Preparation and application of vanadium-based adsorption arsenic removal material

Abstract

The invention discloses preparation and application of a vanadium-based adsorption arsenic removal material, and belongs to the technical field of water treatment. The preparation method of the material comprises the following steps: mechanically ball-milling and mixing a vanadium-containing compound, a metal salt compound and ammonium carbonate according to a certain proportion, preparing vanadate by a high-temperature calcination method, and mechanically ball-milling to obtain the arsenic adsorption and removal material. The vanadium-based adsorption arsenic removal material disclosed by the invention is simple in preparation process, cheap and easily available in raw materials and low in cost, and meanwhile, the porous vanadium-based adsorption arsenic removal powder prepared by the method disclosed by the invention is high in arsenic adsorption capacity which is greater than 2000mg / g.

Description

Technical field:

[0001] The invention belongs to the technical field of water treatment, and in particular relates to the preparation and application of a vanadium-based arsenic-removing adsorption material. Background technology:

[0002] Arsenic is a naturally occurring element that can be found in food, water, air, and soil. Arsenic is widely used in insecticides, pesticides, wood preservatives, and tobacco, resulting in increasing levels of arsenic compounds in water and soil each year. There are two types of arsenic: organic and inorganic. Organic arsenic compounds are compounds of arsenic with carbon and other elements. These compounds are generally less toxic than inorganic compounds and are found in some foods, such as fish and shellfish. However, inorganic arsenic compounds are compounds of arsenic with elements other than carbon and are often more toxic and have been linked to cancer. They are found in building products, such as pressure-treated wood, and in contaminated water.

[0003] At present, the more mature arsenic removal technologies mainly include the following: precipitation method, adsorption method, ion exchange method, membrane technology and biotechnology. Among them, the adsorption method is a method of fixing arsenic in water on the surface of the adsorbent through physical action, chemical action or ion exchange, thereby removing arsenic. The adsorption method is a simple and easy water treatment technology, which is the most widely used in my country. At present, the commonly used arsenic adsorbents in water treatment include activated alumina, activated carbon, zeolite, manganese-based adsorption materials, etc. Among them, patent CN 110115978A is a manganese-based adsorption material and its preparation and application. The preparation method is as follows: 1) dissolving manganese salt in an alcohol solvent to form a transparent solution; 2) adding an organic ligand to the transparent solution in step 1) at room temperature, and transferring it to a thermal reaction kettle for thermal synthesis reaction; 3) taking the precipitate generated after the thermal reaction, washing and drying it, and obtaining the manganese-based adsorption material. Manganese-based adsorption materials have a huge adsorption capacity for phosphorus and arsenic, and have good adsorption kinetics. They can be used for deep phosphorus removal of sewage plant tail water and emergency pollution treatment of phosphorus and arsenic in ecological environment protection, but the preparation process of manganese-based adsorption materials is complicated and costly. The vanadium-based material synthesized by the present invention is a porous powder structure with a specific surface area greater than 15m2 / g, and has good adsorption performance for arsenic. In addition, its preparation method is simple, the raw material price is low, and it has high application value. Summary of the invention:

[0004] This invention provides a preparation and application of a vanadium-based adsorption and arsenic removal material, which is characterized in that the method is carried out in the following steps:

[0005] A certain proportion of vanadium-containing compounds, metal salt compounds and ammonium carbonate are mechanically ball-milled and mixed, and vanadate is prepared by high-temperature calcination, and arsenic adsorption and removal material is obtained by mechanical ball-milling.

[0006] The vanadium-containing compound is one or more of vanadium trioxide, vanadium dioxide, vanadium pentoxide and ammonium metavanadate.

[0007] The metal salt compound is one of sodium carbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, sodium chloride, potassium chloride, sodium acetate, potassium acetate, sodium nitrate, potassium nitrate, manganese acetate, cobalt acetate, nickel acetate, iron acetate, copper acetate, manganese chloride, cobalt chloride, nickel chloride, iron chloride, copper chloride, manganese nitrate, cobalt nitrate, nickel nitrate, iron nitrate, and copper nitrate.

[0008] Vanadium-containing compound: metal salt compound: ammonium carbonate = 1: (1-5): (0.5-3).

[0009] Arsenic includes zero-valent arsenic, trivalent arsenic, and pentavalent arsenic. The concentration of arsenic in wastewater is 0.01-5000 mg / L.

[0010] The adsorption temperature of the vanadium-based adsorbent is 0-50°C, the adsorption time is 1 hour-10 days, the solution pH value is 3-11, and the dosage of the vanadium-based adsorbent is 0.1-10 g / kg.

[0011] The present invention has the following beneficial effects: the present invention adopts the calcination method to prepare the vanadium-based adsorption and arsenic removal material, the process is safe and simple, less time-consuming and low-cost; the prepared adsorbent is a porous material with a specific surface area greater than 15m2 / g and a large adsorption capacity, and has significant application prospects. Specific implementation method:

[0012] The present invention will be further described below in conjunction with examples, but the present invention is not limited to the following examples.

[0013] Example 1

[0014] Preparation of vanadium-based adsorption and arsenic removal materials:

[0015] Vanadium trioxide, sodium carbonate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:1:0.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0016] Application of vanadium-based adsorption arsenic removal materials:

[0017] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 0.01mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 0.1g / kg, the adsorption temperature is 0°C, the adsorption time is 30h, and the pH value is 3. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 99.9%.

[0018] Example 2

[0019] Preparation of vanadium-based adsorption and arsenic removal materials:

[0020] Vanadium trioxide, potassium carbonate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:1:1, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0021] Application of vanadium-based adsorption arsenic removal materials:

[0022] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 0.05mg / L. Under sufficient stirring conditions, when the dosage of arsenic removal adsorbent is 0.2g / kg, the adsorption temperature is 50°C, the adsorption time is 36h, and the pH value is 11. After conventional mixing and adsorption, the removal rate of trivalent arsenic is 90.0%.

[0023] Example 3

[0024] Preparation of vanadium-based adsorption and arsenic removal materials:

[0025] Vanadium trioxide, sodium acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:1:2, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0026] Application of vanadium-based adsorption arsenic removal materials:

[0027] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 0.1mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 0.3g / kg, the adsorption temperature is 25°C, the adsorption time is 60h, and the pH value is 7. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 95.0%.

[0028] Example 4

[0029] Preparation of vanadium-based adsorption and arsenic removal materials:

[0030] Vanadium pentoxide, potassium acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:1:3, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0031] Application of vanadium-based adsorption arsenic removal materials:

[0032] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 0.5mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 0.5g / kg, the adsorption temperature is 25°C, the adsorption time is 48h, and the pH value is 7. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 96.0%.

[0033] Example 5

[0034] Preparation of vanadium-based adsorption and arsenic removal materials:

[0035] Vanadium pentoxide, sodium nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:2:0.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0036] Application of vanadium-based adsorption arsenic removal materials:

[0037] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 1mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 1g / kg, the adsorption temperature is 25°C, the adsorption time is 30h, and the pH value is 7. After conventional mixing and adsorption, the trivalent arsenic removal rate is 97.0%.

[0038] Example 6

[0039] Preparation of vanadium-based adsorption and arsenic removal materials:

[0040] Vanadium pentoxide, potassium nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:3:0.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0041] Application of vanadium-based adsorption arsenic removal materials:

[0042] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 25mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 2g / kg, the adsorption temperature is 25°C, the adsorption time is 36h, and the pH value is 7. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 97.5%.

[0043] Example 7

[0044] Preparation of vanadium-based adsorption and arsenic removal materials:

[0045] Ammonium metavanadate, silver nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:4:0.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0046] Application of vanadium-based adsorption arsenic removal materials:

[0047] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 50mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 3g / kg, the adsorption temperature is 30°C, the adsorption time is 60h, and the pH value is 8. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 97.9%.

[0048] Example 8

[0049] Preparation of vanadium-based adsorption and arsenic removal materials:

[0050] Ammonium metavanadate, manganese acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:5:0.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0051] Application of vanadium-based adsorption arsenic removal materials:

[0052] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 50mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 4g / kg, the adsorption temperature is 30°C, the adsorption time is 72h, and the pH value is 10. After conventional mixing and adsorption, the trivalent arsenic removal rate is 98.0%.

[0053] Example 9

[0054] Preparation of vanadium-based adsorption and arsenic removal materials:

[0055] Ammonium metavanadate, cobalt acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:5:0.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0056] Application of vanadium-based adsorption arsenic removal materials:

[0057] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 100mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 5g / kg, the adsorption temperature is 30°C, the adsorption time is 96h, and the pH value is 10. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 99.0%.

[0058] Example 10

[0059] Preparation of vanadium-based adsorption and arsenic removal materials:

[0060] Ammonium metavanadate, nickel acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:2:2, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0061] Application of vanadium-based adsorption arsenic removal materials:

[0062] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 200mg / L. Under sufficient stirring conditions, when the dosage of arsenic removal adsorbent is 6g / kg, the adsorption temperature is 30°C, the adsorption time is 90h, and the pH value is 7. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 99.5%.

[0063] Embodiment 11

[0064] Preparation of vanadium-based adsorption and arsenic removal materials:

[0065] Ammonium metavanadate, ferric acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:2:3, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0066] Application of vanadium-based adsorption arsenic removal materials:

[0067] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 250mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 7g / kg, the adsorption temperature is 30°C, the adsorption time is 96h, and the pH value is 7. After conventional mixing and adsorption, the trivalent arsenic removal rate is 98.5%.

[0068] Example 12

[0069] Preparation of vanadium-based adsorption and arsenic removal materials:

[0070] Ammonium metavanadate, manganese chloride and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:3:2, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0071] Application of vanadium-based adsorption arsenic removal materials:

[0072] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 300mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 8g / kg, the adsorption temperature is 30°C, the adsorption time is 102h, and the pH value is 5. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 97.5%.

[0073] Embodiment 13

[0074] Preparation of vanadium-based adsorption and arsenic removal materials:

[0075] Ammonium metavanadate, cobalt chloride and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:3:3, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0076] Application of vanadium-based adsorption arsenic removal materials:

[0077] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 400mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 9g / kg, the adsorption temperature is 20°C, the adsorption time is 114h, and the pH value is 7. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 98.0%.

[0078] Embodiment 14

[0079] Preparation of vanadium-based adsorption and arsenic removal materials:

[0080] Ammonium metavanadate, nickel chloride and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:4:1, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0081] Application of vanadium-based adsorption arsenic removal materials:

[0082] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 500mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 10g / kg, the adsorption temperature is 20°C, the adsorption time is 138h, and the pH value is 7. After conventional mixing and adsorption, the trivalent arsenic removal rate is 96.5%.

[0083] Embodiment 15

[0084] Preparation of vanadium-based adsorption and arsenic removal materials:

[0085] Ammonium metavanadate, ferric chloride and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:4:2, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0086] Application of vanadium-based adsorption arsenic removal materials:

[0087] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 1mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 0.1g / kg, the adsorption temperature is 20°C, the adsorption time is 126h, and the pH value is 7. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 97.9%.

[0088] Example 16

[0089] Preparation of vanadium-based adsorption and arsenic removal materials:

[0090] Vanadium dioxide, manganese nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:4:3, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0091] Application of vanadium-based adsorption arsenic removal materials:

[0092] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 25mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 0.5g / kg, the adsorption temperature is 30°C, the adsorption time is 132h, and the pH value is 7. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 98.5%.

[0093] Embodiment 17

[0094] Preparation of vanadium-based adsorption and arsenic removal materials:

[0095] Vanadium dioxide, cobalt nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:5:1, and then vanadate arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0096] Application of vanadium-based adsorption arsenic removal materials:

[0097] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 50mg / L. Under sufficient stirring conditions, when the dosage of arsenic removal adsorbent is 0.8g / kg, the adsorption temperature is 30°C, the adsorption time is 164h, and the pH value is 7. After conventional mixing and adsorption, the trivalent arsenic removal rate is 95.5%.

[0098] Embodiment 18

[0099] Preparation of vanadium-based adsorption and arsenic removal materials:

[0100] Vanadium dioxide, nickel nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:5:2, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0101] Application of vanadium-based adsorption arsenic removal materials:

[0102] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 100mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 1g / kg, the adsorption temperature is 30°C, the adsorption time is 146h, and the pH value is 7. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 98.7%.

[0103] Embodiment 19

[0104] Preparation of vanadium-based adsorption and arsenic removal materials:

[0105] Ammonium metavanadate, ferric nitrate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:5:3, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0106] Application of vanadium-based adsorption arsenic removal materials:

[0107] In this embodiment, the pentavalent arsenic content in 1L of arsenic-containing waste liquid is 250mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 5g / kg, the adsorption temperature is 10°C, the adsorption time is 134h, and the pH value is 7. After conventional mixing and adsorption, the pentavalent arsenic removal rate is 99.0%.

[0108] Embodiment 20

[0109] Preparation of vanadium-based adsorption and arsenic removal materials:

[0110] Ammonium metavanadate, copper chloride and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:2:2.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0111] Application of vanadium-based adsorption arsenic removal materials:

[0112] In this embodiment, the trivalent arsenic content in 1L of arsenic-containing waste liquid is 300mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 10g / kg, the adsorption temperature is 30°C, the adsorption time is 72h, and the pH value is 7. After conventional mixing and adsorption, the trivalent arsenic removal rate is 99.8%.

[0113] Embodiment 21

[0114] Preparation of vanadium-based adsorption and arsenic removal materials:

[0115] Ammonium metavanadate, copper acetate and ammonium carbonate are mixed by mechanical ball milling in a ratio of 1:3:2.5, and then vanadate adsorption and arsenic removal material is obtained by high-temperature calcination and mechanical ball milling.

[0116] Application of vanadium-based adsorption arsenic removal materials:

[0117] In this embodiment, the zero-valent arsenic content in 1L of arsenic-containing waste liquid is 400mg / L. Under sufficient stirring conditions, when the dosage of the arsenic removal adsorbent is 9g / kg, the adsorption temperature is 10°C, the adsorption time is 90h, and the pH value is 7. After conventional mixing and adsorption, the zero-valent arsenic removal rate is 98.3%.

Claims

1. Preparation and application of a vanadium-based adsorption and arsenic removal material, characterized in that The method proceeds as follows: A vanadium-containing compound, a metal salt compound and ammonium carbonate in a certain molar ratio are mechanically ball-milled and mixed, and high-temperature calcination and mechanical ball-milling are performed to obtain a vanadate adsorption and arsenic removal material.

2. According to claim 1, the preparation and application of a vanadium-based arsenic removal adsorption material is characterized in that The vanadium-containing compound is one or more of vanadium trioxide, vanadium dioxide, vanadium pentoxide and ammonium metavanadate.

3. According to claim 1, the preparation and application of a vanadium-based arsenic removal adsorption material is characterized in that The metal salt compound is one of sodium carbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, sodium chloride, potassium chloride, sodium acetate, potassium acetate, sodium nitrate, potassium nitrate, manganese acetate, cobalt acetate, nickel acetate, iron acetate, copper acetate, manganese chloride, cobalt chloride, nickel chloride, iron chloride, copper chloride, manganese nitrate, cobalt nitrate, nickel nitrate, iron nitrate, and copper nitrate.

4. According to claim 1, the preparation and application of a vanadium-based arsenic removal adsorption material is characterized in that The certain ratio is vanadium-containing compound: metal salt compound: ammonium carbonate = 1: (1-5): (0.5-3).

5. According to claim 1, the preparation and application of a vanadium-based arsenic removal adsorption material is characterized in that The arsenic includes zero-valent arsenic, trivalent arsenic and pentavalent arsenic, and the concentration of arsenic in the wastewater is 0.01-5000 mg / L.

6. According to claim 1, the preparation and application of a vanadium-based arsenic removal adsorption material is characterized in that Application of vanadium-based adsorbents in the removal of arsenic from arsenic-containing wastewater The adsorption temperature is 0-50°C, the adsorption time is 1 hour-10 days, and the solution pH is 3-11. The dosage of the vanadium-based adsorbent is 0.1-10 g / kg.