A method for co-disposing hazardous waste incineration slag in cement kiln

Abstract

The present invention relates to the technical field of hazardous waste incineration slag treatment, and specifically to a method for cement kiln coordinated disposal of hazardous waste incineration slag; the present invention provides a new method for harmless treatment of hazardous waste incineration slag, using cement kiln to treat hazardous waste incineration slag, a small amount of heavy metals in the incineration slag in the cement kiln in a closed alkaline environment has been wrapped and melted and solidified in the cement raw material, and it will not cause harm to the environment. On the other hand, it reduces the treatment cost, reduces the landfill area, and saves the limited land required for the landfill of incineration slag. The dioxins in the incineration slag in the cement kiln are treated more thoroughly, with a dioxin removal rate of 98.1%, and the dioxin content in the tail gas meets the emission standards.

Description

Technical Field

[0001] The invention relates to the technical field of hazardous waste incineration slag treatment, in particular to a method for co-disposing hazardous waste incineration slag with a cement kiln. Background Art

[0002] Slag is mainly the residue after the burning of solid waste. Solid waste is burned at high temperature in the incinerator, so that various components in the waste are completely oxidized, decomposed and passivated to become slag, which is mainly composed of glass, metal and various inorganic substances. Its production depends on the composition of the waste. Its main components are manganese dioxide, silicon dioxide, calcium oxide, aluminum oxide, iron oxide, waste metal, and a small amount of unburned organic matter. The slag after incineration belongs to general solid waste.

[0003] Patent document CN113028422A discloses a hazardous waste incineration slag discharging system and process, including a rotary kiln, a recycled water atomization cooling device, a live steam cooling and baking device, a double-screw conveyor, an iron separator, a roller-type sorting filter and a spiral horizontal agitator. The advantages of the present invention are that by using recycled water for atomization cooling treatment, the water content of the overall system is further reduced, and the process cost is further reduced through system circulation. While saving energy, it can also achieve clean production, zero pollution, zero emissions, and resource rationalization of hazardous waste disposal.

[0004] Patent document CN113074375A specifically relates to a hazardous waste incineration and melting system and an incineration and melting method thereof. The hazardous waste incineration and melting system comprises an incineration rotary kiln, a secondary combustion chamber, and a melting chamber; the outlet of the incineration rotary kiln is connected to the secondary combustion chamber; the top of the secondary combustion chamber is provided with a flue gas outlet, and the bottom is provided with a slag outlet and connected to the melting chamber; the flue gas generated in the melting chamber enters the secondary combustion chamber from the slag outlet. The slag of this system moves in opposite directions to the high-temperature flue gas, and the two can fully contact, which can not only increase the temperature of the slag, so that the residual combustibles are further burned out, but also completely decompose the dioxin-like harmful substances therein.

[0005] At present, the treatment method for hazardous waste incineration slag is landfill, and no secondary treatment is performed. However, practice has shown that hazardous waste incineration slag after landfill will still cause secondary pollution, causing harm to water bodies and soil. In addition, the landfill treatment method also occupies limited land resources and increases treatment costs. In addition, dioxins produced during the incineration process are difficult to remove and cause harm to the environment. Summary of the invention

[0006] The present invention aims to solve the technical problem that dioxins in tail gas are difficult to remove in the prior art, thereby providing a method for co-disposing hazardous waste incineration slag in a cement kiln.

[0007] Specifically, the present invention provides the following technical solutions:

[0008] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0009] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0010] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0011] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0012] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0013] Preferably, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0014] Preferably, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0015] Preferably, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0016] Preferably, in the above-mentioned method for co-disposal of hazardous waste incineration slag in cement kiln, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 20-30:10-15:55-70:0.003-0.05.

[0017] Preferably, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 25 to 30 minutes.

[0018] Preferably, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0019] S1: Add 0.02-0.5 parts of 1,1'-ferrocenedicarboxylic acid, 2.5-5.3 parts of 2-aminoterephthalic acid, 50-100 parts of an organic solvent, 0.6-2.5 parts of hydrochloric acid with a content of 20-30% by mass, and 1-4 parts of manganese nitrate into a stirring kettle, heating and stirring to react for 50-100 minutes;

[0020] S2: Add 100-120 parts of cyclodextrin, 30-50 parts of vanadium tetrachloride, 500-800 parts of organic solvent, and 4-8 parts of hydrochloric acid with a content of 20-30% by mass into a stirring kettle, and heat and stir to react for 60-150 minutes;

[0021] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 5-10 parts of triethylamine and 0.5-3 parts of cerium methacrylate, heat up and stir to react for 20-50 minutes, remove the organic solvent by vacuum distillation, place in a constant temperature oven at 115-125°C for a preset time of 40-60 hours, cool the solution to room temperature after being kept at a constant temperature, and a dioxin remover can be obtained.

[0022] Preferably, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is one or more combinations of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

[0023] Preferably, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is one or more combinations of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, anhydrous ethanol or anhydrous methanol.

[0024] Preferably, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 70-80°C.

[0025] The technical mechanism of the present invention for preparing dioxin remover is as follows:

[0026] A trace amount of manganese organometallic skeleton is generated by 1,1'-ferrocenedicarboxylic acid and manganese nitrate, and a vanadium organometallic skeleton is generated by vanadium tetrachloride and cyclodextrin. The two organometallic skeletons are combined together through amino and cerium methacrylate addition to obtain a dioxin remover.

[0027] The beneficial effects achieved by the present invention are:

[0028] The present invention provides a new method for harmless treatment of hazardous waste incineration slag, using cement kilns to treat hazardous waste incineration slag. In the cement kiln in a closed alkaline environment, a small amount of heavy metals in the incineration slag have been wrapped, melted and solidified in the cement raw material, which will not cause harm to the environment. If inorganic sulfur and chlorine exceed the kiln entry standard, water washing is required, and the material is fed under the condition of ensuring that it does not affect the normal production of the cement kiln, while elements such as calcium, iron, and silicon are beneficial to the production of cement kilns.

[0029] On the one hand, the present invention reduces secondary pollution to the environment, achieving the purpose of energy saving and environmental protection, and on the other hand, reduces processing costs, reduces the landfill area, and saves the limited land required for landfilling of incineration slag.

[0030] The dioxins in the incineration slag in the cement kiln of the present invention are treated more thoroughly, with a dioxin removal rate of 98.1%, and the dioxin content in the tail gas meets the emission standards. DETAILED DESCRIPTION

[0031] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the art or the product instructions are used.

[0032] In the description of the present invention, unless otherwise specified, the terms "upper", "lower", etc. indicate positions or state relationships, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0033] In the following examples, the instruments used without indicating the manufacturer are all conventional products that can be purchased through regular channels. The methods described are conventional methods unless otherwise specified, and the raw materials described can be obtained from public commercial channels unless otherwise specified.

[0034] Example 1

[0035] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0036] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0037] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0038] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0039] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0040] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0041] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0042] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0043] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 20:10:55:0.01.

[0044] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 25 minutes.

[0045] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0046] S1: 0.02 kg 1,1'-ferrocene dicarboxylic acid, 2.5 kg 2-aminoterephthalic acid, 50 kg organic solvent, 0.6 kg 20% ​​by mass hydrochloric acid, and 1 kg manganese nitrate were added into a stirring kettle, and the temperature was raised and stirred for reaction for 50 min;

[0047] S2: Add 100 kg of cyclodextrin, 30 kg of vanadium tetrachloride, 500 kg of organic solvent, and 4 kg of 20% by mass hydrochloric acid into a stirring tank, heat and stir to react for 60 minutes;

[0048] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 5 kg of triethylamine and 0.5 kg of cerium methacrylate, heat up and stir to react for 20 minutes, remove the organic solvent by distillation under reduced pressure, place in a constant temperature oven at 115°C for 40 hours, cool the solution to room temperature at the constant temperature, and obtain a dioxin remover.

[0049] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is α-cyclodextrin.

[0050] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is N,N-dimethylformamide.

[0051] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 70°C.

[0052] Example 2

[0053] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0054] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0055] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0056] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0057] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0058] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0059] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0060] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0061] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 24:12:60:0.02.

[0062] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 25 minutes.

[0063] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0064] S1: 0.15 kg 1,1'-ferrocene dicarboxylic acid, 3.1 kg 2-aminoterephthalic acid, 65 kg organic solvent, 1.2 kg 20% ​​by mass hydrochloric acid, and 2 kg manganese nitrate were added into a stirring kettle, and the temperature was raised and stirred for reaction for 60 min;

[0065] S2: 105 kg of cyclodextrin, 35 kg of vanadium tetrachloride, 600 kg of organic solvent, and 5 kg of 20% by mass hydrochloric acid were added into a stirred tank, and the temperature was raised and stirred to react for 75 minutes;

[0066] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 6 kg of triethylamine and 1.2 kg of cerium methacrylate, heat up and stir to react for 30 minutes, remove the organic solvent by distillation under reduced pressure, place in a constant temperature oven at 115°C for 45 hours, cool the solution to room temperature at a constant temperature, and obtain a dioxin remover.

[0067] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is β-cyclodextrin.

[0068] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is N,N-dimethylacetamide.

[0069] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 70°C.

[0070] Example 3

[0071] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0072] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0073] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0074] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0075] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0076] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0077] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0078] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0079] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 26:13:65:0.04.

[0080] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 30 minutes.

[0081] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0082] S1: 0.4 kg 1,1'-ferrocene dicarboxylic acid, 4.5 kg 2-aminoterephthalic acid, 85 kg organic solvent, 1.8 kg 25% by mass hydrochloric acid, and 3 kg manganese nitrate were added into a stirring kettle, and the temperature was raised and stirred for reaction for 80 min;

[0083] S2: Add 110 kg of cyclodextrin, 40 kg of vanadium tetrachloride, 700 kg of organic solvent, and 6 kg of 25% by mass hydrochloric acid into a stirring tank, heat and stir to react for 100 min;

[0084] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 8 kg of triethylamine and 2 kg of cerium methacrylate, heat up and stir to react for 40 minutes, remove the organic solvent by vacuum distillation, place in a constant temperature oven at 125°C for 50 hours, cool the solution to room temperature at a constant temperature, and obtain a dioxin remover.

[0085] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is γ-cyclodextrin.

[0086] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is N-methylpyrrolidone.

[0087] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 80°C.

[0088] Example 4

[0089] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0090] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0091] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0092] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0093] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0094] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0095] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0096] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0097] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 30:15:70:0.05.

[0098] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 30 minutes.

[0099] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0100] S1: 0.5 kg 1,1'-ferrocene dicarboxylic acid, 5.3 kg 2-aminoterephthalic acid, 100 kg organic solvent, 2.5 kg 30% by mass hydrochloric acid, and 4 kg manganese nitrate were added into a stirring kettle, and the temperature was raised and stirred to react for 100 min;

[0101] S2: Add 120 kg of cyclodextrin, 50 kg of vanadium tetrachloride, 800 kg of organic solvent, and 8 kg of 30% by mass hydrochloric acid into a stirring tank, heat and stir to react for 150 min;

[0102] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 10 kg of triethylamine and 3 kg of cerium methacrylate, heat up and stir to react for 50 minutes, remove the organic solvent by vacuum distillation, place in a constant temperature oven at 125°C for a preset time of 60 hours, cool the solution at the constant temperature to room temperature, and you can get a dioxin remover.

[0103] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is α-cyclodextrin.

[0104] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is tetrahydrofuran.

[0105] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 80°C.

[0106] Comparative Example 1

[0107] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0108] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0109] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0110] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage tank, and is mixed with rice husks and distillation residues to obtain a mixture (c);

[0111] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0112] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0113] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0114] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0115] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 20:10:55.

[0116] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 25 minutes.

[0117] Comparative Example 2

[0118] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0119] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0120] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0121] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0122] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0123] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0124] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0125] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0126] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 20:10:55:0.01.

[0127] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 25 minutes.

[0128] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0129] S1: Add 2.5 kg 2-aminoterephthalic acid, 50 kg organic solvent, 0.6 kg 20% ​​by mass hydrochloric acid, and 1 kg manganese nitrate into a stirring kettle, heat and stir to react for 50 min;

[0130] S2: Add 100 kg of cyclodextrin, 30 kg of vanadium tetrachloride, 500 kg of organic solvent, and 4 kg of 20% by mass hydrochloric acid into a stirring tank, heat and stir to react for 60 minutes;

[0131] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 5 kg of triethylamine and 0.5 kg of cerium methacrylate, heat up and stir to react for 20 minutes, remove the organic solvent by distillation under reduced pressure, place in a constant temperature oven at 115°C for 40 hours, cool the solution to room temperature at the constant temperature, and obtain a dioxin remover.

[0132] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is α-cyclodextrin.

[0133] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is N,N-dimethylformamide.

[0134] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 70°C.

[0135] Comparative Example 3

[0136] A method for co-disposing hazardous waste incineration slag in a cement kiln, the operating steps of which are:

[0137] S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material (a);

[0138] S2: the oversize material is fed into a hammer crusher, and the undersize material after crushing is mixed with material (a) to obtain material (b);

[0139] S3: sending material (b) to a magnetic separation belt conveyor, and the material after three-stage magnetic separation enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture (c);

[0140] S4: The mixture (c) is sent to a mixer for uniform mixing, and then pumped to a cement kiln decomposition furnace for incineration.

[0141] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the screening equipment in S1 is a 120 mm drum screen.

[0142] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the size of the crushed undersize material in S2 does not exceed 5 mm.

[0143] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

[0144] In this example, in the above-mentioned cement kiln coordinated disposal of hazardous waste incineration slag method, the mass ratio of material (b): rice husk: distillation residue: dioxin decomposition catalyst in S3 is 20:10:55:0.01.

[0145] In this example, in the above-mentioned method for co-disposal of hazardous waste incineration slag in a cement kiln, the mixing agitator in S4 stirs for 25 minutes.

[0146] In this example, in the above-mentioned method for the coordinated disposal of hazardous waste incineration slag by a cement kiln, the preparation method of the dioxin decomposition catalyst is as follows:

[0147] S1: 0.02 kg 1,1'-ferrocene dicarboxylic acid, 2.5 kg 2-aminoterephthalic acid, 50 kg organic solvent, 0.6 kg 20% ​​by mass hydrochloric acid, and 1 kg manganese nitrate were added into a stirring kettle, and the temperature was raised and stirred for reaction for 50 min;

[0148] S2: Add 100 kg of cyclodextrin, 30 kg of vanadium tetrachloride, and 500 kg of organic solvent into a stirred tank, heat and stir to react for 60 minutes;

[0149] S3: Combine the products in the kettles of S1 and S2 in a reaction kettle, add 5 kg of triethylamine and 0.5 kg of cerium methacrylate, heat up and stir to react for 20 minutes, remove the organic solvent by distillation under reduced pressure, place in a constant temperature oven at 115°C for 40 hours, cool the solution to room temperature at the constant temperature, and obtain a dioxin remover.

[0150] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the cyclodextrin is α-cyclodextrin.

[0151] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the organic solvent is N,N-dimethylformamide.

[0152] In this example, in the above-mentioned method for preparing a dioxin decomposition catalyst, the reaction temperature in S1-S3 is 70°C.

[0153] The dioxin content and removal rate of the flue gas generated during the incineration process of the above specific implementation plan are shown in the following table:

[0154]

[0155]

[0156] According to the Standard of the People's Republic of China GB 18484-2020 "Pollution Control Standard for Hazardous Waste Incineration", "Table 3 Emission Concentration Limits of Flue Gas Pollutants from Hazardous Waste Incineration Facilities. Among them, the emission of dioxin-type air pollutants is ≤ 0.5ngTEQ / Nm 3 .

[0157] Although the present invention has been described in detail above by general description, specific implementation methods and experiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A method for co-disposal of hazardous waste incineration slag in a cement kiln, the operating steps of which are: S1: After the hazardous waste incineration slag is screened, the screened material is sent to the material pit to obtain material a; S2: The oversize material is sent to the hammer crusher, and the undersize material after crushing is mixed with material a to obtain material b; S3: Send material b to a magnetic separation belt conveyor, and after three-stage magnetic separation, the material enters a hazardous waste storage pool, and is mixed with rice husks, distillation residues, and a dioxin remover to obtain a mixture c; S4: sending the mixture c into a mixer for uniform mixing, and then pumping it to a cement kiln decomposition furnace for incineration; The mass ratio of material b: rice husk: distillation residue: dioxin remover in S3 is 20-30: 10-15: 55-70: 0.003-0.05; The dioxin remover preparation method is as follows: H1: Add 0.02-0.5 parts of 1,1'-ferrocenedicarboxylic acid, 2.5-5.3 parts of 2-aminoterephthalic acid, 50-100 parts of organic solvent, 0.6-2.5 parts of hydrochloric acid with a content of 20-30% by mass, and 1-4 parts of manganese nitrate into a stirring kettle, and heat and stir to react for 50-100 minutes; H2: Add 100-120 parts of cyclodextrin, 30-50 parts of vanadium tetrachloride, 500-800 parts of organic solvent, and 4-8 parts of hydrochloric acid with a content of 20-30% by mass into a stirring kettle, and heat and stir to react for 60-150 minutes; H3: Combine the products in the kettles of H1 and H2 in a reaction kettle, add 5-10 parts of triethylamine and 0.5-3 parts of cerium methacrylate by mass, heat up and stir to react for 20-50 minutes, remove the organic solvent by vacuum distillation, place in a constant temperature oven at 115-125°C for a preset time of 40-60 hours, cool the solution to room temperature after being kept at a constant temperature, and you can get a dioxin remover.

2. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The screening equipment in S1 is a 120mm drum screen.

3. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The size of the material under the sieve after crushing in S2 does not exceed 5 mm.

4. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The oversize material in S2 is cyclically crushed until all of it does not exceed 5 mm.

5. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The cyclodextrin is one or more combinations of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

6. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The organic solvent is one or more combinations of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, anhydrous ethanol or anhydrous methanol.

7. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The reaction temperature in H1-H3 is 70-80°C.

8. The method for co-disposal of hazardous waste incineration slag in a cement kiln according to claim 1, characterized in that: The S4 mixer was stirred for 25-30 minutes.

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