WO2018233613A1

WO2018233613A1 - Method for processing waste incineration fly ash by using biogas residues

Info

Publication number: WO2018233613A1
Application number: PCT/CN2018/091900
Authority: WO
Inventors: 张大磊; 于淼成; 赵建雪; 赵峰
Original assignee: 青岛理工大学; 青岛洁华环境科技有限公司
Priority date: 2017-06-20
Filing date: 2018-06-20
Publication date: 2018-12-27
Also published as: CN107497094A

Abstract

In the present disclosure, a method for processing waste incineration fly ash by using biogas residues is designed. The method for processing waste incineration fly ash by using biogas residues comprises: digging out fly ash at a polluted site, and transferring the fly ash to a storage yard; laying an impermeable layer in the storage yard, laying a flow guide material at the bottom, laying a mixture layer comprising biogas residues, a carbon source, sulfate, nutritional additives and fly ash on the upper part thereof, and placing a mixture layer comprising a titanium material and a nano-iron material on the upper part of the mixture layer; and in the operating process, irregularly injecting a carbon source solution from the upper part of the storage yard, irregularly collecting leachate into a leachate collection system by means of a flow guide material on the bottom, and then making the leachate flow back to the top of the storage yard for spraying and recharging. By processing the fly ash by using the method, heavy metals are fixed on the storage yard, and dioxin in the fly ash is rapidly degraded.

Description

Method for treating waste incineration fly ash by using biogas residue

Cross-reference to related applications

The present application claims priority to Chinese Patent Application No. 2017104713073 , entitled "A Method for Disposing Waste Incineration Fly Ash Using Biogas Residues ", submitted to the Chinese Patent Office on June 20, 2017, the entire contents of which are incorporated by reference. In this application.

Technical field

The present disclosure relates to the field of environmental protection, and in particular to a method for treating waste incineration fly ash using biogas residue.

Background technique

Waste incineration fly ash is classified as hazardous waste due to its high concentration of heavy metals and dioxin-like POPs. During its transportation and open-pit filling, it is easy to form dust into the atmosphere, not only in the air. The dust content will increase the ecological toxicity of smog, cause serious pollution to the atmosphere, and endanger the health and ecological environment of residents.

Fly ash is a kind of hazardous waste. At present, it is mainly landfill, but landfill occupies a large amount of land. How to convert it into harmless waste in the landfill process needs to be considered.

Summary of the invention

In view of the deficiencies of the prior art, the present disclosure devises a method for treating waste incineration fly ash by using biogas residue, which can fix heavy metals in fly ash in the yard and rapidly degrade dioxin in fly ash.

Embodiments of the present disclosure are implemented by the following schemes:

The method for treating waste incineration fly ash using biogas residue includes the following steps:

An anti-seepage layer is laid in the yard for the disposal of fly ash, and a diversion material is laid at the bottom, and a mixed layer of biogas residue, carbon source, sulfate, nutritive additive and fly ash is laid on the upper part, and titanium material and nanometer are placed on the upper part of the mixed layer. Mixed layer of iron material; during operation, the carbon source solution is injected from the upper part of the stack from time to time, and the leachate is collected from the bottom deflecting material to the leachate collection system from time to time, and then the leachate is returned to the top of the yard for spraying. Refill.

After the fly ash is treated by the method, the heavy metal in the fly ash can be fixed in the yard, and the dioxin in the fly ash is rapidly degraded. Further, first, the sulfate reducing bacteria in the biogas residue converts the sulfate into a sulfide by using a carbon source, and the heavy metal reacts with the sulfide to form a precipitate of extremely low solubility, which greatly reduces the amount of dissolution. At the same time, the dioxin in the fly ash is extracted into the solution by using a carbon source solution such as ethanol, and the dioxin pollutant enters the leachate, and is sprayed with the leachate to the top of the stack, and is retained by the nano-iron material in the titanium-containing material. Under the action of the material, a photocatalytic effect is formed to generate hydroxyl radicals, which further promotes the dechlorination effect of dioxins; in addition, by controlling the pH of the leachate, the nano-iron material releases a certain amount of iron ions. Under the action of trace hydroxyl radicals generated by photocatalysis, combined with iron ions and low pH, Fenton catalytic effect will be produced, which will more effectively dechlorinize dioxins and effectively degrade dioxin pollution. During the process, the biodegradability of the leachate is improved, and then the leachate is infiltrated into the mixed layer and is better utilized by the microorganisms in the biogas residue. In addition, the advanced oxidation of nano-iron and titanium-containing materials can lead to more efficient degradation of organic pollution.

Optionally, in an embodiment of the present disclosure, the fly ash, the biogas residue, the carbon source, the sulfate, and the nutritional additive in the mixed layer are added in a mass ratio of 1: (0.01-0.5): (0.01-0.5) : (0.05-0.3): (0.05-0.1).

Optionally, in an embodiment of the present disclosure, the carbon source in the mixed layer includes organic waste, including kitchen waste, domestic garbage, and the like.

Optionally, in an embodiment of the present disclosure, the mixed layer has a thickness of 1-8 m.

Optionally, in an embodiment of the present disclosure, the mixed layer of the titanium-containing material and the nano-iron material has a thickness of not more than 1 m.

The mixing ratio of the titanium-containing material and the nano-iron material is (0.01-100): 1.

Optionally, in one embodiment of the present disclosure, the spraying interval of the leachate flowing back to the top of the stack for spraying and refilling is 1-48 hours.

Optionally, in one embodiment of the present disclosure, the leachate is refluxed to the top of the yard for spraying and recharging to adjust the pH of the leachate, so that the pH of the recirculated leachate is 2-6.

Optionally, in an embodiment of the present disclosure, the biogas residue comprises organic wastewater, solid organic waste or sludge.

Optionally, in an embodiment of the present disclosure, the mixed layer thickness of the titanium-containing material and the nano-iron material does not exceed 1 m.

Optionally, in an embodiment of the present disclosure, during operation, the frequency of the carbon injection source solution in the upper portion of the stack is once per 1-100 days of the carbon injection source solution.

Optionally, in an embodiment of the present disclosure, the nutritional additive comprises one or more of a nitrogen source, a phosphorus source, and a trace element source.

Alternatively, in one embodiment of the present disclosure, the sulfate salt comprises an inorganic salt or waste containing sulfate.

Optionally, in one embodiment of the present disclosure, the sulfate comprises sodium sulfate.

Alternatively, in one embodiment of the present disclosure, the sulfate is gypsum.

Optionally, in an embodiment of the present disclosure, the nutritional additive comprises a mixture of potassium phosphate, ammonium nitrate, and cobalt nitrate, and one or more of the trace element sources are added.

Optionally, in an embodiment of the present disclosure, the trace element source comprises a nutrient containing one or more elements of boron, zinc, copper, manganese, cobalt, and the carbon source solution comprises ethanol, methanol, acetic acid. One or more solutions that can be used both as a microbial carbon source and as a POP, such as dioxins in fly ash.

Optionally, in an embodiment of the present disclosure, the titanium-containing material is a titanium dioxide material.

Alternatively, in one embodiment of the present disclosure, the titanium-containing material may be replaced by other photocatalytic materials. Fly ash includes fly ash after biochemical, physical or chemical disposal. The fly ash can be untreated fly ash or fly ash after biochemical or physicochemical treatment.

Compared with the traditional fly ash processing method, this method has the following advantages:

1. Through the titanium-containing material, the photocatalytic effect is formed, synergistically with the adsorption of nano-iron and the advanced oxidation effect of Fenton, the dioxin pollution in the fly ash is quickly disposed, and the microbial metabolism in the biogas residue is coordinated and the dioxin pollution is treated to form an advanced Oxidation and biochemical synergistic treatment of dioxin pollution;

2. The use of biogas residue to dispose of fly ash to waste waste, that is, the disposal of fly ash, and the pollution of biogas residue is also harmless;

3. Sulfate-reducing bacteria in biogas residue make full use of sulfate to immobilize heavy metals, which is ecologically safe compared with direct use of chemical curing agent to fix heavy metals.

4. The addition of phosphorus source, nitrogen source and trace elements further promotes the activity of microorganisms in biogas residue and enhances its ability to treat POPs pollution.

DRAWINGS

In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings to be used in the embodiments will be briefly described below. It should be understood that the following drawings show only certain embodiments of the present disclosure, and thus It should be seen as a limitation on the scope, and those skilled in the art can obtain other related drawings according to these drawings without any creative work.

1 is a schematic view of a method of treating waste incineration fly ash using biogas residue of the present disclosure.

Icons: 1-acid addition device; 2-mixed layer of titanium-containing material and nano-iron material; 3-impermeable layer; 4-mixed layer; 5-flow material; 6-leachate storage tank.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described in the following with reference to the accompanying drawings in the embodiments of the present invention. The embodiments are a part of the embodiments of the invention, and not all of the embodiments. The components of the embodiments of the invention, which are generally described and illustrated in the figures herein, may be arranged and designed in various different configurations.

Therefore, the following detailed description of the embodiments of the present invention are not intended to limit the scope of the claimed All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.

It should be noted that similar reference numerals and letters indicate similar items in the following figures. Therefore, once an item is defined in one figure, it is not necessary to further define and explain it in the subsequent figures.

Referring to FIG. 1 , a method for treating waste incineration fly ash by using biogas residue according to an embodiment of the present application includes laying an anti-seepage layer 3 in a yard for fly ash disposal, and laying a flow guiding material 5 at the bottom, and laying the upper part thereof. The invention comprises a mixed layer 4 of biogas residue, carbon source, sulfate, nutritive additive and fly ash, and a mixed layer 2 containing titanium material and nano iron material is placed on the upper part of the mixed layer 4; during operation, the carbon source is injected from the upper part of the stack from time to time. The solution, from time to time, collects the leachate through the bottom flow guiding material 5 into the leachate collection system, and then returns the leachate to the top of the yard for spraying back.

Among them, the mixed ash, biogas residue, carbon source, sulfate and nutritional additives in the mixed layer 4 are added in a ratio of 1: (0.01-0.5): (0.01-0.5): (0.05-0.3): (0.05-0.1) ).

Optionally, the mixed layer 4 has a thickness of 1-8 m; the mixed layer 2 of the titanium-containing material and the nano-iron material has a thickness of not more than 1 m.

Optionally, the mixing ratio of the titanium-containing material to the nano-iron material is (0.01-100): 1.

Among them, the spraying interval of leachate refluxing to the top of the yard for spraying and refilling is 1-48 hours.

Optionally, the leachate is refluxed to the top of the yard for pH adjustment of the leachate, and the pH of the recirculated leachate is 2-6. Optionally, the biogas residue includes organic wastewater, solid organic waste or sludge.

During operation, the frequency of carbon injection solution in the upper part of the yard is once per 1-100 days of carbon injection solution.

Optionally, the nutritional additive comprises one or more of a nitrogen source, a phosphorus source, and a trace element source, and the sulfate includes an inorganic salt or waste containing sulfate.

Alternatively, the sulfate salt comprises sodium sulfate. Alternatively, the sulfate is gypsum.

Optionally, the nutritional additive comprises a mixture of potassium phosphate, ammonium nitrate, and cobalt nitrate, with one or more of a source of trace elements added.

Optionally, the trace element source comprises a nutrient containing one or more elements of boron, zinc, copper, manganese, cobalt, and the carbon source solution comprises a solution containing one or more of ethanol, methanol, and acetic acid. Alternatively, the titanium-containing material may be replaced by other photocatalytic materials, including fly ash after biochemical, physical or chemical disposal.

Alternatively, the titanium-containing material is titanium dioxide.

The mechanism of the process for treating heavy metals and dioxins in fly ash is that first, the sulfate reducing bacteria in the biogas residue converts the sulfate into sulfide by using a carbon source, and the heavy metal reacts with the sulfide to form a precipitate with extremely low solubility, which is greatly reduced. Its amount of dissolution. At the same time, the dioxin in the fly ash is extracted into the solution by using a carbon source solution such as ethanol, and the dioxin pollutant enters the leachate, and is retentively sprayed to the top of the stack with the leachate, and is retained by the nano-iron material in the titanium-containing material. Under the action of the material, a photocatalytic effect is formed to generate hydroxyl radicals, which further promotes the dechlorination effect of dioxins. In addition, by controlling the pH of the leachate, the nano-iron material releases a certain amount of iron ions; The resulting trace of hydroxyl radicals, combined with low pH, produces a Fenton effect in the mixed layer (a mixed layer of titanium-containing material and nano-iron material), which is more efficient in dechlorination, thereby effectively degrading dioxin pollution. At the same time, the biodegradability of the leachate is improved, and then the leachate is infiltrated into the mixed layer and is better utilized by the microorganisms in the biogas residue.

Compared with the traditional fly ash processing method, the method has at least the following advantages:

Example 1

The embodiment provides a method for treating waste incineration fly ash by using biogas residue, which comprises digging out the contaminated site fly ash and transferring it to the yard; laying the anti-seepage layer 3 in the yard and laying the flow guiding material at the bottom 5 The upper part is provided with a mixed layer of biogas residue, sodium sulfate, kitchen waste, nutritional additive and fly ash, and the mixing ratio is fly ash, biogas residue, kitchen waste, sodium sulfate and nutritional additives, and the ratio is 1: 0.2:0.2:0.15:0.1, layer height 5m, titanium material and nano-iron material are placed on the upper part of the mixed layer 4, the layer height is 0.1m; during the operation, the ethanol solution is injected from the upper part of the yard every 1-5 days, and then The leachate is collected into the leachate collection system through the bottom flow guiding material 5, and then the leachate is returned to the upper portion of the stack for recirculation every 1-2 days, and the pH is adjusted to 4 before reflux.

After 60 days of disposal, the dissolution rate of heavy metals in fly ash decreased by 95%, Pb decreased from 5 mg/L to less than 0.1 mg/L, Cd decreased from 3 mg/L to less than 0.1 mg/L, and the removal rate of dioxin and other pollutants More than 99%, the dioxin content is up to standard. The nutritional additive of this embodiment is a mixture of potassium phosphate, ammonium nitrate and cobalt nitrate, and a trace amount of zinc element is added.

Example 2

The embodiment provides a method for treating waste incineration fly ash by using biogas residue, which comprises digging out the contaminated site fly ash and transferring it to the yard; laying the anti-seepage layer 3 in the yard and laying the flow guiding material at the bottom 5 The upper part is provided with a mixed layer of biogas residue, gypsum, kitchen waste, nutritional additive and fly ash 4, and the mixing ratio is fly ash, biogas residue, kitchen waste, gypsum and nutritional additive by mass ratio of 1:0.1: 0.2:0.05:0.05, the layer height is 8m, and the titanium-containing material and the nano-iron material layer are not disposed on the upper part of the mixed layer 4; during the operation, the alcohol solution is injected from the upper part of the stack every 1-5 days, and then the leachate is passed through the bottom guide. The flow material 5 is collected into a leachate collection system, and then the leachate is returned to the upper portion of the yard for recirculation every 1-2 days, and the leachate pH is adjusted to 4 during recharge.

After 75 days of disposal, the dissolution rate of heavy metals in fly ash decreased by 95%, b decreased from 5 mg/L to less than 0.1 mg/L, d decreased from 3 mg/L to less than 0.1 mg/L, and the removal rate of pollutants such as dioxins More than 99%, the dioxin content is up to standard. The nutritional additive is a mixture of potassium phosphate, ammonium nitrate and cobalt nitrate, and a trace amount of manganese and copper are added, and the titanium-containing material is titanium dioxide.

Example 3

The concentration of POPs in the treated fly ash was 926 mg/kg.

The embodiment provides a method for treating waste incineration fly ash by using biogas residue, which comprises digging out the contaminated site fly ash and transferring it to the yard; laying the anti-seepage layer 3 in the yard and laying the flow guiding material at the bottom 5 The upper part is laid with a mixed layer of biogas residue, sodium sulfate, domestic garbage and fly ash 4, and the mixing ratio is fly ash, biogas residue, domestic garbage, sodium sulfate, and the proportion by mass is 1:0.1:0.1:0.05, the layer height is 5m, no nutrient additive added, titanium material and nano-iron material are placed on the upper part of the mixed layer 4, the layer height is 0.1m; during the operation, the carbon source solution is injected from the upper part of the yard every 1-5 days, and then the leachate is passed through the bottom. The flow guiding material 5 is collected into the leachate collection system, and then the leachate is returned to the upper part of the yard for recirculation every 1-2 days, and the leachate pH is adjusted to 4 during the recharge.

After 75 days of disposal, the dissolution rate of heavy metals in fly ash decreased by 95%, Pb decreased from 5 mg/L to less than 0.1 mg/L, Cd decreased from 3 mg/L to less than 0.1 mg/L, and the removal rate of dioxin and other pollutants More than 99%, the dioxin content is up to standard, and the titanium-containing material is titanium dioxide.

Example 4

The embodiment provides a method for treating waste incineration fly ash by using biogas residue, which comprises digging out the contaminated site fly ash and transferring it to the yard; laying the anti-seepage layer 3 in the yard and laying the flow guiding material at the bottom 5 The upper part is provided with a mixed layer of biogas residue, sodium sulfate, kitchen waste, nutritional additives and fly ash, and the mixing ratio is fly ash, biogas residue, kitchen waste, sodium sulfate and nutritional additives, and the ratio is 1: 0.4:0.2:0.2:0.07, layer height 5m, titanium material and nano-iron material are placed on the upper part of the mixed layer 4, the layer height is 0.2m; during the operation, the ethanol solution is injected from the upper part of the yard every 1-7 days, and then The leachate is collected into the leachate collection system through the bottom flow guiding material 5, and then the leachate is returned to the upper portion of the stack for recirculation every 1-2 days, and the pH is adjusted to 2 before reflux.

After 60 days of disposal, the dissolution rate of heavy metals in fly ash decreased by 95%, Pb decreased from 5 mg/L to less than 0.1 mg/L, Cd decreased from 3 mg/L to less than 0.1 mg/L, and the removal rate of dioxin and other pollutants More than 99%, the dioxin content is up to standard. The nutritional additive of the example of the present example is a mixture of potassium phosphate, ammonium nitrate and cobalt nitrate, and a trace amount of zinc element is added, and the titanium-containing material is titanium dioxide.

Example 5

The embodiment provides a method for treating waste incineration fly ash by using biogas residue, which comprises digging out the contaminated site fly ash and transferring it to the yard; laying the anti-seepage layer 3 in the yard and laying the flow guiding material at the bottom 5 The upper part is provided with a mixed layer of biogas residue, sodium sulfate, kitchen waste, nutritional additives and fly ash, and the mixing ratio is fly ash, biogas residue, kitchen waste, sodium sulfate and nutritional additives, and the ratio is 1: 0.05:0.4:0.25:0.06, layer height 8m, titanium material and nano-iron material are placed on the upper part of the mixed layer 4, the layer height is 0.1m; during the operation, the ethanol solution is injected from the upper part of the yard every 1-5 days, and then The leachate is collected into the leachate collection system through the bottom flow guiding material 5, and then the leachate is returned to the upper portion of the stack for recirculation every 1-2 days, and the pH is adjusted to 3 before reflux.

Example 6

The embodiment provides a method for treating waste incineration fly ash by using biogas residue, which comprises digging out the contaminated site fly ash and transferring it to the yard; laying the anti-seepage layer 3 in the yard and laying the flow guiding material at the bottom 5 The upper part is provided with a mixed layer of biogas residue, sodium sulfate, kitchen waste, nutritional additive and fly ash, and the mixing ratio is fly ash, biogas residue, kitchen waste, sodium sulfate and nutritional additives, and the ratio is 1: 0.5:0.5:0.3:0.1, layer height 5m, titanium material and nano-iron material are placed on the upper part of the mixed layer 4, the layer height is 0.2m; during the operation, the ethanol solution is injected from the upper part of the yard every 1-5 days, and then The leachate is collected into the leachate collection system through the bottom flow guiding material 5, and then the leachate is returned to the upper portion of the stack for recirculation every 1-2 days, and the pH is adjusted to 6 before reflux.

The above is only a preferred embodiment of the present disclosure, and is not intended to limit the disclosure, and various changes and modifications may be made to the present disclosure. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the present disclosure are intended to be included within the scope of the present disclosure.

Industrial applicability

The method for treating waste incineration fly ash using the biogas residue of the present disclosure uses a carbon source to convert the sulfate into a sulfide, and the heavy metal reacts with the sulfide to form a precipitate of extremely low solubility, which greatly reduces the amount of dissolution. At the same time, the dioxin in the fly ash is extracted into the solution by using the carbon source solution, and the dioxin pollutant enters the leachate, and is sprayed to the top of the stack with the leachate recirculation, and is retained by the nano-iron material in the titanium-containing material. Under the action, a photocatalytic effect is formed to generate hydroxyl radicals, which further promotes the dechlorination effect of dioxins; in addition, by controlling the pH of the leachate, the nano-iron material releases a certain amount of iron ions. Under the action of trace hydroxyl radicals generated by photocatalysis, combined with iron ions and low pH, Fenton catalytic effect will be produced, which will more effectively dechlorinize dioxins and effectively degrade dioxin pollution. During the process, the biodegradability of the leachate is improved, and then the leachate is infiltrated into the mixed layer and is better utilized by the microorganisms in the biogas residue. After the fly ash is treated by the method, the heavy metal in the fly ash can be fixed in the yard, and the dioxin in the fly ash is rapidly degraded. In addition, the advanced oxidation of nano-iron and titanium-containing materials can lead to more efficient degradation of organic pollution.

Claims

A method for treating waste incineration fly ash by using biogas residue, characterized in that it comprises:

An anti-seepage layer is laid in the yard for the disposal of fly ash, a flow guiding material is laid at the bottom, and a mixed layer of biogas residue, carbon source, sulfate, nutritive additive and fly ash is laid on the upper part, and the upper part of the mixed layer is placed a mixed layer of titanium material and nano-iron material;

During operation, the carbon source solution is injected from the upper part of the stack from time to time, and the leachate is collected from the bottom flow guiding material to the leachate collection system from time to time, and then the leachate is returned to the top of the stack for spraying. Refill.
A method for treating waste incineration fly ash using biogas residue according to claim 1, wherein:

The fly ash, the biogas residue, the carbon source, the sulfate salt and the nutritional additive in the mixed layer are added in a ratio of 1: (0.01-0.5): (0.01-0.5): 0.05-0.3): (0.05-0.1).
A method for treating waste incineration fly ash using biogas residue according to claim 1 or 2, wherein:

The mixed layer has a thickness of 1-8 m; the mixed layer of the titanium-containing material and the nano-iron material has a thickness of not more than 1 m.
A method for treating waste incineration fly ash using biogas residue according to claim 3, wherein:

The mixing ratio of the titanium-containing material and the nano-iron material is (0.01-100): 1.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1 to 4, characterized in that:

The spraying interval of the leachate flowing back to the top of the stack for spraying and refilling is 1-48 hours.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1 to 5, characterized in that:

The leachate is subjected to pH adjustment when the leachate is refluxed to the top of the stack for spraying and recharging, so that the pH of the leachate to be recharged is 2-6.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1 to 6, wherein:

The biogas residue includes organic wastewater, solid organic waste or sludge.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1 to 7, wherein:

During operation, the frequency of the carbon source solution is injected in the upper portion of the stack to inject the carbon source solution once every 1-100 days.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1-8, characterized in that:

The nutritional additive includes one or more of a nitrogen source, a phosphorus source, and a trace element source, and the sulfate includes an inorganic salt or waste containing sulfate.
A method for treating waste incineration fly ash using biogas residue according to claim 9, wherein:

The sulfate salt includes sodium sulfate.
A method for treating waste incineration fly ash using biogas residue according to claim 9 or 10, wherein:

The sulfate is gypsum.
A method for treating waste incineration fly ash using biogas residue according to claim 9, wherein:

The nutritional additive comprises a mixture of potassium phosphate, ammonium nitrate, and cobalt nitrate, while one or more of the trace element sources are added.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1 to 12, characterized in that:

The trace element source includes a nutrient containing one or more elements of boron, zinc, copper, manganese, cobalt, and the carbon source solution includes a solution containing one or more of ethanol, methanol, and acetic acid.
A method for treating waste incineration fly ash using biogas residue according to any one of claims 1 to 13, characterized in that:

The titanium-containing material is titanium dioxide, and the titanium-containing material may be replaced by other photocatalytic materials including fly ash after biochemical, physical or chemical treatment.