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    • 专利摘要:
    The invention relates to a process for obtaining valuable substances from organic compounds contained in waste or chemical elements contained therein. The process comprises the following successive steps: a) mixing the waste (1) with a base so that a liquid medium is formed, b) heating the medium in a reactor (3) to a temperature of 100.degree. C. to 140.degree Hydrolyzing the organic compounds present in the medium and withdrawing (c) the vapor which forms, c) passing (d) the liquid medium remaining in step (b) in the reactor (3) into a separating device (5) for separating any liquid medium present therein solid inorganic phase.
    公开号:AT520454A2
    申请号:T50842/2017
    申请日:2017-10-03
    公开日:2019-04-15
    发明作者:
    申请人:Dr Michael Schelch；Dr Wolfgang Staber；
    IPC主号:
    专利说明:

    Dr. Michael Sheikh and Dr. Wolfgang Staber
    description
    Process for the recovery of valuable materials
    The invention relates to a process for obtaining valuable substances from organic compounds contained in waste or chemical elements contained therein.
    In the context of the subject invention, the term waste in particular includes sewage sludge, liquid manure, cattle manure, slaughterhouse animal meal and biowaste or biomass. Such wastes contain a variety of complex chemical compounds and often have a very high water content. Components of these compounds are, for example, amino groups or phosphate groups, which are interesting molecular constituents for obtaining valuable substances. Due to the high water content of the waste and the complexity of the chemical compounds is an economic utilization of the aforementioned molecular constituents, in particular a recovery of recyclables from these molecular constituents, currently difficult. The problem is exacerbated by any heavy metals and / or heavy metal salts contained in the waste.
    Sewage sludge contains, for example, nitrogen and phosphorus suitable for fertilization, but often has a high content of heavy metals and / or residues of medicines and can therefore not or only partially be used directly as a fertilizer. Currently, the use of sewage sludge as a fertilizer in Europe is subject to a directive which sets limits for heavy metal concentrations. Sometimes the application of sewage sludge as a fertilizer regional even prohibited. A separation of the heavy metals and / or heavy metal salts from sewage sludge is currently not possible with an economically acceptable cost.
    Sewage sludge that can not be used as fertilizer is currently being incinerated or gasified. The high water content of sewage sludge makes this an extremely energy-intensive and mostly uneconomic recovery. The resulting vapor in the evaporation of sewage sludge is also usually expensive to post-treat. In particular, in evaporation, the molecular components incorporated in the complex chemical compounds and useful for recovering valuable material are also lost.
    In addition to sewage sludge, the recovery or treatment of a large number of other wastes, such as in particular the waste already mentioned above, is very problematic. In addition, the wastes are often of pasty or solid consistency, so that they are only partially pumpable and the handling of the waste is also a logistical challenge.
    The invention is therefore based on the object to provide a method which eliminates the mentioned in the utilization of waste existing barriers to use and thus enables economic recovery of recyclables from the waste.
    The object is achieved according to the invention by a method of the type mentioned with the following successive steps: a) mixing the waste with a base so that a liquid medium is formed, b) heating the medium in a reactor to a temperature of 100 ° C. to 140 ° C for hydrolyzing the organic compounds contained in the medium and withdrawal of the forming vapor, c) passing the remaining in step b) in the liquid medium in a separating device for separating any solid contained in the liquid medium solid inorganic phase.
    Through the steps a) and b) of the process according to the invention, the organic compounds of the waste are brought into solution in a liquid medium, so that a very easily transportable medium is obtained. Since the hydrolysis according to step b) in a
    Temperature is carried out from 100 ° to 140 ° C, organic salts are formed from the organic compounds contained in the medium without decomposition and with a high degree of conversion, which dissolve in the liquid medium. At least the majority of any unhydrolyzed organic compounds have a lower density than the other liquid medium so that they float on top of the medium. Recyclables can be recovered from the vapor formed in step b), for example from a nitrogen-containing vapor an ammonia solution. The remaining in step b) medium is still well flowable and therefore has a low viscosity. Any inorganic constituents already sediment in step b) in the reactor, whereby they are separated very effectively in step c). The inorganic fraction obtained by step c) contains insoluble inorganic constituents in the medium, for example heavy metal salts, pebbles or sand. In particular, any heavy metal salts are quantitatively separated from the medium. Recyclable materials, in particular any heavy metals, can be obtained from the inorganic fraction. In contrast to the ashes remaining in a combustion, any heavy metal salts contained in the inorganic fraction are not bound in an inorganic matrix, so that the further treatment of the inorganic fraction is possible in a simpler manner. Due to the early removal of any inorganic constituents, a further treatment, at least largely independent of secondary reactions, of the medium still containing organic compounds is possible in the following. In addition, subsequently from the medium, in particular by further preferred method variants of the invention, ashless combustible organic compounds can be obtained.
    By means of the method according to the invention, it is therefore possible to eliminate the hitherto existing barriers to use, such as heavy metals contained in the waste and the often very large water content of the waste, whereby an economic recovery of a variety of recyclables from chemical compounds contained in waste is possible.
    In particular, step a) is already carried out in the reactor. Particularly preferably, step a) is carried out in a separate mixer, whereby first the
    Medium formed and then introduced into the reactor. This can be transported very well. Furthermore, it is preferred if in step a) the waste and the base are heated to 60 ° C to 70 ° C. As a result, the pumpability of the medium is improved, it being possible for the first, otherwise only in step b), decomposition reactions of the organic compounds to take place in the medium.
    Preferably, in step a) the waste is mixed with an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous potassium carbonate solution, an aqueous sodium carbonate solution or with a mixture of at least two of these solutions. In particular, the waste in question, for example sewage sludge, often itself contains potassium. These bases are known industrial chemicals whose handling is advantageously well-proven and unproblematic.
    Furthermore, it is preferred if in step a) the amount and / or the concentration of the base is or are chosen such that the liquid medium formed has a pH of 9.0 to 14.0, in particular of at least 12.0 , wherein preferably the quantitative ratio of dry matter contained in the waste to the base is 1: 1 to 1: 2. As a result, the organic compounds are hydrolyzed to a particularly large extent. In addition, at this pH, in particular in combination with the heating of the medium taking place in step b) above 100 ° C., all or almost all microorganisms are killed.
    In step b), the liquid medium is preferably heated with stirring to its boiling temperature. The possible risk of bumping is thereby reduced.
    According to a further preferred variant, a sulfide solution, in particular a potassium sulfide or a sodium sulfide solution, is added in step b). Sulfides dissolve in the liquid medium and, together with any heavy metals present in the medium, form sparingly soluble heavy metal sulfides which precipitate in the medium. The precipitated heavy metals are separated in the subsequent step c) and are part of the mentioned solid inorganic phase. The addition of a sulfide solution is particularly advantageous if the waste used has a high heavy metal content and / or is free of sulfur-containing compounds. Since potassium hydroxide solution or sodium hydroxide solution is already preferably used in step a), potassium sulfide or sodium sulfide solution is particularly preferred as the sulfide solution.
    The vapor obtained in step b) is preferably utilized in accordance with the following successive steps: bl) passing the vapor from the first reactor into a first wash column, b2) mixing the vapor with sulfuric acid or phosphoric acid, a solution being obtained in the bottom of the wash column, and b) passing the solution obtained in step b2) into an electrochemical cell having a cathode space and an anode space and electrolyzing the solution, sulfuric acid or phosphoric acid being recovered in the cathode space, b4) recycling the recovered material Sulfuric acid or phosphoric acid from the cathode compartment into the wash column and derivation of recyclables formed in the anode compartment.
    Through the steps b1) and b2), an ammonium sulfate (e) or a solution containing ammonium phosphate (e) is obtained in the bottom of the wash column and a vapor free of nitrogen compounds is formed. By step b3), the acid used in step b2) is recovered immediately. This represents a valuable material and will be returned immediately in step b4). Furthermore, in the course of step b3), an ammonia solution and hydrogen are recovered in the anode compartment as further valuable substances, which are discharged according to b4).
    According to a preferred variant, water is introduced into the cathode space in step b3). This causes an osmotic pressure gradient which forces a flow from the cathode space to the anode space, thereby preventing the diffusion of residual organic anions from anode space into the cathode space. This keeps the membrane clean between the anode and cathode compartments and increases the amount of acid recovered in the anode compartment.
    Preferably, the vapor derived in step b2) is compressed and then used in step b) for heating the medium in the first reactor. The compression increases the temperature and the pressure of the vapor. Increasing the pressure of the vapor raises the boiling point of the water contained in the vapor, so that the vapor of the vapor condenses at a temperature> 100 ° C. The phase change heat of the water contained in the liquid medium is thus recovered and used to heat the medium in the first reactor of a subsequent batch to the temperature required for the hydrolysis.
    The solid inorganic phase separated off in step c) is preferably utilized in accordance with the following successive steps: c1) washing the solid inorganic phase with water, c2) returning the wash solution obtained in step c1) to the first reactor used in step b), c3) Discharging the inorganic phase remaining in step cl).
    Step c1) dissolves any organic salts entrained in the solid inorganic phase. This scrubbing solution is returned to the first reactor according to c2), so that these organic salts are introduced into the actual treatment process and, as already described, additional valuable substances are obtained therefrom. As already mentioned, valuable materials can also be obtained from the heavy metal-containing inorganic fraction.
    According to a preferred process variant, the following steps are carried out successively after step b) and before step c): d) passing the liquid medium obtained in step b) into a second reactor, e) heating the medium in the second reactor to a temperature of 50 ° C. to 80 ° C under an absolute pressure of 0.02 bar to 0.9 bar and deduction of the forming vapor.
    According to a preferred alternative process variant, the following steps are carried out successively after step c): d) passing the liquid medium obtained in step c) into a second reactor, e) heating the medium in the second reactor to a temperature of 50 ° C. to 80 ° C under an absolute pressure of 0.02 bar to 0.9 bar and deduction of the forming-containing vapor.
    According to these two process variants, it is therefore intended to forward the medium in a second reactor and to heat there under vacuum. It is possible, step c) - the separation of any solid inorganic phase contained in the liquid medium - to perform at different process times, namely before or after the forwarding of the medium in the second reactor. The provision of a second reactor is particularly advantageous when the medium has a high water content. In particular, in the case of media having a very high water content, for example sewage sludge or manure, a particularly high concentration of the organic compounds in the medium is made possible.
    The lower temperature of not more than 80 ° C. chosen in step e) compared to step b) ensures that the organic compounds formed during the previously carried out hydrolysis (step b)) are not decomposed and therefore remain unchanged in the liquid medium. From the vapor formed in step e), valuable substances can be obtained analogously to the vapor already formed in step b). The liquid medium obtained after step e) contains organic compounds in a particularly high concentration and is easily accessible to further treatment, for example distillation, so that further valuable substances can be obtained.
    The vapor formed in step e) is preferably utilized in accordance with the following successive steps: el) passing the vapor from the second reactor into a second wash column, e2) adding the vapor with sulfuric acid or phosphoric acid, a solution being obtained in the bottom of the wash column, e3 Passing the solution obtained in e2) into an electrochemical cell having a cathode space and an anode space and electrolyzing the solution, sulfuric acid or phosphoric acid being recovered in the cathode space, e4) returning the sulfuric acid or phosphoric acid obtained from the cathode space into the wash column and removing it of recyclables formed in the anode compartment.
    The recovery of this vapor is therefore analogous to the recovery of the obtained in step b) vapor.
    According to a preferred embodiment of the invention, after the last of steps a) to e), the liquid medium obtained according to step c) or step e) is recycled according to the following successive successive steps: f) forwarding, in particular continuous Passing the liquid medium into a third reactor, g) mixing the medium with a thermal oil and heating the medium to 220 ° C to 380 ° C, in particular to at most 300 ° C, preferably to at most 230 ° C, under an absolute pressure of 0.02 bar to 0.9 bar, h) discharging the vapor formed in step g) and recycling the vapor, i) removing the suspension of heat transfer oil remaining in step h) and a solid organic phase and recycling the suspension.
    The medium remaining in step e) is usually of very viscous consistency.
    By step g), the viscous medium is dispersed in the heat transfer oil, whereby a very good heat transfer to the viscous medium is possible. The vapor formed contains organic compounds, in particular alkanes, ketones, esters, alcohols and ethers, and is thus rich in valuable substances. From the remaining suspension, valuable substances can also be obtained, in particular according to further preferred embodiments of the invention, as will be explained below.
    The vapor derived in step h) is preferably utilized in accordance with the following successive steps: hl) removing the vapor formed in a distillation column, h2) cooling the vapor, in particular by spraying water, in the distillation column to condense organic compounds, h3) deriving the in step h2) condensed organic compounds and derivation of the remaining in step h2) vapor.
    The distillation column is therefore operated in such a way that organic compounds which have a lower vapor pressure than water accumulate in the bottom of the distillation column and a vapor containing mainly water vapor rises into the top of the distillation column. The organic compounds represent another valuable material, which is used in particular directly for energy production or for the production of other recyclables. The remaining vapor in particular contains fission gases, which are utilized thermally or materially, for example in heat engines with internal combustion, such as gas engines, diesel engines or gas turbines.
    The suspension of heat carrier oil and solid organic phase derived according to step i) is preferably utilized in accordance with the following successive steps: 11) discharging the suspension into a separator and feeding a water-containing phase, wherein an aqueous phase and a shell on this in the separator 12) returning the floating phase from the separator to the third reactor and passing the aqueous phase into a conversion device, 13) converting polar organic salts dissolved in the aqueous phase in the conversion device into organic compounds, in particular hydrocarbons and carbon dioxide, and to hydrogen, 14) returning the liquid medium obtained in step i3) to the separator.
    The solid organic phase is formed by organic salts. These are initially not accessible to distillation. By step il), these organic salts are converted into an aqueous phase. By step i3), further distillable organic compounds are obtained from the organic salts. By step i4) they come into contact with the heat carrier oil (floating phase), in which they are eluted. According to step i2), the heat transfer oil and thus the recovered further distillable organic compounds is recycled to the third reactor. The further treatment (recovery of valuable material) then takes place according to the already mentioned steps g) and h) and preferably according to the steps hl) to h3).
    In particular, the aqueous phase fed in step il) is the liquid medium obtained in step i4).
    In order to obtain further valuable substances, it is provided according to a further preferred variant that the aqueous phase formed in step II), preferably after at least once carrying out steps i3) and i4), is separated from one another into an electrochemical cell having two membranes permeable by an alkali metal ion Half cells slides and is electrolyzed in this. The aqueous phase still contains potassium carbonate, optionally residues of potassium hydroxide and in particular potassium phosphate and represents an electrolyte solution. By applying DC / DC voltage at the cathode hydrogen and potassium hydroxide is formed. Potassium hydroxide forms from potassium hydroxide. At the anode, phosphoric acid and oxygen are formed. The recovered potassium hydroxide solution is preferably used in step a). Any excess of potassium hydroxide solution is used in particular commercially. The phosphoric acid can be passed, for example, to the wash columns (step b2) and step e2)). The recovered hydrogen is also known to be a valuable material and is for example ideal for energy production in an internal combustion engine or in a fuel cell.
    According to a first alternative preferred variant, the liquid medium obtained in step b), preferably in step c), is pyrolyzed at a temperature of at most 500 ° C. Since the medium has previously been filtered by means of a separation device (step c), the medium is advantageously free of any heavy metal-containing inorganic compounds. Since the medium, with the exception of alkali compounds, further free of all inorganic components, the pyrolysis proceeds without or at least largely without side reactions, so compared to conventional pyrolysis significantly higher yields of liquid products can be achieved.
    According to a second alternative preferred variant, the liquid medium obtained in step b), preferably in step c), is gasified, in particular by means of entrained flow gasification, fluidized bed gasification or fixed bed gasification, preferably countercurrent fixed bed gasification.
    According to a third alternative, preferred variant, the liquid medium obtained in step b), preferably in step c), is burned.
    The carrying out of said thermal processes with the medium from which any solid inorganic phase was previously separated according to step c) is advantageous, since the thermal processes in these variants proceed without or largely without side reactions. In this way, particularly high yields of recyclables are achieved compared to conventional thermal processes.
    Further features, advantages and details of the invention will now be described in more detail with reference to the single figure, Fig. 1, which shows a schematic flow diagram of a method according to an embodiment of the invention.
    In the context of the subject invention, the term "liquid medium" liquids, suspensions and emulsions and mixtures of suspensions and emulsions.
    The invention relates to a process for the recovery of valuable substances from organic compounds contained in waste or chemical elements contained therein. Suitable organic compounds are in particular triacylglycerols (fats and fatty oils), proteins, carbohydrates or lignins. The chemical elements contained in waste and suitable for recovering valuable materials are in particular nitrogen,
    Phosphorus and / or potassium, which are mostly components of the molecules of the organic compounds. You are therefore in an "organic matrix". For example, nitrogen is found in the amino acids of proteins. Organic phosphates, such as phospholipids, which are known to be constituents of cell membranes, nucleic acids or phytates found in corn and soybean, contain phosphorus in bound form. In addition, waste may also contain inorganic phosphates, for example calcium phosphate derived from animal bones. Frequently, the waste is also contaminated with heavy metals, for example, wastewater from biowaste fermentation plants may contain copper or zinc.
    For example, a candidate waste is manure containing potassium as potassium salts, nitrogen as amines or ammonium (NH4) and phosphorus as phosphate (s). Other suitable wastes for the recovery of recyclables are in particular waste from slaughterhouses or sewage sludge, sewage sludge contains phosphorus, potassium and nitrogen in bound form. Nitrogen is particularly involved in amines.
    Between the individual steps of the process passes through a liquid medium formed from the waste, successively different devices and is processed in this. Streams a to s and streams a ', c', e ', k', m ', q' and e "symbolize in Fig. 1 the transport of the liquid medium or the transport of separated from the medium components. Currents denoted by the same letter, such as a, a ', flow into the same device or device component. For transporting the media or its components in particular pipes, pumps, shut-off devices, such as valves, and the like are provided.
    As indicated in FIG. 1, the respective waste 1 is introduced into a mixer 2 (stream a), in which an aqueous potassium hydroxide solution ("potassium hydroxide", stream a ') is introduced and mixed with the waste, so that a liquid, pumpable medium is formed. Any decomposition reactions in the mixer 2 of the organic compounds contained in the waste contribute to a homogenization of the medium and improve its pumpability. Preferably, the medium is in
    Mixture 2 heated to, for example, 60 ° to 70 ° C to accelerate or favor the decomposition reactions. The amount of added potassium hydroxide solution and / or the concentration of the potassium hydroxide solution is or are preferably selected such that the liquid medium formed has a pH of 9.0 to 14.0, in particular of at least 12.0. Particularly preferably, the quantitative ratio of organic dry matter contained in the waste to potassium hydroxide is 1: 1 to 1: 2. The resulting homogenized liquid medium is passed on to a hydrolysis reactor 3 (stream b). The waste 1 and the aqueous potassium hydroxide solution can also be introduced directly into the hydrolysis reactor 3, ie without having been previously mixed with one another in the mixer 2, in particular via a lock system.
    The hydrolysis reactor 3 has a stirrer 3 a and a heating jacket 3b and is operated under ambient pressure and therefore therefore at a pressure of approximately 1.0 bar. In the hydrolysis reactor 3, the liquid medium is heated with stirring to 100 ° C to 140 ° C, in particular to at most 120 ° C, whereby all organic compounds contained in the medium are hydrolyzed alkaline. In this case, organic salts are formed from the majority of the organic compounds, which go into solution in the liquid medium. The anions of the organic salts are derived in a known manner, in particular from organic acids, from proteins or from carbohydrates. In the described embodiment, the anions are derived, for example, from the fatty acids of the triacylglycerols. The organic salts formed therefore usually contain one or more carboxylate group (s) (R-COO-). In the described embodiment arise - due to the use of potassium hydroxide - in particular organic potassium salts.
    From any bound phosphorus - formed by the use of potassium hydroxide - potassium phosphates, at the selected pH of at least 9.0 in particular potassium triphosphates, which go into solution. There are therefore sometimes inorganic potassium salts which dissolve in the medium.
    Any bound nitrogen, such as amino acids derived from proteins, is or are decomposed in a known manner via nucleophilic substitutions, in particular via Sn 2 reactions, at least for the most part into ammonia, organic acids and their salts.
    From existing bound sulfur, for example from sulfur-containing proteins such as cysteine, hydrogen sulfide and / or sulfides are formed in the hydrolysis. Formed sulfides dissolve in the liquid medium and form together with any heavy metals present in the medium sparingly soluble heavy metal sulfides, which precipitate in the medium. If no sulfur-containing compounds have been supplied with the waste, a sulfide solution, in particular a potassium sulfide solution, is introduced into the hydrolysis reactor 3 in a manner not shown, thus causing the precipitation of the heavy metals.
    In particular, carbon dioxide also forms carbon dioxide during the hydrolysis, which reacts with potassium hydroxide solution to give potassium carbonate which is readily soluble in the medium. From any calcium salts, which originate in particular from plants and animal bones, at least the majority of carbon dioxide insoluble calcium carbonates are formed.
    In the medium undissolved or insoluble inorganic constituents, which were optionally previously mixed with the not yet dissolved organic compounds, sediment and form a solid inorganic phase. These inorganic constituents are, for example, pebbles, sand and the calcium salts mentioned and heavy metal sulfides. Depending on the waste, the solid inorganic phase may also contain other ingredients.
    The vapor which forms during the hydrolysis consists of steam and gaseous nitrogen compounds, such as, for example, ammonia or amines, and is conducted by the hydrolysis reactor 3 into a washing column 4 (stream c). The remaining hydrolyzed liquid medium is transferred together with the resulting solid inorganic phase from the hydrolysis reactor 3 in a mechanical separator 5 (stream d) and in this, as will be described, further processed.
    The vapors containing nitrogen compounds which are conducted into the scrubber column 4 are treated with phosphoric acid (H 3 PO 4), which is sprayed from above into the scrubbing column 4 in a known manner (stream c '). As a result, an ammonium phosphate is formed in the bottom of the scrubbing column 4, for example (NH 3 SO 4 PCX or a solution containing it.) A vapor largely free of nitrogen compounds rises in the top of the scrubber column 4. Sulfuric acid (H 2 SO 4) can also be used instead of the phosphoric acid, so that Bottom of the wash column 4 form ammonium sulfates.
    The solution obtained in the bottom of the scrubbing column 4 is passed on to at least one electrochemical cell 6 (stream e), in which the phosphoric acid (H3PO4) or sulfuric acid (H2SO4) used for the described scrubbing process in the scrubbing column 4 is recovered. The electrochemical cell 6 has two half cells separated by a membrane, namely a cathode space and an anode space, wherein the solution from the wash column 4 is introduced into the anode space. By means of electrolysis, ammonia solution and hydrogen are obtained from the respective ammonium salts in the cathode compartment while supplying water (stream e '). In the anode compartment, phosphoric acid or sulfuric acid is recovered with simultaneous formation of oxygen. By supplying water into the cathode compartment, an osmotic pressure gradient is created which causes flow from the cathode compartment to the anode compartment, thereby preventing the diffusion of residual organic anions from the anode compartment into the cathode compartment. This will keep the membrane clean. The recovered ammonia solution and the recovered hydrogen are derived from the cathode space (stream f) and can be utilized in a known manner as recovered recyclables. The recovered phosphoric or sulfuric acid and the oxygen formed are introduced from the anode compartment into the scrubbing column 4 (stream c ').
    The ascending in the top of the scrubbing column 4, largely free of nitrogen compounds vapors is first passed through a compressor 7, whereby the temperature and pressure of the vapor are increased, and then passed into the heating mantle 3b of the hydrolysis reactor 3 (stream g). By increasing the pressure of the vapor, the boiling point of the water contained in the vapor increases, so that the vapor of the vapor in the heating mantle 3b condenses at a temperature> 100 ° C. The phase change heat of the water contained in the liquid medium is thus recovered and used for heating the medium in the hydrolysis reactor 3 of a subsequent batch to the already preferred for hydrolysis temperature of 100 ° C to 140 ° C. The condensate forming from the vapor is discharged from the heating jacket 3b (material flow h), whereby the maintenance of the pressure and thus the high temperature of the previously compressed vapor before its discharge as condensate is ensured by means of a valve 8.
    The hydrolyzed liquid medium is, as already mentioned, transferred from the hydrolysis reactor 3 into the separation device 5, which is, for example, a sieve belt filter or a peeler centrifuge (stream d). By means of the separation device 5, the abovementioned solid inorganic phase is separated from the hydrolyzed liquid medium and subsequently preferably washed with water, whereby in particular any organic salts still present therein, in particular organic potassium salts, are dissolved out. The washing solution obtained during the washing process is recycled in a manner not shown in the hydrolysis reactor 3 and further evaporated together with the next batch in the manner already described. The solid inorganic phase is mechanically removed from the separator 5 and represents a heavy metal-containing inorganic fraction (stream j), from which heavy metals, such as copper, chromium or cadmium, are recovered as recyclables. The filtered liquid medium contains the dissolved organic salts, such as organic potassium salts, dissolved inorganic phosphates, dissolved potassium carbonate and possibly still small amounts of nitrogen compounds and is passed into a reactor 9 (stream i).
    The reactor 9 is preferably identical in construction to the hydrolysis reactor 3, therefore has an agitator 9a and a heating jacket 9b. The filtered liquid medium conducted into the reactor 9 is heated to 50 ° C. to 80 ° C., in particular to at least 70 ° C., under an absolute pressure of 0.02 bar to 0.9 bar. The pressure in the reactor 9 is replaced by a
    Vacuum pump 12 is generated, which, as will be explained, is arranged behind a heat exchanger 11.
    At the conditions mentioned in the reactor 9, any nitrogen compounds still present in the liquid medium, for example ammonia and amines, accumulate in the vapor forming in the reactor 9, which is passed into a scrubbing column 10 (stream k). Furthermore, it is ensured by the conditions prevailing in the reactor 9 that the organic compounds formed in the previous hydrolysis are not decomposed and therefore remain unchanged in the liquid medium.
    In the scrubbing column 10, there is a pressure substantially matching the pressure in the reactor 9. The scrubbing column 10 is operated in a manner analogous to the already mentioned scrubbing column 4. The phosphoric acid or sulfuric acid used for the gas scrubbing in the scrubbing column 10 also originates from the electrochemical cell 6 (stream k '), the solution obtained in the bottom of the scrubbing column 4 is passed in accordance with the electrochemical cell 6 (stream e ").
    As indicated by the stream 1, the at least largely freed from nitrogen compounds vapors from the head of the scrubbing column 10 is passed through a heat exchanger 11 and condensed in this, wherein the heat of condensation is derived from the heat exchanger 11. Water vapor and any fission gases, for example carbon dioxide, are discharged via the vacuum pump 12 already mentioned.
    The remaining after heating in the reactor 9, still warm medium is of liquid or viscous consistency still contains dissolved organic salts, dissolved inorganic phosphates, dissolved potassium carbonate and possibly even small amounts of nitrogen compounds and further up to about 20% water.
    This medium is passed on in a reactor 13, in particular via a valve 8 'slowly metered into this (mass flow m). The reactor 13 is preferably identical in construction to the hydrolysis reactor 3, therefore has an agitator 13a and a heating jacket 13b.
    In the reactor 13 is a heat transfer oil, such as a paraffin, which improves the heat transfer to the medium. By intensive stirring with the agitator 13a, the medium is suspended in the heat transfer oil and heated via the heating mantle 13b to a temperature of 220 ° C to 380 ° C, preferably up to 300 ° C, more preferably up to 230 ° C. For heating, for example, a correspondingly heated thermal oil is passed through the heating jacket 13b. Alternatively, for example, hot exhaust gases can be introduced from a combined heat and power plant. The absolute pressure in the reactor 13 is 0.02 bar to 0.9 bar and is generated by means of a vacuum pump 16, the exact position of which follows from the description below.
    The vapor forming in the reactor 13 from the medium comprises volatile organic compounds, in particular alkanes, ketones, esters, alcohols and ethers, and water, and is passed on to a distillation column 14, which is likewise evacuated with evacuated reactor 13 (stream n). In the distillation column 14, the organic compounds contained in the introduced vapor are condensed by spraying water. The distillation column 14 is operated in such a way that the organic compounds which have a lower vapor pressure than water accumulate in the bottom of the distillation column 14, and a vapor containing mainly steam rises in the top of the distillation column 14. The accumulated in the bottom of the distillation column 14 high-boiling organic compounds are derived (stream o) and represent another valuable material, which is used in particular directly for energy or for the production of other recyclables. The vapor containing mainly water vapor is discharged from the top of the distillation column 14 from this (stream p) and then condensed in a heat exchanger 15. Any fission gases formed in the distillation column 14, for example carbon dioxide, are passed together with the vapor from the top of the distillation column 14 into the heat exchanger 15 and discharged therefrom by means of the vacuum pump 16. The fission gases can be used in particular thermally or materially, for example in heat engines with internal combustion, such as gas engines, diesel engines or gas turbines.
    In the reactor 13 remains a suspension of the heat transfer oil and a solid phase, which of inorganic and organic salts (in the embodiment, in particular potassium salts). Were used in accordance with phosphorus-containing waste, the solid phase further includes phosphates (in the embodiment in particular Kaliumpho sphate).
    The organic and inorganic salts are polar compounds which are initially inaccessible to distillation. Due to the high temperatures in the reactor 13, at least some of the salts present usually decompose into likewise distillable organic compounds which are passed on to the distillation column 14 (stream n). In order to recover further, likewise distillable organic compounds from the organic and inorganic salts remaining in the suspension, the procedure is as described below.
    The suspension of thermal oil and the solid organic and inorganic salts is transferred from the reactor 13 in a separator 17 (stream q). Furthermore, a water-containing reflux (stream q ') originating from a conversion device 18 is fed into the separator 17. In this return, in the separator 17, the organic and inorganic salts suspended in the thermal oil are eluted, i. the salts are "dissolved out" of the thermal oil. In the separator 17 forms - due to the different densities - a floating phase 20, which is formed by the heat transfer oil, and an organic phase containing aqueous phase 21. The floating heat transfer oil is continuously from the separator 17 slides back into the reactor 13 (mass flow m '), in which it again improves the heat transfer to the medium. In addition, the heat transfer oil in the separator 17 also serves as an extractant for organic compounds which are contained in the return (stream q ') and are passed into the reactor 13 in this way. These organic compounds are recovered from the organic salts dissolved in the aqueous phase as explained below.
    To obtain distillable organic compounds from the organic salts, the aqueous phase 21, which is an electrolyte solution, is passed from the separator 17 into a conversion device 18 (stream r). The conversion device 18 is constructed, for example, according to the not yet published Austrian patent application A50387 / 2016 and works according to the method described there for electrochemical conversion. The aqueous phase is continuously introduced and discharged in particular in at least one single-cell, designed as a flow cell electrolytic cell, which has an electrode stack of at least two connected to a voltage source contact electrodes, wherein it flows through the electrode package. The process parameters (residence time of the electrolytic solution in the electrolytic cell, the temperature of the aqueous phase, the pH of the electrolytic solution, the ion concentration of the electrolytic solution, the current and the voltage of the voltage source) are adjusted so that the organic salts are decomposed in the electrolytic solution, wherein from the inorganic and organic salts at the anode organic compounds of different classes, including alkanes, are formed. Further, at the anode carbon dioxide and oxygen and at the cathode mainly hydrogen is formed. The hydrogen has a hydrogenating effect, so that organic compounds of various classes are also formed in the area of the cathode. One possible reaction in the conversion device 18 is a Kolbe electrolysis, in which the organic salts are converted, for example, to alkanes, to further organic compounds and to carbon dioxide. Formed carbon dioxide reacts with the still existing potassium hydroxide to potassium carbonate. Furthermore, the organic compounds may also be partially oxidized. As indicated in Fig. 1, the conversion in the conversion device 18 is preferably carried out while supplying water. As a result, the conductivity of the electrolyte solution is improved, since a possible exceeding of the limit conductivity of a saturated salt solution is avoided. In addition, the returned from the conversion device 18 in the separator 17 return (stream q ') is correspondingly hydrous, whereby the already described elution of the organic salts in the separator 17 and taking place in this phase separation are made possible.
    The liquid mixture obtained in the conversion device 18 is returned to the separator 17 (stream q ') and comes there with the heat transfer oil in contact. The organic compounds formed in the course of the conversion are lipophilic, so that they now dissolve well in the additionally acting as extractant heat transfer oil well. The aqueous phase of the liquid mixture collects in the lower region of the precipitator 17. By the mentioned recycling of the heat carrier oil into the reactor 13, therefore, the distillable organic compounds formed in the conversion apparatus 18 are returned to the reactor 13 (stream m '). By means of the conversion device 18, it is thus possible to transfer organic salts (hydrocarbons) obtained in the bottom of the reactor 13 and dissolved in an aqueous phase, from which further valuable substances are obtained in the manner already described (streams η, o and p). The aqueous phase obtained in the reactor 13 can be treated several times in the manner described, so that the organic and inorganic salts are substantially completely removed from the aqueous phase and recovered from these recyclables.
    If no further conversion step of the aqueous phase via the conversion device 18 is provided, the almost completely freed of organic salts aqueous phase from the separator 17 in an electrochemical cell 19 is passed (stream s). The aqueous phase also contains inorganic salts, in the exemplary embodiment in particular potassium salts, potassium carbonate, potassium hydroxide and potassium phosphate and represents an electrolyte solution. Potassium carbonate was, as already explained, formed in the hydrolysis in the hydrolysis reactor 3 and in the conversion device 18. Potassium hydroxide is derived from the added potassium hydroxide solution. Potassium phosphate is derived from any phosphorous contained in the waste, which has been reacted with the potassium hydroxide in the hydrolysis reactor 3, as also already mentioned.
    The electrochemical cell 19 is preferably divided with a membrane permeable to potassium ions into two half-cells - an anode space and a cathode space. By applying DC / DC voltage, the potassium ions migrate through the membrane into the cathode compartment and together with the water supplied form hydrogen and potassium hydroxide at the cathode, whereby potassium hydroxide is formed. in the
    Anode space form at the anode phosphoric acid, oxygen and carbon dioxide. The potassium hydroxide solution is removed from the cathode compartment, the phosphoric acid is removed from the anode compartment, and the gases formed are also diverted away from oxygen and hydrogen. By supplying water into the cathode compartment, the diffusion loss of phosphate through the membrane is kept low and blockage of the membrane is effectively avoided. Furthermore, the feed line causes an osmotic gradient in the direction of the anode space.
    The recovered potassium hydroxide solution is preferably used in the manner already described in the mixer 2 (stream a '). Any excess of potassium hydroxide solution is used in particular commercially. The phosphoric acid can be passed, for example, to the wash columns 4 and 10 and used for the described washing processes (streams c 'and k'). The recovered potassium hydroxide solution and the phosphoric acid obtained are further valuable substances. The hydrogen obtained in the electrochemical cell 19 is also known to be a valuable material and is, for example, ideal for energy production in an internal combustion engine or in a fuel cell.
    The invention is not limited to the embodiment described. Instead of potassium hydroxide solution (stream a '), an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution may be used. Furthermore, mixtures of such solutions can also be used. Sodium hydroxide solution and sodium carbonate solution are particularly advantageous for the hydrolysis of already sodium-containing wastes, for example in the case of waste of marine origin, in particular waste containing algae. In the electrochemical cell 19, a potassium hydroxide solution (potassium hydroxide solution) and / or a Natriumhydroxidlsöung (sodium hydroxide solution) can be obtained analogously to the manner already described. Any carbon dioxide formed in the electrochemical cell 19 is dissipated.
    According to an alternative embodiment, it is provided to recover valuable substances from the liquid or viscous medium remaining after heating in reactor 9 (stream m) by means of thermal processes. As already mentioned, the medium contains dissolved organic salts, dissolved inorganic phosphates and up to about 20% water.
    A first possibility is pyrolysis of the medium originating from the reactor 9. By the upstream hydrolysis of the medium in the hydrolysis reactor 3, the molecular weight of the organic molecules contained in the waste was significantly reduced. Thereby, it is possible to carry out the pyrolysis at a low temperature for pyrolysis, wherein the medium is preferably pyrolyzed at a temperature of at most 500 ° C. For example, potassium acetate could have been formed as the organic salt during the hydrolysis. This decomposes in the pyrolysis already at about 300 ° C in acetone and potassium carbonate.
    Further, since the medium has been filtered by the separator 5, the medium is free of any heavy metal-containing inorganic compounds. In contrast to conventional pyrolysis in which the heavy metals are produced in the pyrolysis coke, the pyrolysis coke formed in the pyrolysis of a medium originating from the reactor 9 is unproblematic in this respect. Since the medium, with the exception of alkali compounds, is free of all inorganic components, the pyrolysis proceeds without or at least largely without side reactions. As a result, significantly higher yields of liquid products are achieved in the pyrolysis of the originating from the reactor 9 medium compared to conventional pyrolysis.
    According to a second possibility, the medium originating from the reactor 9 is burnt.
    According to a third possibility, the medium originating from the reactor 9 is gasified. The gasification takes place in particular by means of an entrainment gasification, a fluidized bed gasification or a fixed bed gasification. Particularly suitable is the fixed bed gasification in a countercurrent fixed-bed gasifier, in which the medium is heated in a particularly gentle manner, whereby high yields of liquid organic compounds are achieved.
    In the electrochemical cells 6 and 19, the mentioned valuable substances (phosphoric acid, ammonia solution, potassium hydroxide solution and sodium hydroxide solution) can also be obtained by means of capacitive deionization.
    Reference numerals 1 ....................... Waste 2 ....................... Mixer 3 ....................... Hydrolysis reactor 3 a ..................... Stirrer 3b ..................... Heating mantle 4 ....................... Washing column 5. ...................... Separator 6 ....................... electrochemical cell 7 ....................... Compressor 8 ....................... Valve 9 ....................... Reactor 9a ..................... Stirrer 9b .. ................... Heating mantle 10 ........................ Washing column 11 ...... ............... Heat exchanger 12 ..................... Vacuum pump 13 .......... ........... Reactor 13a ...................... Agitator 13b ................ ... heating jacket 14 ........................ Distillation column 15 ..................... Heat exchanger 16 ..................... V akuumpumpe 17 ..................... Separator 18 .. ................... Conversion device 19 ........................ electrochemical cell 20 ..... ................ Floating phase 21 ..................... aqueous phase
    权利要求:
    Claims (23)
    [1]
    A process for the recovery of valuable substances from organic compounds contained in waste (1) or chemical elements contained therein, comprising the following successive steps: a) mixing the waste (1) with a base to form a liquid medium, b) heating the medium in a reactor (3) to a temperature of 100 ° C to 140 ° C for hydrolyzing the organic compounds contained in the medium and withdrawal (c) of the forming vapor, c) forwarding (d) of the step b) in the reactor (3) remaining liquid medium in a separation device (5) for the separation of any solid inorganic phase contained in the liquid medium.
    [2]
    2. The method according to claim 1, characterized in that step a) is already carried out in the reactor (3).
    [3]
    3. The method according to claim 1, characterized in that step a) is carried out in a separate mixer (2).
    [4]
    4. The method according to claim 3, characterized in that in step a) the waste and the base are heated to 60 ° C to 70 ° C.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that in step a) the waste with an aqueous potassium hydroxide solution (a '), an aqueous sodium hydroxide solution, an aqueous potassium carbonate solution, an aqueous sodium carbonate solution or with a mixture of at least two of these solutions is mixed.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that in step a) the amount and / or the concentration of the base are chosen such that the liquid medium formed has a pH of 9.0 to 14 , 0, in particular of at least 12.0, wherein preferably the quantitative ratio of dry matter contained in the waste to the base is 1: 1 to 1: 2.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that in step b) the liquid medium is heated with stirring to its boiling temperature.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that in step b) a sulfide solution, in particular a potassium sulfide or a sodium sulfide solution, is added.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the vapors obtained in step b) is recycled according to the following successive steps: bl) passing (c) the vapor from the reactor (3) in a wash column (4), b2) adding the vapor with sulfuric acid or phosphoric acid (c '), wherein a solution is obtained in the bottom of the scrubbing column (4) and the vapor is discharged from the head of the scrubbing column (4) (g), b3) forwarding (e) in step b2) obtained solution in an electrochemical cell (6) having a cathode space and an anode space and electrolyzing the solution, wherein in the cathode space sulfuric acid or phosphoric acid is recovered, b4) returning (c ') the recovered sulfuric acid or phosphoric acid from the cathode compartment into the wash column (4) and discharge (f) of recyclables formed in the anode compartment.
    [10]
    10. The method according to claim 9, characterized in that in step b3) water is introduced into the cathode space (e ').
    [11]
    11. The method according to claim 9 or 10, characterized in that the vapor derived in step b2) is compressed and then used in step b) for heating the medium in the reactor (3).
    [12]
    12. The method according to any one of claims 1 to 11, characterized in that the separated in step c) solid inorganic phase is recycled according to the following successive steps: cl) washing the solid inorganic phase with water, c2) returning the in step cl) washing solution obtained in the reactor (3) used in step b), c3) discharging (j) the inorganic phase remaining in step cl).
    [13]
    13. The method according to any one of claims 1 to 12, characterized in that after step b) and before step c), the following steps are carried out successively: d) passing the liquid medium obtained in step b) into a second reactor (9), e ) Heating the medium in the second reactor (9) to a temperature of 50 ° C to 80 ° C under an absolute pressure of 0.02 bar to 0.9 bar and deduction (k) of the forming vapor.
    [14]
    14. The method according to any one of claims 1 to 12, characterized in that after step c) the following steps are carried out successively: d) forwarding (m) of the liquid medium obtained in step c) in a second reactor (9), e) heating of the medium in the second reactor (9) to a temperature of 50 ° C to 80 ° C under an absolute pressure of 0.02 bar to 0.9 bar and deduction (k) of the forming-containing vapor.
    [15]
    15. The method according to claim 13 or 14, characterized in that the vapor formed in step e) is utilized according to the following successive steps: el) passing (k) the vapor from the second reactor (9) into a second washing column (10), e2) adding (k ') the vapor with sulfuric acid or phosphoric acid, a solution being obtained in the bottom of the wash column (10), e3) passing (e ") the solution obtained in e2) into an electrochemical cell (6) having a cathode space and an anode chamber and electrolyzing the solution, sulfuric acid or phosphoric acid being recovered in the cathode compartment, e4) returning (k ') the sulfuric acid or phosphoric acid recovered from the cathode compartment into the wash column (4) and discharging (f) the valuable materials formed in the anode compartment ,
    [16]
    16. The method according to any one of claims 13 to 15, characterized in that after the last of steps a) to e) - depending on the order after step c) or after step e) - obtained liquid medium according to the following successive steps is recycled f) forwarding (m), in particular continuous forwarding of the liquid medium in a third reactor (13), g) mixing the medium with a heat transfer oil and heating the medium to 220 ° C to 380 ° C, in particular to at most 300 ° C, preferably to at most 230 ° C, under an absolute pressure of 0.02 bar to 0.9 bar, h) Deriving (n) of the vapor formed in step g) and recycling the vapor, i) Deriving (q) the in step h) remaining suspension of heat transfer oil and a solid organic phase and recycling the suspension.
    [17]
    17. The method according to claim 16, characterized in that the vapor derived in step h) is recycled according to the following successive steps: hl) deriving (n) the vapor formed in a distillation column (14), h2) cooling the vapor, in particular by Spraying water in the distillation column (14) to condense organic compounds, h3) deriving (o) the organic compounds condensed in step h2) and deriving the vapor (p) remaining in step h2).
    [18]
    18. The method according to claim 16, characterized in that the according to step i) derived suspension of heat transfer oil and solid organic phase is recycled according to the following successive steps: 11) deriving (q) of the suspension in a separator (17) and feeding (q ') an aqueous phase, wherein in the separator (17) form an aqueous phase (21) and a floating on this phase (20), 12) returning (m') of the floating phase (20) from the separator (17) in the third reactor (13) and passing the aqueous phase (21) into a conversion device (18), 13) converting polar organic salts dissolved in the aqueous phase (21) in the conversion device (19) into organic compounds, in particular hydrocarbons and carbon dioxide , and to hydrogen, 14) returning (q ') of the liquid medium obtained in step i3) into the separator (17).
    [19]
    19. The method according to claim 18, characterized in that the water-containing phase which is fed in step il), the liquid medium obtained in step i4).
    [20]
    20. The method according to claim 18 or 19, characterized in that in step il) formed aqueous phase (21), preferably after at least once performing steps i3) and i4), in an electrochemical cell (19) with two by an alkali metal -Iron permeable membrane slides separated half-cells (s) and is electrolyzed in this.
    [21]
    21. The method according to any one of claims 1 to 15, characterized in that in step b), preferably in step c), obtained liquid medium is pyrolyzed at a temperature of at most 500 ° C.
    [22]
    22. The method according to any one of claims 1 to 15, characterized in that in step b), preferably in step c), the liquid medium obtained is gasified, in particular by means of entrained flow gasification, fluidized bed gasification or fixed bed gasification, preferably a countercurrent fixed bed gasification ,
    [23]
    23. The method according to any one of claims 1 to 15, characterized in that in step b), preferably the medium obtained in step c), is burned.
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    同族专利:
    公开号 | 公开日
    EP3692012A1|2020-08-12|
    US20200299204A1|2020-09-24|
    WO2019068524A1|2019-04-11|
    AT520454B1|2021-12-15|
    AT520454A3|2021-10-15|
    引用文献:
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    WO2021073844A1|2019-10-15|2021-04-22|Michael Schelch|Energy management method and system|FR2808792B1|2000-05-12|2003-03-21|Ecopsi|PROCESS FOR TREATING AN EFFLUENT CONTAINING IN PARTICULAR NITROGEN AND / OR PHOSPHORUS AND / OR ORGANIC MATERIALS AND / OR HEAVY METALS|
    GB0126458D0|2001-11-03|2002-01-02|Accentus Plc|Ammonia removal|
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    DE102008055508A1|2008-12-11|2010-06-17|Herzberg, Patrik Von|Process for the treatment of waste|
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    DE102011105473A1|2011-06-20|2012-12-20|Sabine Ludewig|Processing ammonium-containing substances of biogenic origin, comprises evaporating water from biogenic materials by uniform entry into hot alkaline model, hydrolyzing organic component and converting into true solution|
    KR101624258B1|2014-07-01|2016-05-26|주식회사이피에스솔루션|Nitrogen and Phosphorus removal, recovery apparatus and method thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50842/2017A|AT520454B1|2017-10-03|2017-10-03|Process for the recovery of valuable materials|ATA50842/2017A| AT520454B1|2017-10-03|2017-10-03|Process for the recovery of valuable materials|
    US16/753,297| US20200299204A1|2017-10-03|2018-09-25|Method for recovering valuable substances|
    PCT/EP2018/076020| WO2019068524A1|2017-10-03|2018-09-25|Method for recovering valuable substances|
    EP18781999.0A| EP3692012A1|2017-10-03|2018-09-25|Method for recovering valuable substances|
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