Inorganic-biological hybrid and its preparation method and application

Abstract

The present application discloses an inorganic-biological hybrid and its preparation method and application, belonging to the field of wastewater treatment technology. The inorganic-biological hybrid is a hybrid of multi-walled carbon nanotubes and activated sludge from a denitrification biofilter. It is used in a hydrogen-based membrane bioreactor (H2-MBfR) to denitrify wastewater. The inorganic-biological hybrid can attach to a hollow fiber membrane to form a biofilm, thereby increasing the concentration of H2 and NO3. ‑ The diffusion rate in the biofilm can be reduced, thereby effectively alleviating the dual-substrate diffusion limitation of H2-MBfR, thereby improving its H2 utilization and reducing the risk of explosion.

Description

Technical Field

[0001] The present application belongs to the technical field of wastewater treatment, and specifically relates to an inorganic-biological hybrid and a preparation method and application thereof. Background Art

[0002] Nitrate nitrogen (NO3 - ) is ubiquitous in surface water and groundwater around the world. Heterotrophic denitrification is a process for removing NO3 - One of the most commonly used technical means, mainly due to its high denitrification efficiency, low operating cost and simple operation. However, in the face of low carbon-nitrogen ratio wastewater (C:N<4), heterotrophic denitrification needs to supplement organic carbon sources as electron donors (such as acetate and methanol, etc.), resulting in a sharp decline in the operating efficiency of the biochemical denitrification process and causing organic matter residues in the wastewater. As a supplement to heterotrophic denitrification, autotrophic denitrification effectively avoids the consumption of organic carbon sources, is compatible with low carbon-nitrogen ratio wastewater, and broadens the application scenarios of denitrification.

[0003] Hydrogen-based membrane bioreactor (H2-MBfR) is an autotrophic denitrification technology that uses H2 as an electron donor. H2 diffuses through the hollow fiber membrane in the membrane bioreactor and provides electrons to the autotrophic denitrification biofilm on the hollow fiber membrane in a bubble-free form, thereby achieving hydrogen autotrophic denitrification of wastewater. Since clean and green H2 is used as an electron donor, H2-MBfR not only avoids the problem of secondary pollution of the effluent, but also significantly reduces indirect carbon emissions in the denitrification process. However, NO3 - Diffusion from the water phase side into the biofilm, while H2 diffuses from the hollow fiber membrane side into the biofilm, resulting in H2 and NO3 in the biofilm - The substrate concentration mismatch. H2 and NO3 on the biofilm - The mismatch of substrate concentration reduces H2 utilization and increases the risk of explosion. Therefore, how to achieve minimum H2 loss is one of the key technical bottlenecks limiting the widespread application of H2-MBfR. Summary of the invention

[0004] 1. Problem to be solved

[0005] The present application aims to solve the problems of low H2 utilization rate and high explosion risk in the denitrification process using hydrogen-based membrane bioreactors, and provides an inorganic-biological hybrid and its preparation method and application. The inorganic-biological hybrid is hybridized by multi-walled carbon nanotubes and activated sludge from a denitrification biofilter. The inorganic-biological hybrid is used in a hydrogen-based membrane bioreactor for wastewater denitrification. The inorganic-biological hybrid can attach to the hollow fiber membrane to form a biofilm, thereby increasing the conversion of H2 and NO3 - The diffusion rate in the biofilm can effectively alleviate the dual-substrate diffusion limitation of H2-MBfR, thereby improving its H2 utilization and reducing the risk of explosion.

[0006] 2. Technical solution

[0007] In order to solve the above problems, the technical solutions adopted in this application are as follows:

[0008] In a first aspect, the present application provides an inorganic-biological hybrid, which is formed by hybridizing multi-walled carbon nanotubes (MWCNTs) and activated sludge from a denitrifying biological filter.

[0009] In a second aspect, the present application provides a method for preparing the above-mentioned inorganic-biological hybrid, the method comprising the following steps:

[0010] S1, multi-walled carbon nanotubes (MWCNTs) were added into N-methylpyrrolidone (NMP) and then ultrasonically treated to form a uniform MWCNTs dispersion;

[0011] S2, adding activated sludge from a denitrification biofilter to the stirred MWCNTs dispersion, stirring and mixing to form an inorganic-biological hybrid precursor solution;

[0012] S3, after the inorganic-biological hybrid precursor solution is allowed to stand for stratification, the supernatant is removed to obtain the inorganic-biological hybrid.

[0013] Furthermore, in the above step S1, the ultrasonic treatment time is 2.0 to 6.0 h.

[0014] Furthermore, in the above step S1, the concentration of the MWCNTs dispersion is 0.1-1.0 g / L.

[0015] Furthermore, in the above step S2, the MLSS of the activated sludge from the denitrification biological filter is 1.0-10 g / L.

[0016] Furthermore, in the above step S2, the volume ratio of the MWCNTs dispersion to the activated sludge is 1:0.1 to 1:10.

[0017] Furthermore, in the above step S2, the addition rate of activated sludge is 1.0~100 mL / min.

[0018] Furthermore, in the above step S2, the stirring and mixing time is 5.0 to 30 min.

[0019] Furthermore, in the above step S3, the standing time is 10 to 60 min.

[0020] In a third aspect, the present application provides the use of the above-mentioned inorganic-biological hybrid or its preparation method in wastewater denitrification.

[0021] Furthermore, the above application is to use inorganic-biological hybrids to enhance hydrogen-based membrane bioreactors for wastewater denitrification, specifically inorganic-biological hybrids attached to hollow fiber membranes to form biofilms, and the formation of biofilms can increase H2 and NO3 - The diffusion rate in the biofilm is increased, thereby effectively alleviating the dual substrate diffusion limitation of H2-MBfR and improving its H2 utilization.

[0022] Furthermore, the above wastewater is low carbon-nitrogen ratio wastewater.

[0023] Furthermore, the nitrate nitrogen concentration of the above-mentioned low carbon-nitrogen ratio wastewater is 15~200 mg / L.

[0024] Furthermore, the carbon-nitrogen ratio of the above-mentioned low carbon-nitrogen ratio wastewater is 0:1~4:1.

[0025] Furthermore, the above application includes the following steps:

[0026] M1, pumping the inorganic-biological hybrid dispersion into the membrane bioreactor;

[0027] M2, the inorganic-biological hybrid is filtered and retained on the hollow fiber membrane assembly of the membrane bioreactor; the inorganic-biological hybrid can attach to the hollow fiber membrane to form a biofilm, increasing the H2 and NO3 - The diffusion rate in the biofilm can effectively alleviate the dual-substrate diffusion limitation of H2-MBfR and improve its H2 utilization rate.

[0028] M3, nutrient solution is introduced into the membrane bioreactor, and hydrogen is introduced into the hollow fiber membrane to acclimate the inorganic-biological hybrid;

[0029] M4, after the acclimation is completed, the wastewater is pumped into the membrane bioreactor for denitrification.

[0030] Furthermore, in the above step M1, the method for preparing the inorganic-biological hybrid dispersion includes: adding culture solution to the inorganic-biological hybrid for washing, and mixing with the culture solution after washing to form the inorganic-biological hybrid dispersion.

[0031] Furthermore, the culture medium formula is 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 mL / L vitamin solution and 12.5 mL / L trace mineral solution.

[0032] Furthermore, the concentration of the inorganic-biological hybrid dispersion is 1.0-10 g / L.

[0033] Furthermore, the cleaning times are 1 to 5. Furthermore, in the step S14, the cleaning times are 3.

[0034] Furthermore, in the above step M2, the hollow fiber membrane assembly is a hollow fiber membrane made of polypropylene, the effective length of the membrane is 10-20 cm, the outer diameter is 100-500 μm, and the membrane pore size is 0.01-0.45 μm.

[0035] Furthermore, in the above step M3, the nutrient solution formula is 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution.

[0036] Furthermore, in the above step M3, the flow rate of hydrogen is 0.01~1 mL / min.

[0037] Furthermore, in the above step M3, the acclimation time is 3 to 7 days.

[0038] Furthermore, in the above step M4, the hydraulic retention time of the low carbon-nitrogen ratio wastewater is 6.0~24 h.

[0039] In a fourth aspect, the present application provides a method for denitrification of low carbon-nitrogen ratio wastewater, specifically comprising:

[0040] N1, pumping the above inorganic-biological hybrid dispersion into the membrane bioreactor;

[0041] N2, the inorganic-biological hybrid is filtered and retained on the hollow fiber membrane assembly of the membrane bioreactor; the inorganic-biological hybrid can attach to the hollow fiber membrane to form a biofilm, increasing the H2 and NO3 - The diffusion rate in the biofilm can effectively alleviate the dual-substrate diffusion limitation of H2-MBfR and improve its H2 utilization rate.

[0042] N3, nutrient solution is introduced into the membrane bioreactor, and hydrogen is introduced into the hollow fiber membrane to acclimate the inorganic-biological hybrid;

[0043] N4, after the acclimation is completed, the wastewater is pumped into the membrane bioreactor for denitrification.

[0044] Furthermore, the nitrate nitrogen concentration of the above-mentioned low carbon-nitrogen ratio wastewater is 15~200 mg / L.

[0045] Furthermore, the carbon-nitrogen ratio of the above-mentioned low carbon-nitrogen ratio wastewater is 0:1~4:1.

[0046] Furthermore, in the above step N1, the method for preparing the inorganic-biological hybrid dispersion includes: adding culture solution to the inorganic-biological hybrid for washing, and mixing with the culture solution after washing to form the inorganic-biological hybrid dispersion.

[0047] Furthermore, the culture medium formula is 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 mL / L vitamin solution and 12.5 mL / L trace mineral solution.

[0048] Furthermore, the concentration of the inorganic-biological hybrid dispersion is 1.0-10 g / L.

[0049] Furthermore, the cleaning times are 1 to 5. Furthermore, in the step S14, the cleaning times are 3.

[0050] Furthermore, in the above step N2, the hollow fiber membrane assembly is a hollow fiber membrane made of polypropylene, the effective length of the membrane is 10-20 cm, the outer diameter is 100-500 μm, and the membrane pore size is 0.01-0.45 μm.

[0051] Furthermore, in the above step N3, the nutrient solution formula is 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution.

[0052] Furthermore, in the above step N3, the flow rate of hydrogen is 0.01~1 mL / min.

[0053] Furthermore, in the above step N3, the acclimation time is 3 to 7 days.

[0054] Furthermore, in the above step N4, the hydraulic retention time of the low carbon-nitrogen ratio wastewater is 6.0~24 h.

[0055] 3. Beneficial effects

[0056] Compared with the prior art, the present application has the following beneficial effects:

[0057] The inorganic-biological hybrid provided in the present application, as well as its preparation method and application, hybridizes multi-walled carbon nanotubes and activated sludge from a denitrification biological filter to form an inorganic-biological hybrid, which is used to enhance the hydrogen-based membrane bioreactor for wastewater denitrification. The inorganic-biological hybrid attaches to the hollow fiber membrane to form a biofilm, which can significantly improve the H2 utilization rate of the H2-MBfR and achieve an H2 utilization rate of ≥80%; at the same time, when treating the same volume of wastewater, the H2-MBfR can reduce the H2 supply by 50%. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 The figures are SEM images, wherein (a) is the SEM image of traditional activated sludge; and (b) is the SEM image of the inorganic-biological hybrid prepared in Example 1.

[0059] Figure 2This is a schematic diagram of the structure of the inorganic-biological hybrid enhanced hydrogen-based membrane bioreactor (H2-MBfR).

[0060] Figure 3 The denitrification rate and H2 utilization rate of traditional hydrogen-based membrane bioreactors and inorganic-biological hybrids were enhanced.

[0061] Figure 4 The denitrification rate and H2 utilization rate of traditional hydrogen-based membrane bioreactors and inorganic-biological hybrids were enhanced. DETAILED DESCRIPTION

[0062] The present application is further described below in conjunction with specific embodiments.

[0063] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0064] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0065] Concentration, amount and other numerical data may be presented in range format herein. It should be understood that such range format is used only for convenience and brevity, and should be flexibly interpreted to include not only the values ​​explicitly recited as range limits, but also all individual values ​​or sub-ranges included within the range, just as each value and sub-range is explicitly recited.

[0066] Example 1

[0067] This embodiment provides an inorganic-biological hybrid and a preparation method thereof.

[0068] The inorganic-biological hybrid is a hybrid of multi-walled carbon nanotubes (MWCNTs) and activated sludge from a denitrifying biological filter, and the preparation method thereof comprises the following steps:

[0069] (1) 1.0 g of multi-walled carbon nanotubes (MWCNTs, Aladdin, C139872) was added to 1.0 L of N-methylpyrrolidone (NMP) and ultrasonicated for 6.0 h to form a 1.0 g / L uniform MWCNTs dispersion.

[0070] (2) 1.0 L of 1.0 g / L activated sludge from a denitrification biofilter (from Nanjing Jiangxinzhou Wastewater Treatment Plant) was added to the stirred MWCNTs dispersion at a rate of 100 mL / min, and then stirred for 10 min to form 2.0 L of an inorganic-biological hybrid precursor solution;

[0071] (3) The inorganic-biological hybrid precursor solution was allowed to stand for 20 min to separate layers, and then centrifuged at 3000 rpm to remove the supernatant to obtain the inorganic-biological hybrid.

[0072] The SEM image of the inorganic-biological hybrid prepared in this example is as follows Figure 1 As shown, (a) is a SEM image of traditional activated sludge, and (b) is a SEM image of the inorganic-biological hybrid prepared in Example 1, indicating that MWCNTs and activated sludge are composited to form an inorganic-biological hybrid.

[0073] Example 2

[0074] This example provides the use of an inorganic-biological hybrid in wastewater denitrification.

[0075] In this embodiment, the application is to use an inorganic-biological hybrid enhanced hydrogen-based membrane bioreactor to remove nitrogen from wastewater. The structural principle of the inorganic-biological hybrid enhanced hydrogen-based membrane bioreactor (H2-MBfR) is as follows: Figure 2 As shown, specifically, inorganic-biological hybrids attach to the hollow fiber membrane to form a biofilm, which can increase the H2 and NO3 - The diffusion rate in the biofilm is increased, thereby effectively alleviating the dual substrate diffusion limitation of H2-MBfR and improving its H2 utilization.

[0076] In this embodiment, the H2-MBfR used includes a hollow fiber membrane assembly made of polypropylene, wherein the effective length of the membrane filament is 10-20 cm, the outer diameter is 100-500 μm, and the membrane pore size is 0.01-0.45 μm; wherein the number of hollow fiber membrane filaments is 80, and the total effective area is 100 cm 2 .

[0077] Example 3

[0078] This example provides the use of an inorganic-biological hybrid in wastewater denitrification.

[0079] In this embodiment, the application is that the inorganic-biological hybrid is attached to the hollow fiber membrane to form a biofilm, and the inorganic-biological hybrid is used to enhance the hydrogen-based membrane bioreactor for wastewater denitrification, which specifically includes the following steps:

[0080] (1) Add culture medium (culture medium formula: 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution) to the inorganic-biological hybrid and wash it three times; then add 1.0 L of culture medium to mix to form a 2.0 g / L inorganic-biological hybrid dispersion; pump 1.0 L of the 2.0 g / L inorganic-biological hybrid dispersion into the H2-MBfR, and then load the inorganic-biological hybrid onto the hollow fiber membrane by filtration;

[0081] (2) The nutrient solution (nutrient solution formula: 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution) was pumped into the H2-MBfR, and H2 was passed into the hollow fiber membrane to acclimate the inorganic-biological hybrid on the hollow fiber membrane for 7 days;

[0082] (3) Low carbon-nitrogen ratio wastewater (nitrate nitrogen concentration of 70 mg / L; carbon-nitrogen ratio of 2.6) was pumped into the H2-MBfR, and H2 was passed into the hollow fiber membrane for denitrification experiments; the hydraulic retention time of the wastewater was controlled to 6.0 h by the pump speed, and the hydrogen flow rate was controlled to 0.4 mL / min by the gas flowmeter.

[0083] The denitrification rate was calculated by testing the nitrate nitrogen concentration in the H2-MBfR effluent at different times; the H2 utilization rate was calculated by testing the H2 concentration in the gas emitted from the H2-MBfR at different times.

[0084] The results are as follows Figure 3 As shown in Figure 2, the denitrification rate of the conventional activated sludge-based H2-MBfR is ~1.2 g / (m 2 d), the H2 utilization rate was 48%; the denitrification rate of the inorganic-biological hybrid H2-MBfR of the present invention was ~1.4 g / (m 2 d), the H2 utilization rate is 76%. Therefore, compared with the traditional activated sludge-based H2-MBfR, the inorganic-biological hybrid-based H2-MBfR of the present invention has a 17% higher denitrification rate and a 58% higher H2 utilization rate.

[0085] Example 4

[0086] This example provides the use of an inorganic-biological hybrid in wastewater denitrification.

[0087] In this embodiment, the application is that the inorganic-biological hybrid is attached to the hollow fiber membrane to form a biofilm, and the inorganic-biological hybrid is used to enhance the hydrogen-based membrane bioreactor for wastewater denitrification, which specifically includes the following steps:

[0088] (1) Add culture medium (culture medium formula: 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution) to the inorganic-biological hybrid and wash it three times; then add 1.0 L of culture medium to mix to form a 2.0 g / L inorganic-biological hybrid dispersion; pump 1.0 L of the 2.0 g / L inorganic-biological hybrid dispersion into the H2-MBfR, and then load the inorganic-biological hybrid onto the hollow fiber membrane by filtration;

[0089] (2) The nutrient solution (nutrient solution formula: 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution) was pumped into the H2-MBfR, and H2 was passed into the hollow fiber membrane to acclimate the inorganic-biological hybrid on the hollow fiber membrane for 7 days;

[0090] (3) Low carbon-nitrogen ratio wastewater (nitrate nitrogen concentration of 140 mg / L; carbon-nitrogen ratio of 2.6) was pumped into the H2-MBfR, and H2 was passed into the hollow fiber membrane for denitrification experiments; the hydraulic retention time of the wastewater was controlled to 8.0 h by the pump speed, and the hydrogen flow rate was controlled to 0.6 mL / min by the gas flowmeter.

[0091] The denitrification rate was calculated by testing the nitrate nitrogen concentration in the H2-MBfR effluent at different times; the H2 utilization rate was calculated by testing the H2 concentration in the gas emitted from the H2-MBfR at different times.

[0092] The results are as follows Figure 4 As shown in Figure 2, the denitrification rate of the conventional activated sludge-based H2-MBfR is ~2.9 g / (m 2 d), the H2 utilization rate was 52%; the denitrification rate of the inorganic-biological hybrid H2-MBfR of the present invention was ~5.4 g / (m 2 d), the H2 utilization rate is 96%, which is close to complete utilization. Therefore, compared with the traditional activated sludge-based H2-MBfR, the denitrification rate of the inorganic-biological hybrid-based H2-MBfR of the present invention is increased by 36%, and the H2 utilization rate is increased by 85%.

Claims

1. An application of an inorganic-biological hybrid in wastewater denitrification, characterized in that: The application is to use inorganic-biological hybrids to enhance hydrogen-based membrane bioreactors for wastewater denitrification; The inorganic-biological hybrid is formed by hybridizing multi-walled carbon nanotubes and activated sludge from a denitrification biological filter; The preparation method of the inorganic-biological hybrid comprises the following steps: S1, adding multi-walled carbon nanotubes into N-methylpyrrolidone, and forming a uniform multi-walled carbon nanotube dispersion after ultrasonic treatment; S2, adding activated sludge from a denitrification biofilter to the stirred multi-walled carbon nanotube dispersion, stirring and mixing to form an inorganic-biological hybrid precursor solution; S3, after the inorganic-biological hybrid precursor solution is allowed to stand for stratification, the supernatant is removed to obtain the inorganic-biological hybrid.

2. The use according to claim 1, characterized in that: The concentration of the multi-walled carbon nanotube dispersion is 0.1-1.0 g / L; and / or The MLSS of the activated sludge from the denitrification biofilter is 1.0-10 g / L; and / or The volume ratio of the multi-walled carbon nanotube dispersion to the activated sludge is 1:0.1-1:

10.

3. The use according to claim 2, characterized in that: In step S1, the ultrasonic treatment time is 2.0 to 6.0 h; and / or In step S2, the activated sludge is added at a rate of 1.0-100 mL / min; and / or In step S2, the stirring and mixing time is 5.0 to 30 min; and / or In step S3, the standing time is 10 to 60 min.

4. The use according to claim 3, characterized in that: The wastewater is low carbon-nitrogen ratio wastewater.

5. The use according to claim 3 or 4, characterized in that: The application comprises the following steps: M1, pumping the inorganic-biological hybrid dispersion into the membrane bioreactor; M2, the inorganic-biological hybrid is filtered and retained on the hollow fiber membrane assembly of the membrane bioreactor; the inorganic-biological hybrid is attached to the hollow fiber membrane to form a biofilm; M3, a nutrient solution is introduced into the membrane bioreactor, and hydrogen is introduced into the hollow fiber membrane to acclimate the inorganic-biological hybrid; the nutrient solution formula is 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution; M4, after the acclimation is completed, the wastewater is pumped into the membrane bioreactor for denitrification.

6. The use according to claim 5, characterized in that: The concentration of the inorganic-biological hybrid dispersion is 1.0-10 g / L; the preparation method of the inorganic-biological hybrid dispersion comprises: adding culture solution to the inorganic-biological hybrid for washing, and mixing with the culture solution after washing to form the inorganic-biological hybrid dispersion; the culture solution formula is 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 mL / L vitamin solution and 12.5 mL / L trace mineral solution.

7. The use according to claim 6, characterized in that: The flow rate of the hydrogen is 0.01-1 mL / min; and / or The acclimatization time is 3 to 7 days; and / or The hydraulic retention time of the wastewater is 6.0~24 h.

8. A method for denitrification of low carbon-nitrogen ratio wastewater, characterized in that: The method comprises the following steps: N1, pumping the inorganic-biological hybrid dispersion of the inorganic-biological hybrid described in claim 1 into a membrane bioreactor; N2, the inorganic-biological hybrid is filtered and retained on the hollow fiber membrane assembly of the membrane bioreactor; the inorganic-biological hybrid is attached to the hollow fiber membrane to form a biofilm; N3, a nutrient solution is introduced into the membrane bioreactor, and hydrogen is introduced into the hollow fiber membrane to acclimate the inorganic-biological hybrid; the nutrient solution formula is 50 mM phosphate buffer solution, 5 ml / L vitamin solution and 12.5 ml / L trace mineral solution; N4, after the acclimation is completed, the wastewater is pumped into the membrane bioreactor for denitrification.

9. The method according to claim 8, characterized in that The concentration of the inorganic-biological hybrid dispersion is 1.0-10 g / L; the preparation method of the inorganic-biological hybrid dispersion comprises: adding culture solution to the inorganic-biological hybrid for washing, and mixing with the culture solution after washing to form the inorganic-biological hybrid dispersion; the culture solution formula is 1.0 g / L sodium acetate, 50 mM phosphate buffer solution, 5 mL / L vitamin solution and 12.5 mL / L trace mineral solution.

10. The method according to claim 9, characterized in that The flow rate of the hydrogen is 0.01-1 mL / min; and / or The acclimatization time is 3 to 7 days; and / or The hydraulic retention time of the wastewater is 6.0~24 h.

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