C and 1050 ⁰ C and with a mixture containing water vapor, at least one combustible gas , Oxygen and carbon dioxide, until the organic fraction in the material mixture used to a value of below 100 ppm, corresponding to 100 grams of organic content per ton of material mixture, decomposed, wherein a solid inorganic product mixture and a gas mixture formed in a second step, said gas mixture formed at a temperature between 950 and 1050 ⁰ C for at least one second in low molecular weight compounds and / or elements splits, in a third step, the resulting low molecular weight compounds and / or elements at a temperature of 200 to 800 ⁰ C. into water t, on the one hand to separate the resulting mixture of Kchlenstoffmonoxid and hydrogen, called syngas short, and on the other hand, the remaining low molecular weight compounds and / or elements in the water, briefly referred to as Waschwcssar retain, in a fourth step, the mixed with steam syngas according to customary ancestors catalytically converts to liquid hydrocarbons and / or alcohols and the resulting as by-products gaseous hydrocarbons and carbon dioxide inflicts the required in the first step combustible gas, and the resulting in the first step solid inorganic product mixture, the wash water obtained in the third step and the resulting in the fourth step Hydrocarbons and / or alcohols win. 2. The method according to claim 1, characterized in that the said material M'oonung at least one, in particular contains two starting materials selected from the group consisting of: Soil: soil contaminated with solvents, oil, tar or heavy metals in particular, or organically and inorganically contaminated earth constituents, such as building rubble, or sand contaminated with heavy metals and / or precious metals, coal: in particular highly sulfur and lignin-containing coal or activated carbon laden with solvent vapors, Slag: in particular slag from industrial furnaces, blast furnaces, thermal power plants or waste incineration plants, Dust: in particular filter dust from electrostatic precipitators or dry residues from wet, semi-wet or dry flue gas cleaning in waste incineration plants or industrial furnaces, Sludges: in particular sewage sludge accumulating or contaminated with heavy metals, in particular in sewage treatment, galvanic sludges, sludges from munitions and explosives production and residues of solvent distillation and dye and varnish production, Foodstuffs: in particular residues, surpluses or by-products of food production or foodstuffs, in particular coffee grounds, waste from slaughterhouses, Chemicals: in particular by-products in chemical or biochemical analyzes or processes, in particular filter residues, spoiled non-liquid chemicals or low-level radioactive waste from laboratories, Organs: in particular carcasses, tissues and blood materiai from surgery and other solid residues from hospitals, in particular spoiled drugs, rubber and plastics: in particular residues of production and consumption, eg. 3. Pneu, elastomers bonded or blended with metallic or other inorganic materials, thermoplastics and thermosets. 3. The method according to any one of claims 1 to 2, characterized in that the material mixture is selected from a filter dust sewage sludge mixture, a filter dust Kohiemischung and a sand-sewage sludge coal mixture. 4. The method according to any one of claims 1 to 3, characterized in that said material mixture contains at least one, in particular two starting materials selected from the group consisting of: oils and paraffins: such as heavy oil or paraffins, in particular from crude oil refining or waste oil processing, Alcohols and ketones: such as methanol, ethanol or industrial alcohols, or ketones, in particular acetone, Halogenated hydrocarbons: such as trichloroethane, trichlorethylene, chloroform and chlorinated aromatic compounds, in particular chlorobenzenes or polychlorinated biphenyls, furans or dioxins, or a freon, in particular Freon 113, Inorganic liquids: such as mineral acids and bases with or without heavy metals, in particular hydrochloric acid, dissolved iron chloride, chromium-containing sulfuric acid and dissolved cyanides, nitrites, nitrates and phosphates. 5. The method according to any one of claims 1 to 4, characterized in that said material mixture is selected from a waste oil-chlorinated hydrocarbon mixture and a sand-sludge-halogenated hydrocarbon mixture. 6. The method according to any one of claims 1 to 5, characterized in that the gas mixture mentioned in the first step 10-40Vol .-% water vapor, 10-40Vol .-% combustible gas, in particular methane, 5-20 vol .-% oxygen and 30-70Vol .-% contains carbon dioxide. 7. The method according to any one of claims 1 to 6, characterized in that the reaction time in the first step for liquid material mixtures is between 0.5 and 3 seconds and for solid material mixtures between 20 minutes and two hours. 8. The method according to any one of claims 1 to 7, characterized in that the gaseous mixture mentioned in the first step harmful gases, such as flue gases from furnaces, exhaust gases from internal combustion engines or exhaust air from ventilation ducts, are warden. 9. The method according to any one of claims 1 to 8, characterized in that the reaction mentioned in the first step is carried out in liquid material mixtures in a gas burner, which mi t operated with the synthesis gas-Wasserdarnpfgemisch obtained in the third step. 10. The method according to any one of claims 1 to 9, characterized in that the second step is carried out in a Nachbrennkammer. 11. The method according to any one of claims 1 to 10, characterized in that the reaction mentioned in the first'i step is carried out in solid and muddy material mixtures in a Festioffeurung which is operated with the synthesis gas-steam mixture obtained in the third step. 12. The method according to any one of claims 1 to 11, characterized in that the oxygen required in the first step is residual oxygen, which is contained in the exhaust air from furnaces, internal combustion engines or in the exhaust air from ventilation systems. 13. The method according to any one of claims 1 to 12, characterized in that the water required in the third step is wastewater, leachate from landfills, contaminated water or seawater.