CN102826646A - Catalytic iron internal electrolysis biological fluidization filler and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of waste water treatment, and discloses a biological fluidization filler for catalytic iron internal electrolysis and a preparation method thereof. The biological fluidized filler for internal electrolysis of catalytic iron disclosed by the invention comprises the following components and percentage by weight: 10-15% of shell, 80-90% of catalytic iron and 0-5% of specific gravity adjusting material. The preparation method of the catalytic iron internal electrolysis biological fluidized filler disclosed by the invention comprises the following steps: pressing the catalytic iron into a catalytic iron internal electrolytic material of a certain shape, filling the catalytic iron internal electrolytic material and the specific gravity adjustment material into the shell, or The electrolytic material in the catalytic iron is directly filled into the housing with regulating function, thus making a fluidizable biofiller. The invention solves the shortcoming that the inner electrolysis of the catalytic iron is easily blocked, and fully retains the technical advantages of the inner electrolytic filling of the catalytic iron, such as cheap and easy to obtain, harmless to the environment, strong reducing ability, good effect, and wide applicable pH range.

Description

A biological fluidized filler for catalytic iron internal electrolysis and its preparation method

technical field

The invention belongs to the field of waste water treatment, and in particular relates to a catalytic iron internal electrolysis biological fluidization filler and a preparation method thereof.

Background technique

In order to improve the microbial biomass and activity in wastewater biological treatment systems, scientists and engineers have developed a variety of biological carrier fillers. According to the different installation methods of packing, it can be divided into fixed type and fluidized type. The former includes soft, semi-soft packing, composite packing, elastic packing, etc. Although these packings are relatively cheap, they require corresponding packing frames for installation, which not only increases the investment and the difficulty of packing replacement, but also affects the related water under the packing. Maintenance and replacement of processing equipment (such as aeration, stirring, water distribution, etc.). The fluidized packing is easy to use and replace, and the dosage can be adjusted at any time according to the actual needs. Therefore, the current fluidized packing has become a hot spot in the research and application of biological carriers, and a variety of different forms of fluidized packing have also been developed, such as "a cycle Type water treatment fluidized packing" (patent application number: 200720128864.7), "a high-efficiency denitrification water treatment fluidized packing" (patent application number: 200720128865.1), "hollow tooth-shaped fluidized packing" (patent application number: 200510116790.0) , "multi-surface fluidized packing" (patent application number: 200610137088.7), "improved biological fluidized packing" (patent application number: 200520128198.85), etc. The main purpose of developing these packings is to increase the specific surface area of the packing and reduce the fluidization time. It needs power, improves the use efficiency of fillers, etc., while other functions are relatively small. In order to further improve the removal efficiency of fluidized carrier packing for pollutants, a fluidized packing with biocatalysis has been developed, such as "Preparation method of biocatalytic composite packing for biological fluidized bed" (patent application number: 200410018319.3), The filler is made of a certain proportion of activated carbon, ultra-high molecular weight polyethylene, iron, and manganese through high-temperature roasting at 500-560°C. Due to the existence of iron and manganese, on the one hand, it increases the electron transfer function and improves the metabolic rate of organisms; on the other hand, it can also promote the efficient completion of biochemical processes under anaerobic conditions, expanding the use range of fillers. It can be seen that the production conditions of this type of filler are relatively high, which limits its popularization and application.

Catalytic iron internal electrolysis technology can convert toxic and harmful refractory organic pollutants in wastewater into low-toxic or non-toxic biodegradable substances by reduction method, and the iron ions produced at the same time can precipitate phosphate and stimulate the metabolism of microorganisms , enhance the film-hanging performance of traditional biological carriers, and promote the proliferation of nitrifying bacteria, so it can be used as a single treatment unit or in combination with biological treatment technologies, such as "a catalytic iron electrolysis sewage treatment method and the filler used therein" (Patent Application No.: 200510029765.9), "A Method for Cooperative Treatment of Industrial Wastewater by Catalytic Iron Reduction and Anaerobic Hydrolysis and Acidification" (Patent Application No.: 20081019601.0). The method has low requirements on external conditions such as pH and is easy to apply, so it has been applied in engineering and achieved ideal results. However, in practical applications, due to the heavy electrolytic filler in the catalytic iron, it usually exists in a static state in the system. Therefore, although the bulk density of the filler used is small and the void ratio of the filler reaches more than 95%, with the extension of the operating time , the inevitable clogging phenomenon hinders the direct contact between the waste water and the filler and reduces the treatment effect. In addition, the installation of traditional catalytic iron packing requires a special support frame, which is difficult to install and replace. Therefore, when using this kind of catalytic iron inner electrolytic filler, we have to consider how to reduce the occurrence of this kind of phenomenon and take various measures, which affects the popularization and application of this technology to a certain extent.

Contents of the invention

The purpose of the present invention is to provide a catalytic iron internal electrolysis biological fluidization filler.

Another object of the present invention is to provide a preparation method of the above-mentioned internal electrolysis biological fluidized filler in catalytic iron.

Technical scheme of the present invention is as follows:

The invention provides a catalytic iron internal electrolysis biofluidization filler, which comprises the following components and weight percentages:

Shell 10-15%,

Catalytic iron 80-90%,

Specific gravity adjustment material 0-5%.

The shell is a polymer material that can be used in existing suspended biological carriers, and is selected from polyethylene or polypropylene materials.

The catalytic iron is selected from one or both of iron shavings or copper shavings; wherein, the iron shavings are scraps after cast iron processing, the carbon content in the iron is 0.05-0.5%, and the thickness of the iron shavings is 1.0-2.0mm. Ductility and tensile strength, except iron shavings, other impurities (such as dust, sundries, etc.) ≤ 2%; copper shavings are made of copper material, with a thickness of 0.5-1.0mm, a length of 5-150mm, an average length of 60mm, and a width of 2-20mm.

The specific gravity adjustment material is selected from foamed plastics or hollow plastic balls and other materials whose apparent specific gravity is smaller than water, or the hemispherical caps directly processed into mesh using polyethylene or polypropylene materials as shells, and each hemispherical cap is made When the non-porous part is hollow, it forms an air bag, which can generate buoyancy, and obtain a shell with a specific gravity adjustment function.

The present invention also provides a method for preparing the above-mentioned catalytic iron internal electrolysis biological fluidized filler, the method comprising the following steps:

The catalytic iron is pressed into a certain shape of the catalytic iron inner electrolytic material, and the catalytic iron inner electrolytic material and the specific gravity adjustment material are filled into the shell, or the catalytic iron inner electrolytic material is directly filled into the outer shell with the adjustment function, thus making it possible Fluidized biofill.

The catalytic iron is pressed into a catalytic iron inner electrolytic material of a certain shape, comprising the following steps: mixing iron shavings and copper shavings according to a mass ratio of 10:1 to 20:1, and pressing them into a bulk specific gravity of 0.15 to 0.30, Spherical or hemispherical crown catalytic iron inner electrolytic material with a diameter of 35-145mm; or first press iron shavings into unit blocks with the same bulk specific gravity, diameter and shape, and then copper-plated and palladium-plated according to the mass ratio of 0.2%-1.0% Or silver plating, etc., can be prepared in the catalytic iron electrolytic material.

The shell is two hemispherical spherical bio-suspension fillers, or the polymer material is processed into two reticular hemispherical spherical caps with an outer diameter of 40-150mm and an inner diameter of 35-145mm, with a porosity of 35- 65%, the non-porous part of each hemispherical crown is hollow to form an air bag; wherein, the polymer material is selected from polyethylene or polypropylene material.

The buoyancy formed by the airbag in water is equal to 0.95-1.05 times of the gravity generated by the combined filler, and the gravity generated by the combined filler includes: the gravity generated by the filler shell itself and the gravity generated by the electrolytic material in the internal catalytic iron, so that the filler itself can Directly suspended or suspended in water under slight turbulent conditions; the shell of the catalytic iron inner electrolysis biofluidization filler obtained by this method also plays the function of adjusting the specific gravity, so the catalytic iron inner electrolysis biofluidization filler The catalytic iron material accounts for 85%-90% of the total weight, the shell material accounts for 10%-15% of the total weight, and the specific gravity adjustment material accounts for 0%.

The addition ratio of the specific gravity adjustment material is equal to 0.95-1.05 times of the gravity generated by the combined filler in terms of the buoyancy formed in water. The gravity generated by the combined filler includes: the gravity generated by the outer shell, the gravity generated by the electrolytic material in the internal catalytic iron, and the specific gravity adjustment The gravity generated by the material itself enables the filler itself to be suspended directly or suspended in water under slightly turbulent conditions. The catalytic iron inner electrolysis biofluidized packing obtained by this method has a catalytic iron material that accounts for 85%-90% of the weight of the entire packing, a specific gravity adjustment material that accounts for 1%-5%, and a shell material that accounts for 10%. -15% between.

As mentioned above, the electrolytic filler block in the catalytic iron must be firmly combined with the shell material and the specific gravity adjustment material, and the principle of bio-adhesive material (as a combined filler shell) outside and the electrolytic filler inside the catalytic iron must be followed to give full play to their respective functions. function. In addition, the shell material must have a large enough gap (35%-65%), even after the biofilm is formed, it can also make the waste water smoothly enter the interior of the electrolytic filler in the catalytic iron.

The invention makes the electrolytic filler in the catalytic iron suspend and fluidize through the clever use of the specific gravity adjustment material, and effectively solves the problem of blockage that may occur during the use of the traditional catalytic iron inner electrolytic filler while ensuring the electrolytic treatment effect in the catalytic iron . In addition, the combination with the existing biological carrier not only strengthens the film-hanging performance of the existing biological adhesion materials, thereby increasing the biomass and activity, but also ensures the reducing conditions for catalyzing the internal electrolysis of iron and reduces the consumption of iron.

The key technology of the invention is the control of the specific gravity adjusting material, that is, in the production process, the buoyancy produced by the specific gravity adjusting material is required to be equal to 0.95 to 1.05 times the gravity of the overall combined packing.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

1. The present invention solves the shortcoming that the electrolysis in the catalytic iron is easy to block, and fully retains the technical advantages of the electrolytic filling in the catalytic iron, such as cheap and easy to obtain, harmless to the environment, strong reducing ability, good effect, and a wide range of applicable pH wait.

2. The preparation method of the filler carrier of the present invention is simple, and the materials are easy to obtain. Some waste materials can be used, and the existing filler or filler manufacturing technology can be fully utilized without special equipment or technology.

3. The packing carrier of the present invention is easy to use and replace, and can be used in different pool shapes, and can also be used in different environmental conditions such as anaerobic, anoxic, and aerobic.

4. The present invention realizes the mutual coupling between catalytic iron electrolysis and biology, and exerts the synergistic effect of the two. The iron ions produced by catalyzing the internal electrolysis of iron can directly change the film-hanging performance of the external biological attachment carrier, so there is no need to perform surface activation treatment on the existing biological carrier, and it also has a strengthening effect on the external organisms. However, because the outside is covered with biofilm, it ensures that the internal catalytic iron electrolysis is in anaerobic and anoxic state, fully exerts its reducing ability, and reduces the consumption of iron.

Detailed ways

The present invention will be further described below in conjunction with embodiment.

Example 1

Leftovers after cast iron processing-iron shavings and copper shavings are made into a spherical catalytic iron unit material with a diameter of 95mm according to a ratio of 10:1, and the bulk specific gravity is 0.15. The carbon content of the iron shavings used is 0.5%, and the thickness of the iron shavings is 2.0mm, with ductility and tensile strength, except for iron shavings, other impurities are 2%, the copper shavings used are processed from copper sheets, the thickness is 1.0mm, the length is 100mm, and the width is 15mm. In addition, polyethylene material is used to make a mesh hemispherical cap with an outer diameter of 100 mm and an inner diameter of 95 mm. Its porosity is 55%. The non-porous part of each hemispherical cap is hollow to form an air bag. The buoyancy of the shell is equal to the shell Its gravity is 0.95 times the sum of the gravity of the spherical catalytic iron unit material. The spherical catalytic iron unit material is placed in two hemispherical crown shells, combined and fixed, and the catalytic iron material in the electrolytic biofluidized filler in the finally obtained catalytic iron accounts for 90% of the total weight, and the outer shell (which itself has a regulating function) accounts for 90% of the total weight. 10% of the total weight, 0% of the specific gravity adjustment material. The obtained filler is placed in a suspended state in the pilot CAST tank for treating wastewater in chemical industry parks, and fluidization can be achieved with aeration. After 7 days, the surface of the biofiller was covered with biofilm, and the microscopic examination found that the biophase was extremely rich, while the interior was in an anoxic state. After long-term operation, it is found that the electrolytic filler in the internal catalytic iron still has good water-passing performance, and there is no clogging phenomenon.

Example 2

The scrap iron shavings and copper shavings processed by cast iron will be made into a hemispherical crown catalytic iron unit material with a diameter of 145mm according to a ratio of 15:1. The bulk specific gravity is 0.2, and the carbon content of the iron shavings used is 0.05%. The thickness is 1.0mm, with ductility and tensile strength. Except for iron shavings, the other impurities are 2%. The copper shavings used are processed from copper sheets. The thickness is 0.5mm, the length is 150mm, and the width is 5mm. The electrolytic material in the catalytic iron is placed in the existing spherical suspension filler with a diameter of 150 mm, and foam plastic is placed at the center of the catalytic iron unit material, so that the buoyancy of the foam plastic is equal to 1.0 times the gravity of the electrolytic biofluidized filler in the entire catalytic iron. The catalytic iron part of the electrolytic biological fluidized filler in the finally formed catalytic iron accounts for 80% of the total weight, the shell accounts for 13%, and the specific gravity adjustment material accounts for 2%. Put this filler directly in the pilot CAST tank for wastewater treatment in chemical industrial parks in a suspended state, and fluidization can be achieved under aeration. After 7 days, the surface of the biofiller was covered with biofilm, and the microscopic examination found that the biophase was extremely rich, while the interior was in an anoxic state. After long-term operation, it is found that the electrolytic filler in the internal catalytic iron still has good water-passing performance, and there is no clogging phenomenon. The same suspension carrier was directly placed in the pilot test hydrolysis acidification tank for the treatment of wastewater in the chemical industry park, making it in a suspended fluidized state. After 10 days, the outside of the filler was also covered with microorganisms. Long-term operation found that there is no blockage inside.

Example 3

The scrap iron shavings and copper shavings processed by the cast iron will be made into a hemispherical crown catalytic iron unit material with a diameter of 36mm according to the ratio of 20:1, the bulk specific gravity is 0.3, and the carbon content of the iron shavings used is 0.1%. The thickness is 1.5mm, with ductility and tensile strength. Except for iron shavings, other impurities are 1%. The copper shavings used are processed from copper sheets. The thickness is 0.5mm, the length is 50mm, and the width is 10mm. Put the inner electrolytic material into a shell with a diameter of 38mm, add a specific gravity adjustment material made of foam (the buoyancy generated by the foam is equal to 0.95 times the gravity of the entire combined packing that is finally formed), and fix the shell to form a material that can be suspended in water. The catalytic iron internal electrolysis biological fluidized packing, the catalytic iron carrier in the fluidized packing accounts for 85% of the total weight, the shell accounts for 10%, and the specific gravity adjustment material accounts for 5%. The filler is used to treat glyphosate wastewater, and fluidization is realized under the condition of hydraulic agitation, and its long-term treatment effect is better than that of the fixed catalytic iron internal electrolysis filler system, and the phosphorus removal rate is increased by about 20%. And after one month of operation, no clogging phenomenon was found, and the treatment effect did not decline.

The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative efforts. Therefore, the present invention is not limited to the embodiments herein. Improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims (10)

1. A biological fluidization filler for electrolysis in catalytic iron, characterized in that: the electrolytic biological fluidization filler in catalytic iron comprises the following components and weight percentages: Shell 10-15%, Catalytic iron 80-90%, Specific gravity adjustment material 0-5%. 2. The biofluidized filler for catalytic iron inner electrolysis according to claim 1, characterized in that: the shell is a polymer material that can be used for existing suspended biological carriers, and is selected from polyethylene or polypropylene materials. 3. The biological fluidized filler for electrolysis in catalytic iron according to claim 1, characterized in that: the catalytic iron is selected from one or both of iron shavings and copper shavings. 4. The biofluidized filler for catalytic iron internal electrolysis according to claim 3, characterized in that: the iron shavings are scraps after cast iron processing, the carbon content in the iron is 0.05-0.5%, and the thickness of the iron shavings is 1.0-2.0 mm, except iron shavings, other impurities ≤ 2%; the copper shavings are made of red copper, with a thickness of 0.5-1.0mm, a length of 5-150mm, and a width of 2-20mm. 5. The biofluidized filler for electrolysis in catalytic iron according to claim 1, characterized in that: the specific gravity adjustment material is selected from foamed plastics or hollow plastic balls, or is directly processed into a net using polyethylene or polypropylene materials Shaped hemispherical crowns are used as the shell, and the non-porous part of each hemispherical crown is hollow when manufactured to form an air bag, and a shell with a specific gravity adjustment function is obtained. 6. The preparation method of any one of claims 1 to 5, wherein the catalytic iron internal electrolysis biological fluidized filler is characterized in that: the method comprises the following steps: pressing the catalytic iron into a catalytic iron internal electrolytic material of a certain shape; The inner iron electrolytic material and the specific gravity adjustment material are filled into the casing, or the catalytic iron inner electrolytic material is directly filled into the outer casing with regulating function, thereby making a fluidizable biological filler. 7. The preparation method of electrolytic biological fluidized filler in catalytic iron according to claim 6, characterized in that: described catalytic iron is pressed into a certain shape of electrolytic material in catalytic iron, comprising the following steps: iron shavings and copper The shavings are mixed according to the mass ratio of 10:1 to 20:1, and pressed into a spherical or hemispherical crown catalytic iron inner electrolytic material with a bulk specific gravity of 0.15 to 0.30 and a diameter of 35 to 145mm; or the iron shavings are first pressed into the same stacked The specific gravity, diameter, and shape of the unit block are then plated with copper, palladium, or silver according to the mass ratio of 0.2% to 1.0%, so that the catalytic iron inner electrolytic material can be prepared. 8. The preparation method of electrolytic biological fluidized filler in catalytic iron according to claim 6, characterized in that: the shell is a spherical biological suspension filler with two hemispherical crowns, or the polymer material is processed into an outer diameter Two mesh hemispherical caps with a diameter of 40-150 mm and an inner diameter of 35-145 mm, with a porosity of 35-65%, and the non-porous part of each hemispherical cap is hollow to form an air bag; wherein, the polymer material is selected from polyethylene or polypropylene material. 9. The preparation method of electrolytic biological fluidized filler in catalytic iron according to claim 8, characterized in that: the buoyancy formed by the airbag in water is equal to 0.95-1.05 times of the gravity produced by the combined filler, and the combined filler produces Gravity includes: the gravity generated by the packing shell itself and the gravity generated by the internal catalytic iron inner electrolytic material; the catalytic iron inner electrolysis biofluidized packing obtained by this method, the catalytic iron material part accounts for 85%-90% of the total weight, and the outer shell The material accounts for 10%-15% of the total weight. 10. The preparation method of electrolytic biofluidized filler in catalytic iron according to claim 6, characterized in that: the proportion of adding the specific gravity adjustment material is equal to 0.95-1.05 times of the gravity generated by the combined filler because of the buoyancy it forms in water , the gravity generated by the combined filler includes: the gravity generated by the shell, the gravity generated by the electrolytic material in the internal catalytic iron, and the gravity generated by the specific gravity adjustment material itself. In this way, the obtained electrolytic biofluidized filler in the catalytic iron is produced. The catalytic iron material It accounts for 85%-90% of the weight of the whole packing, the specific gravity adjustment material accounts for 1%-5%, and the shell material accounts for 10%-15%.