Metallurgical coke composite modifier based on waste ceramic filter tube, preparation method and metallurgical coke production method

Abstract

This invention discloses a metallurgical coke composite modifier based on waste ceramic filter tubes, its preparation method, and a metallurgical coke production method, belonging to the field of solid waste treatment technology. This invention modifies waste ceramic filter tubes by reducing high-valence metal ions in the filter tubes using coke dust. The modified waste ceramic filter tube particles are then fused with waste plastic particles through roller extrusion to prepare a metallurgical coke composite modifier, which is added to coking coal to produce metallurgical coke. This invention uses the prepared metallurgical coke composite modifier for coking, achieving both volume reduction, harmlessness, and resource recovery of waste ceramic filter tubes, providing a new approach to waste plastic decomposition, and producing metallurgical coke with excellent performance indicators, including a low reactivity index (CRI) and a high post-reaction strength index (CSR).

Description

Technical Field

[0001] This invention belongs to the field of solid waste treatment technology, specifically relating to a composite modifier for metallurgical coke based on waste ceramic filter tubes, its preparation method, and a method for producing metallurgical coke. Background Technology

[0002] Metallurgical coke, as a core raw material in blast furnace ironmaking, casting, and non-ferrous metal smelting, directly determines the energy efficiency, technical and economic indicators, and final product quality of the production process. Traditionally, high-quality metallurgical coke relies on scarce coal resources such as prime coking coal and bituminous coal, and is prepared through high-temperature dry distillation. It requires low reactivity, high shatter resistance, and excellent hot properties (such as high post-reaction strength). However, when bituminous coal is coked alone, the coke often exhibits numerous cracks, and honeycomb coke is frequently present at the coke root, making it difficult for the final coke strength to meet the requirements of high-quality metallurgical coke. Furthermore, the modifiers (such as boron compounds) added during coking in existing technologies are mainly compounded from chemical raw materials, resulting in high production costs for coking plants.

[0003] With increasingly stringent requirements for industrial flue gas emissions, ceramic filter tubes, key components of high-temperature dust removal systems in coking plants, need to be replaced in a timely manner to prevent flue gas emissions from exceeding standards. As a result, discarded ceramic filter tubes have become a large amount of industrial solid waste that coking plants need to centrally process.

[0004] Patent document CN116511208A discloses a resource-based treatment method for waste catalytic ceramic fiber filter tubes, which involves classifying and processing the waste catalytic ceramic fiber filter tubes and extracting valuable elements using a wet process. Chinese invention patent CN115445436A discloses a regeneration treatment method for waste catalyst ceramic fiber filter tubes, which regenerates and reuses the ceramic filter tubes through calcination.

[0005] The aforementioned methods all have significant limitations. High-temperature physical regeneration methods are limited by deep clogging of the filter tubes and chemical poisoning, typically allowing only 1-2 reuses, after which they still need to be treated as solid waste. Wet recycling of valuable components involves a long process, high energy consumption, and generates large amounts of acidic and alkaline wastewater containing heavy metals and fluorine, posing serious secondary pollution problems. Therefore, the quality issues of metallurgical coke and the resource utilization of waste ceramic filter tubes are two major problems that the coking industry urgently needs to solve. Summary of the Invention

[0006] The purpose of this invention is to provide a composite modifier for metallurgical coke based on waste ceramic filter tubes, its preparation method, and a method for producing metallurgical coke, which can solve the problems of the difficulty in resource utilization of waste ceramic filter tubes and the poor performance of metallurgical coke in the prior art.

[0007] The objective of this invention can be achieved through the following technical solutions: A method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes includes the following steps: Step 1: Crush, grind and sieve the waste ceramic filter tubes and waste plastics respectively to obtain waste ceramic filter tube particles and waste plastic particles respectively; Step 2: Thoroughly mix the waste ceramic filter tube particles and coke dust, and calcine at high temperature to obtain modified waste ceramic filter tube particles; Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles, and then crush and screen them to obtain the metallurgical coke composite modifier.

[0008] Furthermore, the waste ceramic filter tube is produced from aluminum silicate fiber and carries a vanadium-titanium catalyst.

[0009] Furthermore, the waste plastic is made of at least one of PET and PS.

[0010] This invention modifies waste ceramic filter tubes by using coke dust to reduce high-valence metal ions, such as V₂O₅, in the waste ceramic filter tubes, thereby reducing V₂O₅. 5+ Restore to V 3+ and V 4+ This process consumes the remaining active material in the waste ceramic filter tubes, while simultaneously reducing the valence state of vanadium (vanadium toxicity decreases with decreasing valence state), thus reducing its toxicity and ultimately solidifying it in the coke, achieving the goal of resource utilization of the waste ceramic filter tubes.

[0011] Simultaneously, this invention fuses waste plastic particles with modified waste ceramic filter tube particles through roller extrusion. The modified waste ceramic filter tube particles are embedded in the waste plastic particles and added to coking coal as a modifier. During co-coking, the waste ceramic filter tube particles act as an inert skeleton, trapping and bearing the depositable carbon released by the thermal decomposition of waste plastic. At the same time, the coke dust added during the modification of waste ceramic filter tubes, being carbon itself, can serve as a substrate for carbon deposition. The three work together to provide a substrate for the coke to bond and solidify to form a carbon skeleton. Waste plastic is a high-quality hydrogen donor and flow agent rich in aromatics. Its addition can improve the quality and flowability of the colloidal body, promote the development and fusion of the mesophase, reduce the carbon interlayer spacing, increase the microcrystal height, and make the structure more ordered, thereby strengthening the final carbon skeleton.

[0012] Furthermore, the particle size of the waste ceramic filter tube particles is ≤0.075mm.

[0013] Furthermore, the particle size of the waste plastic particles is ≤1mm.

[0014] Furthermore, the mass ratio of the waste ceramic filter tube particles to the coke dust is (1:4) to (1:6).

[0015] Furthermore, the high-temperature calcination temperature is 600℃~900℃, and the duration is 15~20min.

[0016] Furthermore, the mass ratio of the modified waste ceramic filter tube particles to the waste plastic particles is (1:1) to (1:1.5).

[0017] Furthermore, the particle size of the metallurgical coke composite modifier is ≤1mm.

[0018] The present invention also provides a metallurgical coke composite modifier based on waste ceramic filter tubes, which is prepared by the above preparation method.

[0019] This invention also provides a method for producing metallurgical coke, which uses the metallurgical coke composite modifier described above to produce metallurgical coke, comprising the following steps: Step 1: Crush the coking coal, add the metallurgical coke composite modifier and mix evenly to obtain a mixture; Step 2: Add mist water to the mixture, controlling the moisture content to 10%, to obtain blended coal; Step 3: The blended coal is compacted to form coal cakes, which are then loaded into a coking reactor for high-temperature coking. The coking process is then carried out and cooled to obtain metallurgical coke.

[0020] This invention adds a metallurgical coke composite modifier, prepared from waste ceramic filter tubes, to coking coal. The coking process is then carried out using existing methods, ensuring the finished coke meets quality requirements while simultaneously processing the waste ceramic filter tubes. The waste ceramic filter tubes contain a large amount of aluminosilicate fibers. Aluminosilicate fibers can weaken the catalytic effect of alkaline minerals on the coke gasification reaction, thereby reducing the rate of dissolution reaction (C + CO2 → 2CO) in the blast furnace. This improves the coke's coke strength (CSR) after reacting with CO2 at high temperatures, allowing it to maintain a good skeletal structure in the lower part of the blast furnace, which is beneficial for the permeability of the fuel column. Using this metallurgical coke composite modifier in the coking process ultimately results in a highly ordered, dense coke with few defects.

[0021] Furthermore, the mass ratio of the composite modifier for coking coal and metallurgical coke is (98:2) to (99.5:0.5).

[0022] Furthermore, the conditions for the high-temperature coking are as follows: The temperature was increased to 700℃ at a rate of 15℃ / min, and then increased to 1050℃ at a rate of 5℃ / min, and held for 5 hours.

[0023] The beneficial effects of this invention are: (1) This invention prepares a new type of modifier by mixing waste ceramic filter tubes generated in the flue gas treatment industry with waste plastics and coke dust, thereby realizing the reduction, harmlessness and resource utilization of waste ceramic filter tubes, providing a new way to dispose of waste plastics and reducing their harm to the environment and human body.

[0024] (2) This invention optimizes the pretreatment method of waste ceramic filter tubes and waste plastics. Compared with conventional mechanical mixing, the waste ceramic filter tubes are first mixed with coke and roasted together. The coke is used to reduce the high-valence metal ions in the waste ceramic filter tubes and reduce their toxicity. Then, the waste ceramic filter tubes are fused with waste plastics by roller extrusion. The modified waste ceramic filter tube particles are embedded in the waste plastic particles to obtain a modifier. Using the method of this invention, in the co-coking process, the waste ceramic filter tube particles act as an inert skeleton to intercept and carry the depositable carbon released by the thermal decomposition of waste plastics. At the same time, the coke added in the process of modifying waste ceramic filter tubes is carbon itself and can serve as a base for carbon deposition. The three work together to provide a base for the coke to bond and solidify to form a carbon skeleton, which can effectively ensure the bonding effect of waste ceramic filter tubes and waste plastics.

[0025] (3) When using the modifier of the present invention for coking, compared with the boron-based modifier used in the prior art, the waste ceramic filter tubes, waste plastics and coke dust used in the present invention have lower costs. The modifier produced reduces the gasification reactivity of coke and further improves the post-reaction strength of metallurgical coke to meet the requirements of ironmaking. Moreover, waste ceramic filter tubes are hazardous waste. Using the present invention can treat waste ceramic filter tubes, reduce hazardous waste treatment costs, and ultimately reduce the production costs of coking enterprises. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] The coking coal used in the following examples and comparative examples is all coking coal; the waste ceramic filter tubes are produced from aluminosilicate fibers and loaded with vanadium-titanium catalysts.

[0028] Example 1 Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0029] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0030] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0031] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0032] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0033] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0034] Example 2 The only difference from Example 1 is that the mass ratio of waste ceramic filter tube particles to coke dust is 1:5.

[0035] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0036] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:5, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0037] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0038] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0039] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0040] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0041] Example 3 The only difference from Example 1 is that the mass ratio of waste ceramic filter tube particles to coke dust is 1:6.

[0042] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0043] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:6, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0044] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0045] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0046] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0047] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0048] Example 4 The only difference from Example 1 is that the waste ceramic filter tube particles are mixed with coke powder and then calcined at a high temperature of 900°C for 20 minutes.

[0049] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0050] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 900℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0051] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0052] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0053] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0054] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0055] Example 5 The only difference from Example 1 is that the waste ceramic filter tube particles are mixed with coke powder and then calcined at a high temperature of 600°C for 20 minutes.

[0056] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0057] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 600℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0058] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0059] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0060] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0061] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0062] Example 6 The only difference from Example 1 is that the mass ratio of modified waste ceramic filter tube particles to waste plastic particles is 1:1.2.

[0063] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0064] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0065] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1.2, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0066] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0067] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0068] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0069] Example 7 The only difference from Example 1 is that the mass ratio of modified waste ceramic filter tube particles to waste plastic particles is 1:1.5.

[0070] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0071] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0072] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1.5, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0073] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0074] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0075] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0076] Example 8 The only difference from Example 1 is the proportion of coking coal and metallurgical coke composite modifier. The mass percentages are: coking coal: 99.5%, metallurgical coke composite modifier: 0.5%.

[0077] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0078] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0079] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0080] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0201kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99.5%, metallurgical coke composite modifier: 0.5%). Mix evenly to obtain a mixture.

[0081] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0082] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0083] Example 9 The only difference from Example 1 is the proportion of coking coal and metallurgical coke composite modifier. The mass percentages are: coking coal: 98.5%, metallurgical coke composite modifier: 1.5%.

[0084] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0085] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0086] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0087] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0203kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 98.5%, metallurgical coke composite modifier: 1.5%). Mix evenly to obtain a mixture.

[0088] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0089] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0090] Comparative Example 1 The only difference from Example 1 is that coking coal is used directly for coking.

[0091] Production of metallurgical coke: Step 1: Crush the coking coal to a particle size of less than 3mm, and weigh out a total of 2kg of coking coal.

[0092] Step 2: Add mist water to the coking coal, controlling the moisture content to 10%, to obtain blended coal.

[0093] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0094] Comparative Example 2 The only difference from Example 1 is that waste ceramic filter tube particles are directly added and mixed with coking coal.

[0095] Production of metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤0.075mm. Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of waste ceramic filter tube particles (dry material mass percentage: coking coal: 99%, waste ceramic filter tube particles: 1%) and mix evenly to obtain a mixture.

[0096] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0097] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0098] Comparative Example 3 The only difference from Example 1 is that waste plastic particles are directly added and mixed with coking coal.

[0099] Production of metallurgical coke: Step 1: Crush, grind and screen the waste plastic (PET material) into waste plastic particles with a particle size ≤1mm. Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of waste plastic particles (dry material mass percentage: coking coal: 99%, waste plastic particles: 1%) and mix evenly to obtain a mixture.

[0100] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0101] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0102] Comparative Example 4 The only difference from Example 1 is that the waste ceramic filter tube particles are not mixed with coke dust and then calcined at high temperature for modification, but are directly mixed with waste plastic particles to prepare a metallurgical coke composite modifier.

[0103] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0104] Step 2: Mix waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain metallurgical coke composite modifier with a particle size ≤1mm.

[0105] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0106] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0107] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0108] Comparative Example 5 The only difference from Example 1 is that the modified waste ceramic filter tube particles are simply mixed with waste plastics to prepare a metallurgical coke composite modifier, without roller extrusion.

[0109] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0110] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0111] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0112] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0113] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0114] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0115] Comparative Example 6 The only difference from Example 1 is that the waste ceramic filter tube particles are mixed with coke powder and then calcined at a high temperature of 500°C for 15 minutes.

[0116] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0117] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 500℃ for 15 minutes to obtain modified waste ceramic filter tube particles.

[0118] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0119] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0202kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 99%, metallurgical coke composite modifier: 1%). Mix evenly to obtain a mixture.

[0120] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0121] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0122] Comparative Example 7 The only difference from Example 1 is the proportion of coking coal and metallurgical coke composite modifier, which is: coking coal: 98% and metallurgical coke composite modifier: 2% by mass.

[0123] Preparation of composite modifiers for metallurgical coke: Step 1: Crush, grind and screen the waste ceramic filter tubes into particles with a particle size ≤ 0.075 mm; crush, grind and screen the waste plastic (PET material) into particles with a particle size ≤ 1 mm.

[0124] Step 2: Weigh coke dust and waste ceramic filter tube particles at a mass ratio of 1:4, mix the waste ceramic filter tube particles and coke dust thoroughly, and calcine at 700℃ for 20 minutes to obtain modified waste ceramic filter tube particles.

[0125] Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles at a mass ratio of 1:1, and then crush and screen them to obtain a metallurgical coke composite modifier with a particle size ≤1mm.

[0126] Production of metallurgical coke: Step 1: Crush the coking coal to make its particle size less than 3mm. Weigh a total of 2kg of coking coal and add 0.0204kg of metallurgical coke composite modifier (dry material mass percentage: coking coal: 98%, metallurgical coke composite modifier: 2%). Mix evenly to obtain a mixture.

[0127] Step 2: Add mist water to the mixture and control the moisture content to 10% to obtain blended coal.

[0128] Step 3: Combine coal and compact it to form a coal cake with a density of 1.00 g / cm³. 3 The material is loaded into a coking reactor and heated to 700°C at a rate of 15°C / min, then heated to 1050°C at a rate of 5°C / min. The temperature is maintained at 1050°C for 5 hours. After high-temperature coking, the material is removed and cooled to room temperature to obtain metallurgical coke.

[0129] The metallurgical cokes prepared in Examples 1-9 and Comparative Examples 1-7 were subjected to performance tests, and the results are shown in Table 1.

[0130] The test was conducted according to the method specified in the standard GB / T4000-2017 "Test Methods for Reactivity and Post-Reaction Strength of Coke".

[0131] Table 1

[0132] As can be seen from Table 1, the high-temperature roasting temperature and time of the modified waste ceramic filter tube particles in Example 1 and Comparative Example 6 are different. If the temperature is too low and the roasting time is insufficient, the coke powder will not fully reduce V2O5. Instead, the remaining active sites will catalyze the dissolution reaction, resulting in the metallurgical coke prepared in Comparative Example 6 having inferior performance compared to Example 1.

[0133] Based on the results of Example 1 and Comparative Example 5, it can be seen that the modified waste ceramic filter tube particles and waste plastic particles are fused together by roller extrusion, so that the two substances form a whole and can form a better modifier. In the process of co-coking with coking coal, it plays the role of carbon skeleton and hydrogen donor, thereby obtaining coke with better performance and achieving a 1+1>2 effect.

[0134] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0135] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes, characterized in that, Includes the following steps: Step 1: Crush, grind and sieve the waste ceramic filter tubes and waste plastics respectively to obtain waste ceramic filter tube particles and waste plastic particles respectively; Step 2: Thoroughly mix the waste ceramic filter tube particles and coke dust, and calcine at high temperature to obtain modified waste ceramic filter tube particles; Step 3: Mix the modified waste ceramic filter tube particles and waste plastic particles, and then crush and screen them to obtain the metallurgical coke composite modifier.

2. The method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes according to claim 1, characterized in that, The waste ceramic filter tube is produced from aluminum silicate fiber and carries a vanadium-titanium catalyst.

3. The method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes according to claim 1, characterized in that, The waste plastic is made of at least one of PET and PS.

4. The method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes according to claim 1, characterized in that, The mass ratio of the waste ceramic filter tube particles to the coke dust is (1:4) to (1:6).

5. The method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes according to claim 1, characterized in that, The high-temperature roasting temperature is 600℃~900℃, and the duration is 15~20min.

6. The method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes according to claim 1, characterized in that, The mass ratio of the modified waste ceramic filter tube particles to the waste plastic particles is (1:1) to (1:1.5).

7. The method for preparing a composite modifier for metallurgical coke based on waste ceramic filter tubes according to claim 1, characterized in that, The particle size of the metallurgical coke composite modifier is ≤1mm.

8. A composite modifier for metallurgical coke based on waste ceramic filter tubes, characterized in that, It is prepared by the preparation method described in any one of claims 1-7.

9. A method for producing metallurgical coke, characterized in that, The production of metallurgical coke using the metallurgical coke composite modifier as described in claim 8 includes the following steps: Step 1: Crush the coking coal, add the metallurgical coke composite modifier and mix evenly to obtain a mixture; Step 2: Add mist water to the mixture, controlling the moisture content to 10%, to obtain blended coal; Step 3: The blended coal is compacted to form coal cakes, which are then loaded into a coking reactor for high-temperature coking. The coking process is then carried out and cooled to obtain metallurgical coke.

10. A method for producing metallurgical coke according to claim 9, characterized in that, The mass ratio of the composite modifier for coking coal and metallurgical coke is (98:2) to (99.5:0.5).

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