METHOD FOR PRODUCING A CHLORIDE SORPTION MATERIAL FOR USE IN WASTE INCINERATION AND APPLICATION OF THE CHLORIDE SORPTION MATERIAL

Abstract

A method for producing a chlorine adsorption material for use in waste incineration, characterized in that the chlorine adsorption material, which is capable of absorbing chlorine-based substances, is produced by mixing natural iron ore minerals and quartz rock and then adding CaO to a mixing system to modify the natural iron ore minerals and quartz rock by ultrasonic impregnation, and wherein the method comprises in particular the following steps: (1) producing iron ore powder by transferring the natural iron ore minerals into a mill and grinding the natural iron ore minerals, and then sieving the ground natural iron ore minerals to obtain the iron ore powder with a particle size of 0.2-0.3 mm;(2) Producing SiO2 by transferring the quartz stone into a tablet press to compress the quartz stone into powder, then drying and dehydrating the resulting powder, and then sieving the dried powder through a 60-100 mesh sieve to obtain SiO2 powder; (3) Producing an SiO2-Fe2O3 support by chemical vapor deposition, introducing the SiO2 powder from step (2) into a quartz tube of a chemical vapor deposition apparatus; weighing the iron ore powder from step (1) in a ratio of SiO2 powder to iron ore powder of 1:1.7-2.7, and transferring the weighed iron ore powder into a sublimator of the chemical vapor deposition apparatus, wherein the quartz tube is arranged vertically relative to and connected with the sublimator, and the quartz tube is provided inside with a platform for arranging the SiO2 powder;Air is introduced into the quartz tube, which is maintained at a vacuum of 0.08 MPa, so that the SiO2 powder is in a fluidized state; the quartz tube is heated to 200 °C to remove water from the SiO2 powder for 2-3 hours; the quartz tube is then heated to 400 °C; nitrogen is introduced into the sublimator and the temperature in the sublimator is regulated to 110 °C; after complete sublimation of the iron ore powder, the temperature of the sublimator is regulated to 400 °C to form a reaction chamber with the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; Holding the reaction chamber at 400°C for 2 hours so that the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder is completely oxidized, and then cooling the support to room temperature, drying the support at room temperature and grinding the support into powder;and finally, placing the powder in a tube furnace, heating to 400°C at a rate of 3°C·min-1 and holding for 1-2 hours, thereby obtaining the SiO2-Fe2O3 support; (4) preparing a solution with Ca(NO3)2·4H2O as a precursor with a solid-liquid ratio of 0.4-1.2 kg / l; (5) transferring the solution prepared in step (4) to a water tank with an ultrasonic cleaning device and then transferring the SiO2-Fe2O3 support prepared in step (3) to the water tank for ultrasonic mixing for 6-9 hours; and (6) calcining the SiO2-Fe2O3 support treated in step (5) at a temperature of 900°C to remove NOxane surface adhering to it and to produce CaO; modifying the SiO2-Fe2O3 support by CaO; Then cooling the modified SiO2-Fe2O3 support to room temperature; grinding the cooled SiO2-Fe2O3 support to a particle size of 0.1-0.2 mm to obtain the chlorine adsorption material.

Description

Technical field

[0001] The present invention relates to the field of chlorine adsorption materials and in particular to the production and application of a chlorine adsorption material for use in waste incineration. State of the art

[0002] Rapid economic growth makes everyday life more convenient, but it also generates a large amount of solid waste. Due to the complex composition of solid waste, which can be toxic, difficult to combust, infectious, pathogenic, etc., its disposal has become a major problem that urgently needs to be addressed. Compared to landfilling, incineration offers advantages such as reduction, controlled hygiene, and energy recovery, and is considered a superior waste management method. However, solid waste generally contains a chlorine source, which can lead to the generation of large quantities of hydrochloric acid (HCl). Therefore, there is a need to control chlorobenzene emissions during the incineration of plastic waste.

[0003] It is common practice to remove HCl during combustion using a combustion gas cleaning and collection device. Based on the physical forms of the adsorbent and the reaction products, combustion gas technology for solid waste incineration can be divided into three types: wet, semi-dry, and dry. In wet technology, an aqueous solution or slurry generally serves as the dechlorinating agent and exhibits good adsorption performance, but also a complex process and high costs. Semi-dry technology utilizes a lime slurry, which is cost-effective, but involves a complex digestion system with a pulp transport pathway that is prone to disruption. Dry technology, on the other hand, achieves dechlorination by adding a dechlorinating agent and demonstrates high efficiency in impurity removal and adsorbent utilization, is user-friendly, and cost-effective.The dechlorinating agent used in dry HCl removal depends on its specific surface area. The larger the specific surface area, the more active the dechlorinating agent, the shorter the dechlorination reaction time, and the higher the chlorine absorption capacity. However, the specific surface area of ​​the active ingredients in the dechlorinating agent is small, which is why it is crucial to determine how to increase the specific surface area of ​​the dechlorinating agent while simultaneously ensuring its potency.

[0004] Patent specification CN101773768A discloses a dry dechlorinating agent for removing HCl from gas and a manufacturing process for it. The dechlorinating agent, comprising the active ingredients Na₂CO₃, CaCO₃, CaO, and MgO, cross-linked bentonite as a porosity enhancer, methylcellulose as a foaming agent, and an extrusion aid, is produced by extruding and forming the aforementioned components into strips, followed by drying and roasting the extruded strips. The manufacturing process of the adsorbent is simple, and it exhibits high dechlorinating activity and high chlorine permeability at low temperatures. However, the adsorbent is not suitable for use at very high temperatures and is not recyclable.

[0005] Patent specification CN106268832A discloses a novel, highly efficient dechlorinating agent and a manufacturing process for it. The dechlorinating agent is produced by adding a partially modified zinc salt and a calcium salt as synergistic additives to one or more of the aforementioned components Na₂CO₃, CaCO₃, CaO, MgO, CuO, ZnO, and their derivatives as active ingredient(s), NH₄HCO₃ as a porosity aid, and at least one of Al₂O₃, diaspore, kaolin, or clay as a carrier, as well as an excipient. A suitable quantity of water is added to the aforementioned components in an appropriate ratio; they are mixed, extruded, formed into strips, dried, and roasted to produce the dechlorinating agent.The adsorbent exhibits high adsorption capacity for HCl at both high and low concentrations and at room temperature, as well as high dechlorination activity, and possesses a chlorine uptake capacity of up to 35% or more. This adsorbent can efficiently and thoroughly remove HCl gas from catalysis, reforming, and other applications within a temperature range of 300–600 °C and with a chlorine permeability of 65% or more. However, the pore volume and specific surface area of ​​diaspore, kaolin, or clay are limited, and the cost of this adsorbent is high.

[0006] The patents listed above describe investigations into dechlorinating agents, but their use is generally only possible at normal or high temperatures. Reusability is limited and even more restricted under certain conditions, and the cost of dechlorinating agents is high. These problems limit the application and production of dechlorinating agents. Object of the invention

[0007] In view of the aforementioned circumstances and the disadvantages of the prior art, the invention is based on the objective of providing a method for producing a chlorine adsorption material with low cost, high efficiency and safety and a simple production process, as well as an application of the chlorine adsorption material.

[0008] To fulfill the aforementioned task, the invention utilizes the following technical solutions. A method for producing a chlorine adsorption material for use in waste incineration comprises producing the chlorine adsorption material capable of absorbing chlorine-based substances by mixing natural iron ores and quartz rock and then adding CaO to a mixing system to modify the natural iron ores and quartz rock by ultrasonic impregnation.

[0009] Furthermore, the chlorine-based substances contain at least hydrogen chloride and chlorobenzene.

[0010] Furthermore, the procedure includes the following steps in detail: (1) Producing iron ore powder by: placing the natural iron ores into a mill and grinding the natural iron ores, and then sieving the ground natural iron ores to obtain the iron ore powder with a particle size of 0.2-0.3 mm; (2) Production of SiO2 by: placing the quartz stone in a tablet press to compress the quartz stone into powder, then drying and dehydrating the resulting powder and then sieving the dried powder through a sieve with 60-100 mesh to obtain SiO2 powder; (3) Producing a SiO2-Fe2O3 support by: chemical vapor deposition; introducing the SiO2 powder from step (2) into a quartz tube of a chemical vapor deposition apparatus; weighing the iron ore powder from step (1) in a ratio of SiO2 powder to iron ore powder of 1:1.7-2.7, and placing the weighed iron ore powder into a sublimator of the chemical vapor deposition apparatus, wherein the quartz tube is arranged vertically relative to and connected with the sublimator, and the quartz tube is provided inside with a platform for arranging the SiO2 powder; introducing air into the quartz tube, which is maintained at a vacuum of 0.08 MPa, so that the SiO2 powder is in a fluidized state; heating the quartz tube to 200 °C to remove water from the SiO2 powder for 2-3 h; Heating the quartz tube to 400 °C;Introducing nitrogen into the sublimator and regulating the temperature in the sublimator to 110°C; after complete sublimation of the iron ore powder, regulating the temperature of the sublimator to 400°C to form a reaction chamber through the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; maintaining the reaction chamber at 400°C for 2 h so that the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder are completely oxidized, and then cooling the support to room temperature, drying the support at room temperature and grinding the support into powder; and finally introducing the powder into a tube furnace, heating to 400°C at a rate of 3°C·min; -1 and holding for 1-2 h, thereby obtaining the SiO2-Fe2O3 support; (4) Prepare a solution with Ca(NO3)2·4H2O as a precursor with a solid-liquid ratio of 0.4-1.2 kg / l; (5) Add the solution prepared in step (4) to a water tank of an ultrasonic cleaning device and then add the SiO2-Fe2O3 carrier prepared in step (3) to the water tank for ultrasonic mixing for 6-9 hours; and (6) Calcining the SiO2-Fe2O3 support treated in step (5) at a temperature of 900 °C to remove NO x to remove surface adhesions and produce CaO; modifying the SiO2-Fe2O3 support with CaO; then cooling the modified SiO2-Fe2O3 support to room temperature; grinding the cooled SiO2-Fe2O3 support to a particle size of 0.1-0.2 mm and thereby obtaining the chlorine adsorption material.

[0011] Preferably, the components and proportions added in steps (1), (2) and (4) are as follows: 52 to 67 parts of the natural iron ore; 25 to 30 parts of the quartz stone; and 0.03 to 0.05 parts of Ca(NO3)2·4H2O.

[0012] Preferably, the flow rate of the air introduced into the quartz tube in step (3) is 80 ml / min. -1 .

[0013] Preferably, the Ca(NO3)2·4H2O from step (4) has a purity level of over 99.9% and a particle size of less than 5 µm.

[0014] Preferably the ultrasonic cleaning device from step (5) has an operating frequency of 40,000 Hz and an operating power of 100 W.

[0015] Preferably, in step (5) the ultrasonic cleaning device maintains the temperature of the water tank at 90 °C during operation.

[0016] Preferably, the calcination time of the SiO2-Fe2O3 support treated in step (5) in step (6) is 1 h.

[0017] The resulting chlorine adsorption material is applied to the adsorption of chlorine-based substances during waste incineration.

[0018] Thanks to the aforementioned technical solutions, the invention exhibits the following advantageous effects: The chlorine adsorption material is produced by mixing raw materials containing natural iron ores and quartz rock, and modifying the iron ores and quartz rock with CaO by ultrasonic impregnation; the resulting chlorine adsorption material has a large pore size, high porosity, and a stable structure, and exhibits higher adsorption efficiency and adsorption capacity for chlorine-based substances during waste incineration and is also reusable; furthermore, the use of inexpensive natural iron ores and quartz rock can reduce the processing costs for chlorine-based substances, ensure good resource utilization, and promote environmental protection. Description of preferred embodiments

[0019] A process for producing a chlorine adsorption material for use in waste incineration includes the following steps: (1) Producing iron ore powder by: placing the natural iron ores into a mill and grinding the natural iron ores, and then sieving the ground natural iron ores to obtain the iron ore powder with a particle size of 0.2-0.3 mm; (2) Production of SiO2 by: placing the quartz stone in a tablet press to compress the quartz stone into powder, then drying and dehydrating the resulting powder and then sieving the dried powder through a sieve with 60-100 mesh to obtain SiO2 powder; (3) Producing a SiO2-Fe2O3 support by: chemical vapor deposition; introducing the SiO2 powder from step (2) into a quartz tube of a chemical vapor deposition apparatus; weighing the iron ore powder from step (1) in a ratio of SiO2 powder to iron ore powder of 1:1.7-2.7, and placing the weighed iron ore powder into a sublimator of the chemical vapor deposition apparatus, wherein the quartz tube is arranged vertically relative to and connected with the sublimator, and the quartz tube is provided inside with a platform for arranging the SiO2 powder; introducing air into the quartz tube, which is maintained at a vacuum of 0.08 MPa, so that the SiO2 powder is in a fluidized state; heating the quartz tube to 200 °C to remove water from the SiO2 powder for 2-3 h; Heating the quartz tube to 400 °C;Introducing nitrogen into the sublimator and regulating the temperature in the sublimator to 110 °C; after complete sublimation of the iron ore powder, regulating the temperature of the sublimator to 400 °C to form a reaction chamber through the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; maintaining the reaction chamber at 400 °C for 2 h so that the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder are completely oxidized, and then cooling the support to room temperature, drying the support at room temperature and grinding the support into powder; and finally introducing the powder into a tube furnace, heating to 400 °C at a rate of 3 °C·min; -1 and holding for 1-2 h, thereby obtaining the SiO2-Fe2O3 support; (4) Prepare a solution with Ca(NO3)2·4H2O as a precursor with a solid-liquid ratio of 0.4-1.2 kg / l; (5) Add the solution prepared in step (4) to a water tank of an ultrasonic cleaning device and then add the SiO2-Fe2O3 carrier prepared in step (3) to the water tank for ultrasonic mixing for 6-9 hours; and (6) Calcining the SiO2-Fe2O3 support treated in step (5) at a temperature of 900 °C to remove NO x to remove surface adhesions and produce CaO; modifying the SiO2-Fe2O3 support with CaO; then cooling the modified SiO2-Fe2O3 support to room temperature; grinding the cooled SiO2-Fe2O3 support to a particle size of 0.1-0.2 mm and thereby obtaining the chlorine adsorption material.

[0020] Preferably, the components and proportions added in steps (1), (2) and (4) are as follows: 52 to 67 parts of the natural iron ore; 25 to 30 parts of the quartz stone; and 0.03 to 0.05 parts of Ca(NO3)2-4H2O.

[0021] Preferably, the flow rate of the air introduced into the quartz tube in step (3) is 80 ml·min. -1 .

[0022] Preferably, the Ca(NO3)2·4H2O from step (4) has a purity level of over 99.9% and a particle size of less than 5 µm.

[0023] Preferably the ultrasonic cleaning device from step (5) has an operating frequency of 40,000 Hz and an operating power of 100 W.

[0024] Preferably, in step (5) the ultrasonic cleaning device maintains the temperature of the water tank at 90 °C during operation.

[0025] Preferably, the calcination time of the SiO2-Fe2O3 support treated in step (5) in step (6) is 1 h.

[0026] The resulting chlorine adsorption material is applied to the adsorption of chlorine-based substances during waste incineration. Design 1

[0027] A process for producing a chlorine adsorption material for use in waste incineration included the following steps: (1) Iron ore powder was produced as follows: Natural iron ores were placed in a mill and the natural iron ores were ground and then sieved to obtain an iron ore powder with a particle size of 0.2-0.3 mm. (2) SiO2 powder was produced as follows: The quartz stone was placed in a tablet press and pressed into powder, dried and dehydrated and sifted through a sieve with 60-100 mesh to obtain SiO2 powder. (3) A SiO2-Fe2O3 support was prepared as follows: By chemical vapor deposition, 2 kg of the SiO2 powder prepared in step (2) were weighed out and placed in a quartz tube of a chemical vapor deposition apparatus; 5.36 kg of the iron ore powder prepared in step (1) were weighed out and placed in a sublimator of the chemical vapor deposition apparatus, the quartz tube being arranged vertically relative to and in contact with the sublimator, the sublimator being provided inside with a platform for arranging the SiO2 powder; at a flow rate of 80 ml / min -1Air was introduced into the quartz tube, which was maintained at a vacuum of 0.08 MPa, so that the SiO2 powder was in a fluidized state; the quartz tube was heated to 200 °C for 2-3 h to remove water from the SiO2 powder; the quartz tube was heated to 400 °C; nitrogen was introduced into the sublimator and it was regulated to a temperature of 110 °C; after complete sublimation of the iron ore powder, the temperature of the sublimator was regulated to 400 °C to form a reaction chamber with the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; The reaction chamber was held at 400 °C for 2 hours to allow the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder to oxidize completely, after which the support was cooled to room temperature and dried at room temperature;and finally the carrier was ground into powder and placed in a tube furnace, which was heated to 400°C at a rate of 3°C·min; -1 was heated and held for 1-2 hours, resulting in the SiO2-Fe2O3 support. (4) Ca(NO3)2·4H2O was used as a precursor to prepare a solution with a solid-liquid ratio of 0.4kg / l, which Ca(NO3)2·4H2O had a purity of over 99.9% and a particle size of less than 5 µm. (5) The solution prepared in step (4) was placed in a water tank of an ultrasonic cleaning device; then the SiO2-Fe2O3 carrier prepared in step (3) was placed in the water tank; and then ultrasonic mixing of the mixing system in the water tank was carried out for 6h with the following operating parameters: operating frequency of 40,000 Hz and an operating power of 100 W, maintaining the mixing temperature at 90 °C during mixing. (6) The SiO2-Fe2O3 support treated in step (5) was calcined at a temperature of 900 °C for 1 h to remove NO x to remove surface adhesions and produce CaO; and the SiO2-Fe2O3 support was modified with CaO, cooled to room temperature and ground to a particle size of 0.1-0.2 mm, thereby obtaining the chlorine adsorption material. Design 2

[0028] A process for producing a chlorine adsorption material for use in waste incineration included the following steps: (1) Iron ore powder was produced as follows: Natural iron ores were placed in a mill and the natural iron ores were ground and then sieved to obtain an iron ore powder with a particle size of 0.2-0.3 mm. (2) SiO2 powder was produced as follows: The quartz stone was placed in a tablet press and pressed into powder, dried and dehydrated and sifted through a sieve with 60-100 mesh to obtain SiO2 powder. (3) A SiO2-Fe2O3 support was prepared as follows: By chemical vapor deposition, 2 kg of the SiO2 powder prepared in step (2) were weighed out and placed in a quartz tube of a chemical vapor deposition apparatus; 3.46 kg of the iron ore powder prepared in step (1) were weighed out and placed in a sublimator of the chemical vapor deposition apparatus, the quartz tube being arranged vertically relative to and in contact with the sublimator, the sublimator being provided inside with a platform for arranging the SiO2 powder; at a flow rate of 80 ml / min -1Air was introduced into the quartz tube, which was maintained at a vacuum of 0.08 MPa, so that the SiO2 powder was in a fluidized state; the quartz tube was heated to 200 °C for 2-3 h to remove water from the SiO2 powder; the quartz tube was heated to 400 °C; nitrogen was introduced into the sublimator and it was regulated to a temperature of 110 °C; after complete sublimation of the iron ore powder, the temperature of the sublimator was regulated to 400 °C to form a reaction chamber with the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; The reaction chamber was held at 400 °C for 2 hours to allow the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder to oxidize completely, after which the support was cooled to room temperature and dried at room temperature;and finally the carrier was ground into powder and placed in a tube furnace, which was heated to 400 °C at a rate of 3 °C·min; -1 was heated and held for 1-2 hours, resulting in the SiO2-Fe2O3 support. (4) Ca(NO3)2·4H2O was used as a precursor to prepare a solution with a solid-liquid ratio of 0.4kg / l, which Ca(NO3)2·4H2O had a purity of over 99.9% and a particle size of less than 5 µm. (5) The solution prepared in step (4) was placed in a water tank of an ultrasonic cleaning device; then the SiO2-Fe2O3 carrier prepared in step (3) was placed in the water tank; and then ultrasonic mixing of the mixing system in the water tank was carried out for 8h with the following operating parameters: operating frequency of 40,000 Hz and an operating power of 100 W, maintaining the mixing temperature at 90 °C during mixing. (6) The SiO2-Fe2O3 support treated in step (5) was calcined at a temperature of 900 °C for 1 h to remove NO x to remove surface adhesions and produce CaO; and the SiO2-Fe2O3 support was modified with CaO, cooled to room temperature and ground to a particle size of 0.1-0.2 mm, thereby obtaining the chlorine adsorption material. embodiment 3

[0029] A process for producing a chlorine adsorption material for use in waste incineration included the following steps: (1) Iron ore powder was produced as follows: Natural iron ores were placed in a mill and the natural iron ores were ground and then sieved to obtain an iron ore powder with a particle size of 0.2-0.3 mm. (2) SiO2 powder was produced as follows: The quartz stone was placed in a tablet press and pressed into powder, dried and dehydrated and sifted through a sieve with 60-100 mesh to obtain SiO2 powder. (3) A SiO2-Fe2O3 support was prepared as follows: By chemical vapor deposition, 2 kg of the SiO2 powder prepared in step (2) were weighed out and placed in a quartz tube of a chemical vapor deposition apparatus; 5.36 kg of the iron ore powder prepared in step (1) were weighed out and placed in a sublimator of the chemical vapor deposition apparatus, the quartz tube being arranged vertically relative to and in contact with the sublimator, the sublimator being provided inside with a platform for arranging the SiO2 powder; at a flow rate of 80 ml / min -1Air was introduced into the quartz tube, which was maintained at a vacuum of 0.08 MPa, so that the SiO2 powder was in a fluidized state; the quartz tube was heated to 200 °C for 2-3 h to remove water from the SiO2 powder; the quartz tube was heated to 400 °C; nitrogen was introduced into the sublimator and it was regulated to a temperature of 110 °C; after complete sublimation of the iron ore powder, the temperature of the sublimator was regulated to 400 °C to form a reaction chamber with the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; The reaction chamber was held at 400 °C for 2 hours to allow the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder to oxidize completely, after which the support was cooled to room temperature and dried at room temperature;and finally the carrier was ground into powder and placed in a tube furnace, which was heated to 400 °C at a rate of 3 °C·min; -1 was heated and held for 1-2 hours, resulting in the SiO2-Fe2O3 support. (4) Ca(NO3)2·4H2O was used as a precursor to prepare a solution with a solid-liquid ratio of 0.8kg / l, which Ca(NO3)2·4H2O had a purity of over 99.9% and a particle size of less than 5 µm. (5) The solution prepared in step (4) was placed in a water tank of an ultrasonic cleaning device; then the SiO2-Fe2O3 carrier prepared in step (3) was placed in the water tank; and then ultrasonic mixing of the mixing system in the water tank was carried out for 9 h with the following operating parameters: operating frequency of 40,000 Hz and an operating power of 100 W, maintaining the mixing temperature at 90 °C during mixing. (6) The SiO2-Fe2O3 support treated in step (5) was calcined at a temperature of 900°C for 1 h to remove NO x to remove surface adhesions and produce CaO; and the SiO2-Fe2O3 support was modified with CaO, cooled to room temperature and ground to a particle size of 0.1-0.2 mm, thereby obtaining the chlorine adsorption material. Design 4

[0030] A process for producing a chlorine adsorption material for use in waste incineration included the following steps: (1) Iron ore powder was produced as follows: Natural iron ores were placed in a mill and the natural iron ores were ground and then sieved to obtain an iron ore powder with a particle size of 0.2-0.3 mm. (2) SiO2 powder was produced as follows: The quartz stone was placed in a tablet press and pressed into powder, dried and dehydrated and sifted through a sieve with 60-100 mesh to obtain SiO2 powder. (3) A SiO2-Fe2O3 support was prepared as follows: by chemical vapor deposition, 2 kg of the SiO2 powder produced in step (2) were weighed out and placed in a quartz tube of a chemical vapor deposition apparatus; 3.46 kg of the iron ore powder produced in step (1) were weighed out and placed in a sublimator of the chemical vapor deposition apparatus, the quartz tube being arranged vertically relative to and in contact with the sublimator, the sublimator being provided inside with a platform for arranging the SiO2 powder; at a flow rate of 80 ml / min -1Air was introduced into the quartz tube, which was maintained at a vacuum of 0.08 MPa, so that the SiO2 powder was in a fluidized state; the quartz tube was heated to 200 °C for 2-3 h to remove water from the SiO2 powder; the quartz tube was heated to 400 °C; nitrogen was introduced into the sublimator and it was regulated to a temperature of 110 °C; after complete sublimation of the iron ore powder, the temperature of the sublimator was regulated to 400 °C to form a reaction chamber with the sublimator and the quartz tube, in order to completely mix the fluidized SiO2 powder with the sublimated iron ore powder; The reaction chamber was held at 400 °C for 2 hours to allow the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder to oxidize completely, after which the support was cooled to room temperature and dried at room temperature;and finally the carrier was ground into powder and placed in a tube furnace, which was heated to 400 °C at a rate of 3 °C·min; -1 was heated and held for 1-2 hours, resulting in the SiO2-Fe2O3 support. (4) Ca(NO3)2·4H2O was used as a precursor to prepare a solution with a solid-liquid ratio of 1.2kg / l, which Ca(NO3)2·4H2O had a purity of over 99.9% and a particle size of less than 5 µm. (5) The solution prepared in step (4) was placed in a water tank of an ultrasonic cleaning device; then the SiO2-Fe2O3 carrier prepared in step (3) was placed in the water tank; and then ultrasonic mixing of the mixing system in the water tank was carried out for 9h with the following operating parameters: operating frequency of 40,000 Hz and an operating power of 100 W, maintaining the mixing temperature at 90 °C during mixing. (6) The SiO2-Fe2O3 support treated in step (5) was calcined at a temperature of 900 °C for 1 h to remove NO x to remove surface adhesions and produce CaO; and the SiO2-Fe2O3 support was modified with CaO, cooled to room temperature and ground to a particle size of 0.1-0.2 mm, thereby obtaining the chlorine adsorption material. Performance test

[0031] The chlorine adsorption materials produced in embodiments 1 to 4 were placed in various waste incineration reactors. The reactors were heated to a temperature of 900 °C for 30 minutes in an atmospheric environment to ensure complete oxidation of the chlorine adsorption material. Subsequently, a combustion-enhancing synthesis gas (consisting of 1% HCl, 21.9% CO, 5.9% CH4, 12.7% H2, 7.8% CO2, and 50.7% N2) was introduced and directed through an air nozzle into the combustion chamber for incineration with the waste. After complete combustion, the HCl content of the combustion gas was measured. A test was also conducted without the addition of chlorine adsorption material to measure the HCl content of the combustion gas. The results obtained were as follows: element Chlorine content without the addition of adsorbent material (ppm) Chlorine content with added adsorbent material (ppm) Design 1 367,2 55,7 Design 2 367,2 60,6 embodiment 3 367,2 45,4 Design 4 367,2 39,9

[0032] The requirements of the Standard for Pollution Control on the Municipal Solid Waste Incineration (GB 18485-2014) specify a limit of 60 ppm (average over 1 hour) or 50 ppm (average over 24 hours) for HCl. This demonstrates that the chlorine adsorption material produced according to the solutions of the invention can enable the adsorption of chlorine-based substances generated during waste incineration and meets the requirements of the relevant regulations in China.

[0033] The above description provides embodiments of the invention. For a person skilled in the art, equivalent modifications, substitutions, and variations that are made within the scope of the invention in accordance with the teachings of the invention without deviating from the fundamental ideas and essence of the invention fall within the scope covered by the invention. 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] CN 101773768 A

[0004] CN 106268832 A

[0005] GB 184852014

[0032]

Claims

[1] Method for producing a chlorine adsorption material for use in waste incineration, characterized by , that: the chlorine adsorption material, which can absorb chlorine-based substances, is produced by mixing natural iron ores and quartz stone and then adding CaO to a mixing system to modify the natural iron ores and quartz stone by means of ultrasonic impregnation. [2] Method for producing chlorine adsorption material for use in waste incineration according to claim 1, characterized by , that: the chlorine-based substances include at least hydrogen chloride and chlorobenzene. [3] Method for producing chlorine adsorption material for use in waste incineration according to claim 1, characterized by that the procedure comprises the following steps in detail: (1) Producing iron ore powder by: placing the natural iron ores into a mill and grinding the natural iron ores, and then sieving the ground natural iron ores to obtain the iron ore powder with a particle size of 0.2-0.3 mm; (2) Production of SiO2 by: placing the quartz stone in a tablet press to compress the quartz stone into powder, then drying and dehydrating the resulting powder and then sieving the dried powder through a sieve with 60-100 mesh to obtain SiO2 powder; (3) Producing a SiO2-Fe2O3 support by: chemical vapor deposition; introducing the SiO2 powder from step (2) into a quartz tube of a chemical vapor deposition apparatus; weighing the iron ore powder from step (1) in a ratio of SiO2 powder to iron ore powder of 1:1.7-2.7, and placing the weighed iron ore powder into a sublimator of the chemical vapor deposition apparatus, wherein the quartz tube is arranged vertically relative to and connected with the sublimator, and the quartz tube is provided inside with a platform for arranging the SiO2 powder; introducing air into the quartz tube, which is maintained at a vacuum of 0.08 MPa, so that the SiO2 powder is in a fluidized state; heating the quartz tube to 200 °C to remove water from the SiO2 powder for 2-3 h; Heating the quartz tube to 400°C;Nitrogen is introduced into the sublimator and the temperature is regulated to 110°C; after complete sublimation of the iron ore powder, the temperature of the sublimator is regulated to 400°C to form a reaction chamber through the sublimator and the quartz tube, allowing the fluidized SiO2 powder to be completely mixed with the sublimated iron ore powder; the reaction chamber is held at 400°C for 2 hours to ensure complete oxidation of the iron and an iron compound on the support formed from the SiO2 powder and the iron ore powder, followed by cooling the support to room temperature, drying it at room temperature, and grinding it into powder; finally, the powder is placed in a tube furnace and heated to 400°C at a rate of 3°C / min. -1 and holding for 1-2 h, thereby obtaining the SiO2-Fe2O3 support; (4) Prepare a solution with Ca(NO3)2·4H2O as a precursor with a solid-liquid ratio of 0.4-1.2 kg / l; (5) Add the solution prepared in step (4) to a water tank of an ultrasonic cleaning device and then add the SiO2-Fe2O3 carrier prepared in step (3) to the water tank for ultrasonic mixing for 6-9 hours; and (6) Calcining the SiO2-Fe2O3 support treated in step (5) at a temperature of 900 °C to remove NO x to remove surface adhesions and produce CaO; modifying the SiO2-Fe2O3 support with CaO; then cooling the modified SiO2-Fe2O3 support to room temperature; grinding the cooled SiO2-Fe2O3 support to a particle size of 0.1-0.2 mm and thereby obtaining the chlorine adsorption material. [4] Method for producing chlorine adsorption material for use in waste incineration according to claim 3, characterized by, that the components and proportions thereof added in steps (1), (2) and (4) are as follows: 52 to 67 parts of the natural iron ore; 25 to 30 parts of the quartz stone; and 0.03 to 0.05 parts of Ca(NO3)2·4H2O. [5] Method for producing chlorine adsorption material for use in waste incineration according to claim 3, characterized by , that: the flow rate of the air introduced into the quartz tube in step (3) is 80 ml·min -1 amounts. [6] Method for producing chlorine adsorption material for use in waste incineration according to claim 3, characterized by , that the Ca(NO3)2·4H2O from step (4) has a purity level of over 99.9% and a particle size of less than 5 µm. [7] Method for producing chlorine adsorption material for use in waste incineration according to claim 3, characterized by, that: the ultrasonic cleaning device from step (5) maintains the temperature of the water tank at 90°C during operation. [8] Method for producing chlorine adsorption material for use in waste incineration according to claim 3, characterized by , that: the ultrasonic cleaning device from step (5) has an operating frequency of 40,000 Hz and an operating power of 100 W. [9] Application of the chlorine adsorption material produced by the process for producing chlorine adsorption material for use in waste incineration according to any one of claims 1 to 7, characterized by , that the manufactured chlorine adsorption material is applied to the adsorption of chlorine-based substances during waste incineration.