Wastewater treatment agents

Abstract

The invention relates to treatment agents for wastewater in pipelines (100) to treat the pollutants of the nitrogen cycle, nitrates in the wastewater and the climate-damaging air pollutants NH3 and N2O online. This is achieved by using a pump (102), a downstream pipeline (108), a container (104) for supplying oxygen via a feed line and a degassing vessel (101) is provided. This makes it possible to use the generated O2 molecules in wastewater to separate the climate toxins NH3, N2O according to Annex 9 and 11 of the TA Luft with increased efficiency (470%) and to enable online CO2eq immission as a negative immission for climate neutrality and to obtain hydrogen H2 from water H2O as an added value.

Description

[0001] The invention relates to treatment agents for wastewater, to climate toxins in wastewater, to wastewater from animals (e.g., pig farming), from humans in sewage treatment plants, to wastewater from biogas plants, to the load of pollutants from the excretions of living beings, to NH3 and NH4+ ammonium, as well as to the immissions of pollutants as nitrates in wastewater and as N2O, nitrous oxide, which, according to TA Luft 2.2, is degraded at the point of onset over 114 years, in order to diagnose the pollutant formation during the aeration of wastewater with atmospheric nitrogen N2 and the lack of oxygen O2 and to avoid the N2 cycle via the nitrates in the groundwater as well as the N2O immission as CO2eq.

[0002] The invention further relates to the concentration of climate toxins, the molecules and the use of the molecules from the separation of H2O in an electrolyzer into H2 and O2 as follows, • H2 for energy production and CO2 savings, • O2 for the chemisorption of the nitrogen cycle according to Annex 9 and Annex 11 of the TA Luft with the climate toxins NH3, NH4+, in wastewater, to avoid N2O nitrous oxide and CO2egq as the dangerous climate gases that cannot be treated at the point of impact (ozone hole).

[0003] The fact is that N2O, as a greenhouse gas, is 300 times more harmful than CO2 from fossil fuels used for energy production in the Earth's near-surface atmosphere. Advantages: Disclosure of emissions from greenhouse gases, diverse uses of O2.

[0004] Accordingly, the achievable added value of using the O2 molecule in wastewater treatment compared to using H2 for energy generation is demonstrated in the numerical example. (su) Advantages, • Utilization of O2 molecules - production of H2 with the added benefits of O2; • Lower O2 sorption efficiency - proportionally higher H2 production; • 5.1 kg NH3 / m3 in the press water, according to Weihrich - negative CO2 immission through chemisorption with the O2 molecule; su • Use of O2 molecules for the decentralized introduction of H2 hydrogen.

[0005] Another task involves different concentrations of nitrogen N2 in the wastewater as nominal quantities, in the form of NH4+, Wastewater treatment plants with 75 mg NH3 / Ltr, Pig manure with 1,540 mg NH3 / Ltr, Pressed water* from biogas containing approximately 5,100 mg NH3 / Litr. In the case of pig manure and a 20-fold concentration of NH3 / Ltr, i.e., 2000%. For biogas and press water up to 4000%, further measures are necessary for wastewater treatment agents. *) according to Weihrich, University of Augsburg.

[0006] The invention further addresses the nitrogen cycle and the detrimental aeration of wastewater. A disadvantage is the introduction of nitrogen into the wastewater and the 300% excess of nitrogen compared to oxygen. Specifically, when nitrogen (N2O) is formed from ammonium (NH3), nitrogen and oxygen react in equal proportions, and atmospheric oxygen is consumed when two-thirds of the nitrogen remains in the wastewater. A significant disadvantage is oxygen deficiency, leading to an expansion of the nitrogen cycle. Due to this expansion, further measures are necessary in wastewater treatment processes.

[0007] The invention further relates to chemisorption of wastewater by O2, a process by which the sorption of NH4+ and NH3 to form N2 and H2O is known. A disadvantage is the formation of N2 in the wastewater. For the removal of the reaction gases, especially nitrogen (N2), from wastewater, further measures are necessary in wastewater treatment agents.

[0008] A nitrogen treatment with O2 is known from publication CH 673 409 A5, according to which gaseous nitrogen oxides NOx in the liquid are treated with liquid O2 in the form of H2O2 to enable chemisorption for the removal of the nitrogen, NOx from the cycle with O2, liquid oxygen O2. For chemisorption in the N2 cycle for liquid pollutants from wastewater according to Annexes 9 and 11 of the TA Luft, further measures are necessary.

[0009] Furthermore, climate pollutants, according to Annex 09 of the TA Luft (Technical Instructions on Air Quality Control), are present in wastewater from biogas plants at an average concentration of 5.1 kg / m³, according to the University of Augsburg, Weihrich, Faculty of Mathematics and Natural Sciences, Master's thesis on the treatment of fermentation residues, by Margarita Müller. These pollutants are treated in various process steps involving distillation and evaporation using process energy in the wastewater. A disadvantage is the distribution in a larger volume (1:1700) through evaporation and the subsequent treatment of NH₃ from NH₄⁺ in the gas phase. A significant disadvantage is: • Inertia of the gas-phase reaction, • physical reactions, • Evaporation and drinking water protection for 40,000 m³ of stored press water containing 5.1 kg NH₃ / m³. In the case of chemisorption with the resulting O₂ molecules from water, further measures are necessary for groundwater and drinking water protection according to Ref. 91, LfU, Hof. (su)

[0010] Furthermore, a joint project between the University of Augsburg and the Bavarian State Office for the Environment (LfU) is known, with the project ending on May 31, 2024, concerning excessive input of (N-) compounds into soils as nitrates, as well as NH3 and N2O emissions into the atmosphere according to the Technical Instructions on Air Quality Control (TA Luft 2.2), according to which the general task is described as being adversely affected by the immission of NH3 and N2O in agriculture compared to wastewater treatment in sewage treatment plants. A disadvantage is the wastewater treatment using N2 from the air and the emission of greenhouse gases (toxins) NH3, N2O, and CO2 equivalent in wastewater treatment plants, along with the primary energy consumption for the air blowers. More details: Paragraph 1 of the project description, LfU Ref. 91 and UNI Augsburg, keyword GÄRAMP. Further measures are necessary for wastewater treatment agents to eliminate the disadvantages of wastewater treatment, such as climate toxins, nitrates in groundwater, and CO2 equivalent emissions from N2O. Disadvantage: Concealing the emissions from wastewater, premature project termination without a final report, among other things.

[0011] The invention further addresses the diagnosis of nitrate levels in wastewater from pig manure and their reduction to approximately 20 mg / L H₂O, in order to achieve a reduction from 1540 mg / L to < 20 mg / L. Further measures are necessary in the wastewater treatment agents to achieve a reduction of 1520 mg or 98.7% in the treated wastewater.

[0012] The invention further addresses the animals and their health, aiming to improve the contact of piglets in barns located above manure pits with greenhouse gases / toxins, particularly the typical cell toxin NH3. Additional measures are necessary regarding wastewater treatment agents for the production of meat from healthy animals.

[0013] Furthermore, the invention deals with the chemical properties and solubility of the gaseous components of air and oxygen in the water, in order to enable the chemical processes in the treatment of NH3, NH4+ in wastewater. The fact is that oxygen O2 dissolves at a concentration of 8.3 mg / L at physical equilibrium at O2 and 25 °C. A disadvantage is the O2 requirement for chemisorption at 1520 mg NH3 per liter H2O, which is 2,900 mg per liter, based on NH3. Accordingly, chemisorption with O2 requires a multiple of the dissolved gas, namely 2900 / 8.3 = 350 times. For a liquid reaction in wastewater treatment agents, further measures are necessary for the climate toxins in wastewater.

[0014] Furthermore, the invention deals with the timeline for the removal of climate toxins in wastewater in the area of ​​the IBK, Lake Constance Conference: • 20% NH3 removal from 2030 onwards in wastewater treatment plants - Austria; • Threshold of 0.1 kg NH3 / h according to Annex 09, TA Luft - Germany.

[0015] The invention described in claim 1, concerning treatment agents for wastewater, is based on the problem, according to the prior art of CO2eq immission from climate toxins in wastewater, the separation of nitrates in wastewater and the prevention of the N2 cycle by NH3 and N2O, of proposing treatment agents for the distribution of oxygen and the sorption of N2-containing pollutants in wastewater for a nominal quantity of 75 mg NH3 / Ltr to 5100 mg NH3 / Ltr in order to avoid nitrate emissions in wastewater and NH3 and N2O immission into the atmosphere according to Annex 9, 11 of the TA Luft. Another task arises in realizing the added value in order to avoid and analyze, on a project-specific basis, the emission of untreated CO2 eq from wastewater, which is 300 times stronger than N2O.

[0016] This problem is solved by the features of the treatment agent for wastewater in pipelines listed in claim 1, comprising a pump, a downstream pipeline, a container for supplying oxygen via a feed line and a degassing container, and in particular by a feed line for H2O2 from a container with H2O2.

[0017] Advantageous further developments and embodiments of the invention are possible through the measures mentioned in dependent claims 2-10.

[0018] The advantages achieved with the invention of water treatment agents consist of pipelines for wastewater, a pump, a downstream pipeline, a container for supplying oxygen via a feed line, a degassing container, in order to enable the versatile online use of O2 molecules for chemisorption and the purification of climate toxins in the N2 cycle of wastewater. Further advantages of the invention are, • Reaction kinetics in wastewater from biogas, slurry, sewage treatment plants - reduction 1 : 1700; • Negative CO2eq emission from wastewater with 5.1 kg NH3 / m3 - 5 t CO2eq / m3 press water; • Climate-neutral pigs, with healthy meat according to Annex 11, TA Luft; • Online chemisorption in wastewater from sewage treatment plants; • Online chemisorption - gas-tight design; • Chemical and physical properties of H2O2 dissolved in water; • Gas / liquid separation - of the reaction gases formed, e.g., N2; • Gas-side closure from the pig pen to the slurry tank; • High availability of the O2 sorbent - molecules formed from H2O; • High added value - regardless of the efficiency of the reaction, due to the climate toxin NH3.

[0019] A key feature of the invention is a degassing vessel in a downstream pipeline. A further advantage: • online chemisorption with O2 • Collection and separation of the formed molecules, • Analysis of the greenhouse gases N2O / CO2eq - operation with air, • Reproducible mass transfer via Reynolds number, • Control range from Re 5,000 to Re over 1,000,000, • Scale-up and transferability of results.

[0020] An advantageous embodiment of the invention is specified in claim 2. The invention described in claim 2 makes it possible to provide a container with a supply line for H2O2. Advantageously, a container with liquid H2O2 with the supply line is provided for pig manure. Advantage achieved: • liquid O2 as a commercial product, • Dosing via dosing pump.

[0021] An advantageous embodiment of the invention is specified in claim 3. The invention described in claim 3 makes it possible to provide a container for gaseous oxygen (O2). Advantageously, a container with gaseous oxygen (O2) and a supply line is provided. Advantage achieved: • Function of oxygen O2, • Added value through the formation of O2 molecules from H2O in an electrolyzer, • Added value through the production of H2 during wastewater treatment.

[0022] An advantageous embodiment of the invention is specified in claim 4. The invention described in claim 4 makes it possible to provide a static mixer in the pipeline. Advantageously, a static mixer is provided in the pipeline. Advantage achieved: • Mixing of O2 and wastewater, optional additional function, online, • Increased turbulent flow and mixing in the pipeline, • Reproducibility, scale-up of results, • Reynolds from 5,000 to 1,000,000.

[0023] An advantageous embodiment of the invention is specified in claim 5. The invention described in claim 5 makes it possible to provide a transport container with a connecting line to the pump for receiving the wastewater.

[0024] A transport container with a connecting line to the pump is advantageous. Benefit achieved: • Wastewater treatment agent connected to a transport container, • Centralized, online treatment of wastewater using mobile transport containers, • Transport containers for industrial and pilot operation.

[0025] An advantageous embodiment of the invention is specified in claim 6. The invention described in claim 6 makes it possible to provide a measuring line from the pipeline. Advantageously, a measuring line is provided from the pipeline. Advantage achieved: • Uniform M+R technology, online • variable length and reaction time, • Reproducibility - adjustable Reynolds numbers • Version as a hose - flexible e.g. 1".

[0026] An advantageous embodiment of the invention is specified in claim 7. The invention described in claim 7 makes it possible to provide a measuring container in the measuring line. Advantageously, a measuring container is provided in the measuring line. Advantage achieved: • Sampling of the wastewater in the measuring container - gas-tight, • Simplicity of sampling - health protection through the formation of molecules, e.g., aromatics in wastewater treatment plants with a Maggi-like odor, uniform.

[0027] An advantageous embodiment of the invention is specified in claim 8. The invention described in claim 8 makes it possible to provide measuring means Ql for diagnosing nitrate. Advantageously, measuring means Ql are provided with (Q = nitrate). Advantage achieved: • Diagnosis of nitrate as residual content - guaranteed value • Quality control of nitrates in treated wastewater, • Securing added value via the residual nitrate content, e.g., 20 mg / L - target value 20 + / - 5 mg / L • Method: Measuring strips, ease of use in agriculture, • Guaranteed performance with variable O2 efficiency.

[0028] An advantageous embodiment of the invention is specified in claim 9. The invention described in claim 9 makes it possible to provide a gas extraction line on the suction side of the pump in pig farming. Advantageously, a gas extraction line is provided on the suction side of the pump. Benefit achieved: • Gas-tight seal of the slurry tank by the pump, • Ventilation of the pig pens via the extraction line, • Extraction of harmful gases, • High-quality food from healthy pigs.

[0029] An advantageous embodiment of the invention is specified in claim 10. The invention described in claim 10 makes it possible to provide a mains connection for electric drives. The advantage of providing a mains connection for electric drives is: • Use of grid energy - billing of CO2 emissions, • Energy savings without wastewater aeration, • Increasing the share of green electricity in the grid.

[0030] Further advantages of the invention are shown in the drawing in Fig. 1 is shown. It shows: Fig. 1. Wastewater treatment products.

[0031] Wastewater treatment agents for pipelines are in Fig.Figure 1 is shown as a schematic diagram, consisting of a pipeline 100 with wastewater, a pump 102, a static mixer 103, in further pipelines 108, a container for oxygen 104, with a supply line to the static mixer 103, a degassing tank 101 for wastewater, a measuring tank 105, a measuring line 106 and a transport container 107, and is set up online in such a way that • that the flow of gases from the manure pit (not shown) is blocked by pump 102, • the container 104 is provided with oxygen O2 and H2O2, • a process simulation is provided with the transport container 107 and the degassing container 101, • the result in measuring container 105 at measuring point Ql as residual nitrate (NO3) - ) is diagnosable.

[0032] In addition to the presentation in Fig.Other representations are possible, which are not listed in detail. It is important that a degassing vessel 101 is present so that the advantages of the invention, such as the use of H2O2 and the O2 molecules formed for chemisorption, can be achieved. The advantage is the degassing of the wastewater, especially N2, to enable the achievement of the target values ​​for nitrates in the wastewater and the reduction of the N2 cycle. Another advantage: • Online treatment of wastewater from tank 107 to tank 101, • Health care for the animals through the gas barrier (pump), • Drinking water protection according to Ref. 91, LfU for biogas plants with 5.1 kg NH3 / m3 in the pressure vessels, according to Weihrich.

[0033] Further advantages are shown as a calculation example, based on 5.1 kg NH3 / m3 wastewater, according to Weihrich, and the use of the O2 molecule, with the added value shown below: 1. General wastewater data N2 nitrogen emission / PE 11 g N2 / day N2 max 12.5 g N2 / day N2 emission / pig 11 * 2.7 / 2 14.85 g N2 / day Breeding pig per year with piglets 7.29 kg NH3 / year O2 solubility in H2O at 25 °C 8.3 mg / L Current CO2 price 2025 Switzerland 120 CHF / t CO2 Germany 55 € / t CO2 a) Chemical reactions in wastewater Ventilation with air, equation 01 NH4+ with air (N + O) >> N2O + N2(residual air) + x H2; Eq. 01 Ventilation with excess N2, lack of O2. b) Chemisorption of NH4+ with O2, Equation 02 2 NH4+ + 2 O2 >> N2 + 4 H2O; Eq. 02 O2 requirement: at 28 kg N2 and 64 kg O2; 2. N2 in wastewater as NH3 Nominal value - sewage treatment plant 75 mg NH3 / Ltr Guideline value - pig manure 1,540 mg NH3 / Ltr Target value for nitrates (NO3) - ) 20 mg / L nitrates Should chemisorption > 98 % Should O2 demand be met by liquid manure: 64 / 28 * 1.540 / 17 * 14 = 2,898 mg / Ltr Solubility of O2 8.3 mg / Ltr H2O O2 Task should be: 2900 / 8.3 350 times; 3. Immission and consequential damage of ventilation Gl 01 Indicator O2, oxygen Emissions according to TA Luft 2.2 as CO2 eq Climate damage: N2O emissions are 300 times higher than CO2eq, N2O reacts with O2: (44 / 16) = 2.75 times the amount of O2, Immission / t O2: (2.75 * 300) = 825 t CO2eq per t O2. Consequential damage caused by 1 t of O2: 2025 at 55 € / t CO2 = 825 t * 55 = 45,000 € / t O2; 2024 at 120 SFr / t CO2 = 825 t * 120 = 99,000 SFr / t O2 4. Added value through the avoidance of consequential damages: 4.1 in humans, EW NH3 emission / year 4.02 kg / EW N2O nitrous oxide / year 12.63 kg / EW O2 proportionally in N2O 4.59 kg O2 / EW Consequential damage at 55 € / t CO2: 4,59 * 45 € = €206 per person per year Saving: 35,000 inhabitants * 206 €7,200,000 / year 4.2 pigs / breeding sows per year NH3 emission / year 5.42 / 7.29 kg N2O nitrous oxide / year 17.06 / 22.9 kg O2 proportionally in N2O 6.19 kg O2 / SW Consequential damage at 55 € / t CO2: 6,19 * 45 € = €278 / SW, year * 6.19 * 99 CHF = 612 CHF / SW, year* *) 12 months 5. Benefits achieved and CO2 savings, after position 1 11 g N2 / day 40,000 inhabitants €8,240,000 / year 80,000 inhabitants €16,480,000 / year 120,000 inhabitants €24,720,000 / year 160,000 inhabitants €32,960,000 / year 6. Key Advantage • Pig manure with liquid oxygen H2O2, • 100% solution of H2O2 in the liquid manure, • Long-term effect of H2O2 on nitrate sorption. 7. Added value, climate protection, drinking water protection through the use of O2 molecules in wastewater. State of the art, Augsburg Ref. 91, LfU, Hof molecule produced from H2O in Electrolyzer De minimis threshold for NH3 0.1 kg NH3 / h Is press water* biogas approx. 40.000 m3 proportionally, NH3 / n. Weihrich 5.1 kg NH3 / m3 in total 204,000 kg NH3 The result of the concealment Drinking water hazard Plant size 800 kWel. Result • Concealing the Drinking water hazard • Catchment area: Innsbruck Lake Constance Conference • Stuttgart area, max. 4 million. 2,000,000 inhabitants *) on the B 32 7.1 Hazard per kg NH3, (concealed) 1 kg N2 with air, 1 / 14 * 44 3.14 kg N2O 3.14 kg N2O * 300 times 0.94 t CO2eq Advantage / kg NH3 negative CO2 emissions • Savings 0.94 t CO2 / kg NH3 7.2 Savings with the formed molecule of O2 Efficiency 100 % 1 kg N2 with O2, 1 / 14 * 32 2.29 kg O2 Target value savings 0.94 t CO2 CO2 requirement for 2.29 kg O2 14.29 kWh at 5 O2 / 1000 kWel. Electrolyzer: 0.8 kg CO2 / kWh 11.43 kg CO2 Result: Savings (940 - 11.43) 928.57 kg CO2 Advantage Added value of H2 • H2 profit: 10 * 2 / 1000 * 14.29 0.29 kg H2 as a molecule • 0.928 t CO2 / kg NH3 negative CO2 emissions • IBK at 204,000 kg, from 2025 (-) 189,300 t CO2eq • H2 at 204,000 kg, from 2025 + 59,160 kg H2 • Protection of drinking water, from 2025 7.3 Savings with 50% efficiency of the O2 molecule 1 kg N2 with 2 O2, 1 / 14 * 64 4.58 kg O2 Target value savings 0.94 t CO2 CO2 requirement for 4.58 kg O2 28.58 kWh 0.8 kg CO2 / kWh 22.86 kg CO2 Result: Savings (940 - 23) 917 kg CO2 Advantage Added value of H2 • H2 profit: 10 * 2 / 1000 * 28.86 0.59 kg H2 as a molecule • 0.917 t CO2 / kg NH3 negative CO2 emissions • IBK at 204,000 kg, from 2025 (-) 187,068 t CO2eq • H2 at 204,000 kg, from 2025 + 120,360 kg H2 • Protection of drinking water, from 2025 onwards 4 million inhabitants • 120 t H2 - THE added value of the negative (-) CO2 emissions • 120,360 kg H2 - instead of 210,000 kg air conditioning imagift NH3, at 810 € / t NH3 * (210) - 170.100 € At 10 € / kg H2 * (120,360) 1.203.600 € Added value 1.033.500 € 7.4 Chemical sorption in wastewater treatment plants for negative immission, climate neutrality NH3 emission / year 4.02 kg / EW N2O nitrous oxide / year 12.63 kg / EW Is the emission at 12.5 g N2 / Day: CO2eq 4.3 t CO2 / year Wastewater approx. 120 Ltr / EW Tag -1 With 40,000 inhabitants 12,5 * 365 * 40.000 182,500 kg N2 / year O2 demand, at 50% efficiency 182,500 * 4.58 kg O2 835,850 kg O2 / year Target value savings 182,500 * 0.94 t CO2 174,370 t CO2eq Advantage: • Negative emission 174,370 t CO2eq • H2 hydrogen production in Electrolyzer 835,850 / 160 * 20 kg H2 = 104,487 kg H2; • Added value at €65 / t CO2: H2 at 10 € / kg €1,044,870 / year CO2 at €65 / t €11,334,050 / year CO2 at 120 CHF / t CHF 20,924,400 / year Benefits achieved: • Biogas: Negative CO2eq immission, elimination of the drinking water hazard through chemisorption with generated O2 molecule; • CO2 absorption according to 7.4 is 4.71 more (174,370 t / 37,000 t SAP / Climeworks), with 471% - zero immission better than the multi-million Euro Agreement*. • Greater added value, with more O2 and less O2 efficiency, • Added value, proportional to the CO2 price: €65 or CHF 120 per ton; • Online, negative CO2 emissions through treatment of the climate toxins NH3, N2O according to Annex 9, 11 of the TA Luft; • Climate neutrality by 2025 through wastewater treatment agents containing the generated molecule O2. • The added value is inversely proportional to the efficiency of the O2 molecules produced. • High CO2 credits in Switzerland at CHF 120 / t CO2. *) June 2025 SAP / Climeworks / Christian Klein / Christoph Gebald with 471% Reference numeral list: 100 pipes 101 degassing containers 102 Pump, with electric drive 103 static mixers 104 containers for O2, H2O2 105 measuring containers with (QI) 106 Measuring lead 107 transport containers 108 connecting pipeline 109 Ql, quality indicator e.g. nitrates QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] CH 673 409 A5

[0008]

Claims

[1] Treatment products for wastewater in pipelines (100) wherein a pump (102), a connecting pipeline (108), a container (104) for supplying oxygen via a supply line and a degassing vessel (101) is provided. [2] Wastewater treatment agent according to the preceding claim, wherein the container (104) is provided with a supply line for H2O2 for pig slurry. [3] Wastewater treatment agent according to one of the preceding claims, wherein the container (104) is provided for gaseous oxygen O2 for municipal wastewater. [4] Wastewater treatment device according to one of the preceding claims, wherein a static mixer (103) is provided in the pipeline (108). [5] Wastewater treatment device according to one of the preceding claims, wherein a transport container (107) is provided with a connecting line to the pump (102) for receiving the wastewater. [6] Wastewater treatment device according to one of the preceding claims, wherein a measuring line (106) is provided from the pipeline (108). [7] Wastewater treatment agent according to one of the preceding claims, wherein a measuring vessel (105) is provided in the measuring line (106). [8] Wastewater treatment agent according to one of the preceding claims, wherein measuring means (109) QI are provided for diagnosing the nitrate. [9] Treatment agent for wastewater from pig farming, according to claim 1, wherein a gas extraction line is provided on the suction side of the pump. [10] Wastewater treatment device according to one of the preceding claims, wherein a mains connection is provided for electric drives.

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