Method for preparing ozone catalyst by using chlorinated waste salt byproduct material

Abstract

The invention relates to the technical field of environmental protection, in particular to a method for preparing an ozone catalyst by using a chlorinated waste salt byproduct material. The method comprises the following steps: carrying out water quenching treatment on the chlorinated waste salt to obtain water-quenched slag and crude brine, and then carrying out sorting treatment on the water-quenched slag to obtain aggregate; carrying out oxidation impurity removal and plate-frame pressure filtration on the crude brine to obtain an intermediate filtrate; sequentially carrying out washing, drying, grinding and sieving treatment on the intermediate filtered substance to obtain an active agent; and preparing the active agent, the aggregate and the binder into a finished product of the catalyst according to the proportion. According to the method, the cost of landfill treatment is saved, the synthesized catalyst is used as a wastewater COD treatment medium, the economic value of solid waste materials is improved, and the clean production and utilization level of a molten salt chlorination process and the high additional value of products are improved by matching with a chlorinated waste salt overall resourceful treatment technology.

Description

Technical Field

[0001] The invention relates to the technical field of environmental protection, and in particular to a method for preparing an ozone catalyst by utilizing chlorinated waste salt byproducts. Background Art

[0002] The process of preparing titanium tetrachloride by chlorination of titanium slag molten salt produces high temperature (700-750℃) molten waste salt slag, the amount of which is about 400kg / t.TiCl 4 , of which the soluble salt content is as high as more than 80%. At present, the "molten salt chlorination waste brine quenching - oxidation impurity removal - magnesium removal - brine reuse" treatment method is used to achieve comprehensive resource recovery and utilization. However, in the waste salt treatment process, there is a secondary treatment of insoluble waste slag (water quenching slag) and iron hydroxide mixture. The main component of the water quenching slag is SiO 2 、TiO 2 , C, Fe 2 O 3 、Al 2 O 3 , Ca, Mg, etc. The main component of the iron hydroxide mixture is Fe(OH) 3 、MnCO 3 、CaCO 3 At present, the landfill method is adopted for treatment. According to the existing resource recovery process, about 100 kg of water-quenched slag and 80 kg of ferric hydroxide mixture are produced for every ton of titanium tetrachloride produced. According to the current landfill treatment, not only tens of thousands of tons of TiO 2 The waste of Fe / Mn resources and the increase of landfill costs and environmental risks. In order to solve the technical problem, a method for preparing an ozone catalyst using chlorinated waste salt byproducts is proposed. Summary of the invention

[0003] In order to solve the technical problems existing in the above-mentioned prior art, the present invention provides a method for preparing an ozone catalyst using chlorinated waste salt by-product material.

[0004] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions: In a first aspect, in one embodiment provided by the present invention, a method for preparing an ozone catalyst using chlorinated waste salt byproduct material is provided, the method comprising the following steps: Performing water quenching treatment on the chlorinated waste salt to obtain water quenched slag and crude brine, and then sorting the water quenched slag to obtain aggregate; The crude brine is subjected to oxidation and impurity removal and plate-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent; The active agent, aggregate and binder are prepared into a finished catalyst in proportion.

[0005] As a further embodiment of the present invention, the chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is subjected to sorting treatment to obtain aggregate, comprising: The water-quenched slag and water are fully mixed with stirring at a mass ratio of 1:4-5, and separated by cyclone action to obtain materials with a particle size of >200um. The materials are dried at 110℃-150℃ and crushed evenly to obtain the aggregate of the catalyst.

[0006] As a further embodiment of the present invention, the chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is subjected to sorting treatment to obtain aggregate, including: The water-quenched slag and water are fully mixed under stirring at a mass ratio of 1:4.3-4.7, and the material with a particle size of >200um is separated by cyclone action. The material is dried at 120℃-140℃ and crushed evenly to obtain the aggregate of the catalyst.

[0007] As a further embodiment of the present invention, the crude brine is subjected to oxidation and impurity removal and plate-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground, and sieved to obtain an active agent, including: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.8-6.2, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment; after drying at 70°C-80°C, it is ground by a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0008] As a further embodiment of the present invention, the step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.9-6.1, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment; after drying at 73°C-77°C, it is ground by a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0009] As a further embodiment of the present invention, the crude brine is subjected to oxidation and impurity removal and plate-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground, and sieved to obtain an active agent, including: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 6.0, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment, dried at 75°C, ground by a ball mill, and passed through an 80-mesh sieve to obtain the active agent.

[0010] As a further embodiment of the present invention, the active agent, aggregate and binder are prepared into a finished catalyst in proportion, including: Aggregates and active agents are mixed uniformly in a mass ratio of 1:0.5-0.8, a binder of 2-5wt% is added, the mixture is stirred rapidly, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo; The catalyst embryo is calcined to obtain a catalyst.

[0011] As a further embodiment of the present invention, the step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 105°C-110°C for 4 hours, place in a muffle furnace for calcination at 900°C-1200°C for 2-4 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0012] As a further embodiment of the present invention, the step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 106°C-109°C for 4 hours, place in a muffle furnace for calcination at 950°C-1150°C for 2.5-3.5 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0013] As a further solution of the present invention, the binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0014] The technical solution provided by the present invention has the following beneficial effects: The present invention uses water-quenched slag pre-treated materials as aggregates and ferric hydroxide mixtures as active additives, making full use of Si, Ti, Al, Fe and Mn elements therein, thereby solving the risk of landfill treatment of water-quenched slag and ferric hydroxide mixtures and saving the cost of landfill treatment. The synthesized catalyst is used as a treatment medium for wastewater COD, thereby improving the economic value of solid waste materials. The supporting chlorinated waste salt overall resource treatment technology improves the clean production and utilization level of the molten salt chlorination process and the high added value of the product.

[0015] These and other aspects of the present invention will be more clearly understood in the following description of the embodiments. It should be understood that the above general description and the following detailed description are only exemplary and explanatory and cannot limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.

[0017] Figure 1 The present invention is a specific flow chart of a method for preparing an ozone catalyst using chlorinated waste salt by-product material according to an embodiment of the present invention.

[0018] Figure 2 This is a schematic diagram of an ozone catalytic oxidation wastewater device in a method for preparing an ozone catalyst using chlorinated waste salt by-product material according to an embodiment of the present invention. DETAILED DESCRIPTION

[0019] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] The flowcharts shown in the accompanying drawings are only examples and do not necessarily include all the contents and operations / steps, nor must they be executed in the order described. For example, some operations / steps may be decomposed, combined or partially merged, so the actual execution order may change according to actual conditions.

[0021] like Figure 1 As shown, the present invention provides a method for preparing an ozone catalyst using a chlorinated waste salt by-product material, and the method for preparing an ozone catalyst using a chlorinated waste salt by-product material comprises the following steps: S1. The chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is sorted to obtain aggregate.

[0022] In the embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are mixed thoroughly with a mass ratio of 1:4-5 under stirring, and the material with a particle size of >200um is separated by cyclone action. After drying at 110℃-150℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0023] In an embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are fully mixed under stirring at a mass ratio of 1:4.3-4.7, and the material with a particle size of >200um is separated by cyclone action. After drying at 120℃-140℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0024] In an embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are fully mixed under stirring at a mass ratio of 1:4.5, and the material with a particle size of >200um is separated by cyclone action. After drying at 130℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0025] It should be noted that water-quenched slag is an insoluble substance produced by the rapid dissolution of 700-720℃ chlorinated waste salt under the action of high-speed water flow, and the NaCl content is controlled to be less than 0.3% after water washing. Cyclone includes one of the following: hydraulic cyclone, aeration cyclone, gravity rotating bed, etc.; the aggregate components are mainly (Ca, Al, Mg)SiO 3 、SiO 2 , Fe 2 O 3 , or add 0.5-1.0wt% of TiO 2 materials.

[0026] S2. The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent.

[0027] In an embodiment of the present invention, the step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.8-6.2, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 70°C-80°C, it is ground in a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0028] In an embodiment of the present invention, the step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.9-6.1, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 73°C-77°C, it is ground in a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0029] In an embodiment of the present invention, the step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 6.0, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 75°C, it is ground by a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0030] S3. Prepare the finished catalyst by proportioning the active agent, aggregate and binder.

[0031] In the embodiment of the present invention, the step S3, preparing the active agent, aggregate and binder into a finished catalyst in proportion, comprises: S31. Aggregates and active agents are uniformly mixed in a mass ratio of 1:0.5-0.8, 2-5wt% of a binder is added, the mixture is rapidly stirred, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo.

[0032] The pressure of the extrusion granulator is controlled at 8-12 MPa, and the size is controlled at Φ2.5 mm×5-8 mm.

[0033] S32, calcining the catalyst embryo to obtain a catalyst.

[0034] In an embodiment of the present invention, the step of calcining the catalyst embryo to obtain the catalyst includes: Dry at 105°C-110°C for 4 hours, place in a muffle furnace for calcination at 900°C-1200°C for 2-4 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0035] In an embodiment of the present invention, the step of calcining the catalyst embryo to obtain the catalyst includes: Dry at 106°C-109°C for 4 hours, place in a muffle furnace for calcination at 950°C-1150°C for 2.5-3.5 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0036] The step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 108°C for 4 hours, place in a muffle furnace for calcination at 1000°C for 3 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0037] The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0038] The present invention uses water-quenched slag pre-treated materials as aggregates and ferric hydroxide mixtures as active additives, making full use of Si, Ti, Al, Fe and Mn elements therein, thereby solving the risk of landfill treatment of water-quenched slag and ferric hydroxide mixtures and saving the cost of landfill treatment. The synthesized catalyst is used as a treatment medium for wastewater COD, thereby improving the economic value of solid waste materials. The supporting chlorinated waste salt overall resource treatment technology improves the clean production and utilization level of the molten salt chlorination process and the high added value of the product.

[0039] Example 1 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1. The chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is sorted to obtain aggregate.

[0040] In an embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are mixed in a mass ratio of 1:4 under stirring, and the material with a particle size of >200um is separated by cyclone action. After drying at 110℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0041] It should be noted that water-quenched slag is the insoluble matter produced by the rapid dissolution of 700℃ chlorinated waste salt under the action of high-speed water flow. After water washing, the NaCl content is controlled to be less than 0.3%. Cyclone includes one of the following: hydraulic cyclone, aerated cyclone, gravity rotating bed, etc.; the aggregate components are mainly (Ca, Al, Mg)SiO 3 、SiO 2 , Fe 2 O 3 , or add 0.5-1.0wt% of TiO 2 materials.

[0042] S2. The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent.

[0043] The step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.8, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 70°C to 80°C, it is ground in a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0044] S3. Prepare the finished catalyst by proportioning the active agent, aggregate and binder.

[0045] The step S3, preparing the catalyst product from the active agent, aggregate and binder in proportion, comprises: S31. Aggregates and active agents are uniformly mixed in a mass ratio of 1:0.5, 2 wt % binder is added, the mixture is rapidly stirred, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo.

[0046] The pressure of the extrusion granulator is controlled at 8-12 MPa, and the size is controlled at Φ2.5 mm×5-8 mm.

[0047] S32, calcining the catalyst embryo to obtain a catalyst.

[0048] The step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 105°C for 4 hours, place in a muffle furnace for calcination at 900°C for 2 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0049] The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0050] Example 2 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1. The chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is sorted to obtain aggregate.

[0051] In an embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are mixed thoroughly with a mass ratio of 1:5 under stirring, and the material with a particle size of >200um is separated by cyclone action. After drying at 150℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO2 The material can be directly reused as raw material of S1.

[0052] S2. The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent.

[0053] The step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 6.2, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 80°C, it is ground by a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0054] S3. Prepare the finished catalyst by proportioning the active agent, aggregate and binder.

[0055] The step S3, preparing the catalyst product from the active agent, aggregate and binder in proportion, comprises: S31, the aggregate and the active agent are evenly mixed in a mass ratio of 1:0.8, 5wt% of a binder is added, the mixture is rapidly stirred, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo.

[0056] The pressure of the extrusion granulator is controlled at 8-12 MPa, and the size is controlled at Φ2.5 mm×5-8 mm.

[0057] S32, calcining the catalyst embryo to obtain a catalyst.

[0058] The step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 105°C-110°C for 4 hours, place in a muffle furnace for calcination at 1200°C for 2-4 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0059] The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0060] Example 3 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1. The chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is sorted to obtain aggregate.

[0061] In an embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are fully mixed under stirring at a mass ratio of 1:4.3, and the material with a particle size of >200um is separated by cyclone action. After drying at 120℃~140℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0062] S2. The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent.

[0063] In an embodiment of the present invention, the step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.9, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 73°C, it is ground in a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0064] S3. Prepare the finished catalyst by proportioning the active agent, aggregate and binder.

[0065] In the embodiment of the present invention, the step S3, preparing the active agent, aggregate and binder into a finished catalyst in proportion, comprises: S31, the aggregate and the active agent are evenly mixed in a mass ratio of 1:0.6, 3wt% of a binder is added, the mixture is rapidly stirred, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo.

[0066] The pressure of the extrusion granulator is controlled at 8-12 MPa, and the size is controlled at Φ2.5 mm×5-8 mm.

[0067] S32, calcining the catalyst embryo to obtain a catalyst.

[0068] In an embodiment of the present invention, the step of calcining the catalyst embryo to obtain the catalyst includes: Dry at 106°C for 4 hours, place in a muffle furnace for calcination at 950°C for 2.5 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0069] The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0070] Example 4 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1. The chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is sorted to obtain aggregate.

[0071] In an embodiment of the present invention, the step S1, quenching the chlorinated waste salt with water to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are fully mixed with stirring at a mass ratio of 1:4.7, and the material with a particle size of >200um is separated by cyclone action. After drying at 140℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0072] S2. The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent.

[0073] In an embodiment of the present invention, the step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 6.1, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 77°C, it is ground by a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0074] S3. Prepare the finished catalyst by proportioning the active agent, aggregate and binder.

[0075] In the embodiment of the present invention, the step S3, preparing the active agent, aggregate and binder into a finished catalyst in proportion, comprises: S31, the aggregate and the active agent are evenly mixed in a mass ratio of 1:0.7, 4wt% of a binder is added, the mixture is rapidly stirred, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo.

[0076] The pressure of the extrusion granulator is controlled at 8-12 MPa, and the size is controlled at Φ2.5 mm×5-8 mm.

[0077] S32, calcining the catalyst embryo to obtain a catalyst.

[0078] In an embodiment of the present invention, the step of calcining the catalyst embryo to obtain the catalyst includes: Dry at 109°C for 4 hours, place in a muffle furnace for calcination at 1150°C for 3.5 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0079] The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0080] Example 5 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1. The chlorinated waste salt is subjected to water quenching treatment to obtain water quenched slag and crude brine, and then the water quenched slag is sorted to obtain aggregate.

[0081] The step S1, quenching the chlorinated waste salt to obtain water-quenched slag and crude brine, and then sorting the water-quenched slag to obtain aggregate, comprises: The water-quenched slag and water are fully mixed under stirring at a mass ratio of 1:4.5, and the material with a particle size of >200um is separated by cyclone action. After drying at 130℃, the powder is evenly crushed to be the aggregate of the catalyst. The separated material with a particle size of ≤200um mainly contains TiO 2 The material can be directly reused as raw material of S1.

[0082] S2. The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent.

[0083] The step S2, oxidizing and removing impurities from the crude brine and performing plate-frame filtration to obtain an intermediate filtrate; and sequentially washing, drying, grinding, and sieving the intermediate filtrate to obtain an active agent, comprises: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 6.0, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment to control the NaCl content to less than 0.3%; after drying at 75°C, it is ground by a ball mill and passed through an 80-mesh sieve to obtain the active agent.

[0084] S3. Prepare the finished catalyst by proportioning the active agent, aggregate and binder.

[0085] In the embodiment of the present invention, the step S3, preparing the active agent, aggregate and binder into a finished catalyst in proportion, comprises: S31, the aggregate and the active agent are mixed evenly in a mass ratio of 1:0.55, 3.5wt% of a binder is added, the mixture is stirred rapidly, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo.

[0086] The pressure of the extrusion granulator is controlled at 8-12 MPa, and the size is controlled at Φ2.5 mm×5-8 mm.

[0087] S32, calcining the catalyst embryo to obtain a catalyst.

[0088] The step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 108°C for 4 hours, place in a muffle furnace for calcination at 1000°C for 3 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

[0089] The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

[0090] Example 6 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1, 700 ℃ chlorinated waste salt is quenched by high-speed slag flushing water. After quenching, the insoluble slag is filtered and washed. When the NaCl content is lower than 0.3%, it is discharged to the pulping tank, and clean water is added in a mass ratio of 1:4 for stirring. It is pumped into the hydrocyclone through a pump, and the slurry with a particle size greater than 200um after cyclone is filtered through a plate and frame. The filter residue is dried at 110 ℃ to obtain aggregate. Its composition is shown in Table 1. SiO 2 The content is 68.80%, Fe 2 O 3 The content reaches 4.92%.

[0091] Table 1 Composition analysis results of coarse slag after drying from cyclone flow / % <![CDATA[Fe 2 THE 3 ]]> CaO MgO <![CDATA[Al 2 THE 3 ]]> <![CDATA[SiO 2 ]]> <![CDATA[TiO 2 ]]> Cl 4.92 8.32 6.41 9.49 68.80 2.01 0.05 S2, the solution after water quenching in S1 is removed by chlorinated tail gas absorption liquid (waste brine) + sodium carbonate, the solution reaction pH is controlled to 6.2, the produced precipitate is controlled to have a NaCl content of less than 0.3% by multi-stage countercurrent, dried at 70°C, ground by a ball mill, and passed through an 80-mesh sieve. The sieved material is the active additive (activator), and its composition is Fe(OH) 3 Content 81.2%, MnCO 3 Content 5.2%, CaCO 3 Content: 6.4%.

[0092] S3. Mix the aggregate and the active agent in a granulator at a mass ratio of 1:0.6, add aluminum dihydrogen phosphate binder, control the extrusion pressure to obtain the catalyst embryo, and then dry and calcine to obtain the catalyst product. Among them, the content of aluminum dihydrogen phosphate accounts for 4% of the total amount of the mixture, the molding strength is 10 MPa, and the size of the embryo is Φ2.5mm×8mm. It is dried at 105℃ for 4 hours, and then placed in a muffle furnace for calcination at a calcination temperature of 1100℃ and a calcination time of 2 hours. After the calcination is completed, it is naturally cooled, and after the surface residue is washed off with deionized water, it is naturally dried to obtain the final ozone catalyst product.

[0093] S4. The obtained ozone catalyst product is applied to the biochemical tail water of coking wastewater. The reaction device is a glass column (inner diameter 4 cm, height 1.0 m), as shown in the schematic diagram Figure 2 When the initial pH of the wastewater was 8.12, the ozone dosage was 180 mg / (L·h), the catalyst mass concentration was 30 g / L, and the reaction time was 60 min, the COD dropped from 146 mg / L to 78 mg / L, and the removal rate reached 46.57%.

[0094] Example 7 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1, 720℃ chlorinated waste salt is quenched under the action of high-speed slag flushing water. After quenching, the insoluble slag is filtered and washed. When the NaCl content is lower than 0.3%, it is discharged to the pulping tank, and clean water is added at a mass ratio of 1:5 for stirring. It is pumped into the hydrocyclone through a pump, and the slurry with a particle size greater than 200um after cyclone is filtered through a plate and frame. The filter residue is dried at 120℃ to obtain aggregate. Its composition is shown in Table 2. SiO 2 The content is 71.49%, Al 2 O 3 The content reaches 8.66%, Fe 2 O 3 The content reaches 4.16%.

[0095] Table 2 Composition analysis results of coarse slag after drying from cyclone flow / % <![CDATA[Fe 2 THE 3 ]]> CaO MgO <![CDATA[Al 2 THE 3 ]]> <![CDATA[SiO 2 ]]> <![CDATA[TiO 2 ]]> Cl 4.16 8.12 5.79 8.66 71.49 1.76 0.02 S2, the solution after water quenching in S1 is removed by chlorinated tail gas absorption liquid (waste brine) + sodium carbonate, the solution reaction pH is controlled to 6.0, the produced precipitate is controlled to have a NaCl content of less than 0.3% by multi-stage countercurrent, dried at 70°C, ground by a ball mill, and passed through an 80-mesh sieve. The sieved material is the active additive (activator), and its composition is Fe(OH) 3 Content 84.11%, MnCO 3 Content 4.05%, CaCO 3 Content: 5.82%.

[0096] S3. Mix the aggregate and the active agent in a granulator at a mass ratio of 1:0.5, add a silica sol binder, control the extrusion pressure to obtain a catalyst embryo, and then dry and calcine to obtain a catalyst product. Among them, the silica sol content accounts for 2.5% of the total amount of the mixture, the molding strength is 8 MPa, and a body with a size of Φ2.5mm×5mm is obtained. It is dried at 110℃ for 4 hours and then placed in a muffle furnace for calcination at a calcination temperature of 900℃ and a calcination time of 4 hours. After the calcination is completed, it is naturally cooled, and after the surface residue is washed off with deionized water, it is naturally dried to obtain the final ozone catalyst product.

[0097] S4. The obtained ozone catalyst product was applied to the biochemical tail water of coking wastewater. When the initial pH of the wastewater was 8.12, the ozone dosage was 180 mg / (L·h), the catalyst mass concentration was 30g / L, and the reaction time was 60min, the COD dropped from 146mg / L to 66mg / L, and the removal rate reached 54.79%.

[0098] Example 8 A method for preparing an ozone catalyst using chlorinated waste salt byproduct material comprises the following steps: S1, 720℃ chlorinated waste salt is quenched by high-speed slag flushing water. After quenching, the insoluble slag is filtered and washed. When the NaCl content is lower than 0.3%, it is discharged to the pulping tank, and clean water is added in a mass ratio of 1:4 for stirring. It is pumped into the aeration cyclone. The slurry with a particle size greater than 200um after cyclone is filtered through a plate and frame. The filter residue is dried at 120℃ to obtain aggregate. Its composition is shown in Table 3. SiO 2 The content is 72.66%, Al 2 O 3 The content reaches 7.70%, Fe 2 O 3 The content reaches 4.12%.

[0099] Table 3 Composition analysis results of coarse slag after drying from cyclone flow / % <![CDATA[Fe 2 THE 3 ]]> CaO MgO <![CDATA[Al 2 THE 3 ]]> <![CDATA[SiO 2 ]]> <![CDATA[TiO 2 ]]> Cl 4.12 8.18 5.86 7.70 72.66 1.46 0.02 S2, the solution after water quenching in S1 is removed by chlorinated tail gas absorption liquid (waste brine) + sodium carbonate, the solution reaction pH is controlled to 6.0, the produced precipitate is controlled to have a NaCl content of less than 0.3% by multi-stage countercurrent, dried at 80°C, ground by a ball mill, and passed through an 80-mesh sieve. The sieved material is the active additive (activator), and its composition is Fe(OH) 3 Content 84.06%, MnCO 3 Content 4.08%, CaCO 3 Content: 5.88%.

[0100] S3. Mix the aggregate and the active agent in a granulator at a mass ratio of 1:0.5, add silica sol + polyvinyl alcohol (ratio 1:1) binder, control the extrusion pressure to obtain the catalyst embryo, and then dry and calcine to obtain the catalyst product. Among them, the binder content accounts for 5% of the total amount of the mixture, the molding strength is 12 MPa, and the size of the green body is Φ2.5mm×8mm. It is dried at 110 ℃ for 4 hours, and then placed in a muffle furnace for calcination at a calcination temperature of 1200 ℃ and a calcination time of 2 hours. After the calcination is completed, it is naturally cooled, and after the surface residue is washed off with deionized water, it is naturally dried to obtain the final ozone catalyst product.

[0101] S4. The obtained ozone catalyst product was applied to the biochemical tail water of coking wastewater. When the initial pH of the wastewater was 8.12, the ozone dosage was 180 mg / (L·h), the catalyst mass concentration was 30g / L, and the reaction time was 60min, the COD dropped from 146mg / L to 62mg / L, and the removal rate reached 57.53%.

[0102] Application Example 1 The obtained ozone catalyst product was applied to low-concentration biochemical effluent from coking wastewater and printing and dyeing wastewater. The reaction device was a glass column (inner diameter 4 cm, height 1.0 m). When the initial pH of the wastewater was 8.1, the ozone dosage was 180 mg / (L·h), the catalyst mass concentration was 30 g / L, and the reaction time was 60 min, the results were shown in the following table, indicating that the removal rate of COD by the prepared ozone catalyst in synergistic ozone oxidation was ≥46%.

[0103]

[0104] COD dropped from 146mg / L to 64mg / L, and the removal rate reached 56.16%.

[0105] Application Example 2 The obtained ozone catalyst product was applied to low-concentration biochemical effluent from coking wastewater and printing and dyeing wastewater. The reaction device was a glass column (inner diameter 4 cm, height 1.0 m). When the initial pH of the wastewater was 8.1, the ozone dosage was 180 mg / (L·h), the catalyst mass concentration was 30 g / L, and the reaction time was 60 min, the results were shown in the following table, indicating that the removal rate of COD by the prepared ozone catalyst in synergistic ozone oxidation was closely related to the influent COD concentration.

[0106]

[0107] Application Example 3 The obtained ozone catalyst product was applied to low-concentration biochemical effluent from coking wastewater and printing and dyeing wastewater. The reaction device was a glass column (inner diameter 4 cm, height 1.0 m). When the initial pH of the wastewater was 8.1, the ozone dosage was 180 mg / (L·h), the catalyst mass concentration was 50 g / L, and the reaction time was 60 min, the results were shown in the following table, indicating that the addition of different ozone catalyst contents also had a great relationship with the COD removal rate. Increasing the catalyst addition amount to 50 g / L increased the COD removal rate by 5-6%.

[0108]

[0109] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. A method for preparing an ozone catalyst using chlorinated waste salt byproducts, characterized in that: The method includes: Performing water quenching treatment on the chlorinated waste salt to obtain water quenched slag and crude brine, and then sorting the water quenched slag to obtain aggregate; The crude brine is subjected to oxidation and impurity removal and plate-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground and sieved to obtain an active agent; The active agent, aggregate and binder are prepared into a finished catalyst in proportion.

2. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 1, characterized in that: The method comprises: subjecting the chlorinated waste salt to water quenching treatment to obtain water quenched slag and crude brine, and then subjecting the water quenched slag to sorting treatment to obtain aggregate, comprising: The water-quenched slag and water are fully mixed with stirring at a mass ratio of 1:4-5, and separated by cyclone action to obtain materials with a particle size of >200um. The materials are dried at 110℃-150℃ and crushed evenly to obtain the aggregate of the catalyst.

3. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 1, characterized in that: The chlorinated waste salt is quenched to obtain quenched slag and crude brine, and then the quenched slag is sorted to obtain aggregates, including: The water-quenched slag and water are fully mixed under stirring at a mass ratio of 1:4.3-4.7, and the material with a particle size of >200um is separated by cyclone action. The material is dried at 120℃-140℃ and crushed evenly to obtain the aggregate of the catalyst.

4. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 1, characterized in that: The crude brine is subjected to oxidation and impurity removal and plate-frame filter pressing to obtain an intermediate filtrate; the intermediate filtrate is sequentially washed, dried, ground, and sieved to obtain an active agent, including: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.8-6.2, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is used, and the precipitate is subjected to multi-stage countercurrent treatment; after drying at 70°C-80°C, it is ground in a ball mill and screened to obtain the active agent.

5. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 1, characterized in that: The method comprises: performing oxidation and impurity removal on the crude brine and plate-frame filter pressing to obtain an intermediate filtrate; and sequentially washing, drying, grinding and sieving the intermediate filtrate to obtain an active agent. During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 5.9-6.1, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is subjected to multi-stage countercurrent treatment; after drying at 73°C-77°C, it is ground in a ball mill and screened to obtain the active agent.

6. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 5, characterized in that: The crude brine is subjected to oxidation and impurity removal and plate-and-frame filter pressing to obtain an intermediate filtrate; The intermediate filtrate is sequentially washed, dried, ground, and sieved to obtain an active agent, including: During the oxidation and impurity removal treatment, the solution reaction pH is controlled to 6.0, and the precipitate produced by co-precipitation of chlorinated tail gas absorption liquid (waste brine) and sodium carbonate is subjected to multi-stage countercurrent treatment, dried at 75°C, ground by a ball mill, and screened to obtain the active agent.

7. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 1, characterized in that: The active agent, aggregate and binder are prepared into a finished catalyst in proportion, including: Aggregates and active agents are mixed uniformly in a mass ratio of 1:0.5-0.8, a binder of 2-5wt% is added, the mixture is stirred rapidly, and the mixture is placed in an extrusion granulator to obtain a catalyst embryo; The catalyst embryo is calcined to obtain a catalyst.

8. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 1, characterized in that: The step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 105°C-110°C for 4 hours, place in a muffle furnace for calcination at 900°C-1200°C for 2-4 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

9. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material as claimed in claim 8, characterized in that: The step of calcining the catalyst embryo to obtain the catalyst comprises: Dry at 106°C-109°C for 4 hours, place in a muffle furnace for calcination at 950°C-1150°C for 2.5-3.5 hours, then naturally cool to room temperature to obtain the desired finished catalyst, rinse with high-purity water, and dry to obtain the final product.

10. The method for preparing an ozone catalyst using chlorinated waste salt byproduct material according to claim 1, characterized in that: The binder is any one or two of liquid aluminum dihydrogen phosphate, silica sol and polyvinyl alcohol.

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