Beryllium dissolution curing agent and stable curing method for beryllium in beryllium-containing material

Abstract

The invention relates to a beryllium dissolution curing agent and a stable curing method for beryllium in a beryllium-containing material, in particular to the technical field of beryllium pollution prevention, and the beryllium dissolution curing agent comprises, by weight, 1-5 parts of phosphorus-containing waste, 1-3 parts of fluorine-containing waste and 0.1-0.5 part of auxiliary salt. The stable curing method comprises the following steps: carrying out wet ball milling on a beryllium-containing material and the beryllium dissolution curing agent in the first aspect to obtain slurry; and carrying out a curing reaction on the obtained slurry, and then carrying out solid-liquid separation to obtain the beryllium stable curing material. According to the beryllium dissolution curing agent provided by the invention, by designing the beryllium dissolution curing agent and utilizing the synergistic effect of the components, effective matching components can be provided for beryllium components in different occurrence states, so that efficient dissolution and curing of beryllium in a material are realized.

Description

Technical Field

[0001] The invention relates to the technical field of beryllium pollution prevention and control, and in particular to a beryllium dissolution solidifying agent and a method for stabilizing the solidification of beryllium in a beryllium-containing material, and in particular to a beryllium dissolution solidifying agent for lithium smelting slag and a method for stabilizing the solidification of beryllium in lithium smelting slag. Background Art

[0002] At present, the main industrial raw materials for lithium extraction include lithium ores such as spodumene and lepidolite. However, a large amount of lithium smelting slag will be produced in the process of lithium extraction. According to statistics, the amount of smelting slag produced in the process of lithium extraction from spodumene is 8-10 tons / ton of lithium carbonate, and the amount of smelting slag produced in the process of lithium extraction from lepidolite is 30-60 tons / ton of lithium carbonate.

[0003] However, since lithium ore contains a certain amount of beryllium-containing minerals, they can easily enter the lithium smelting slag during the smelting process, causing the beryllium leaching toxicity of the slag to far exceed the national standard concentration of 0.02 mg / L, which can easily cause major environmental pollution and become a factor restricting the high-quality green development of the lithium battery industry. Therefore, there is an urgent need to dispose of lithium smelting slag harmlessly, such as reducing the leaching toxicity of beryllium, so as to achieve large-scale disposal and resource utilization of the slag.

[0004] CN117023756A discloses a beryllium (II) mineralizing agent and a method for deep purification of beryllium-containing wastewater, wherein the beryllium (II) mineralizing agent mainly comprises a calcium-containing compound and a phosphate-containing compound, and the method comprises adjusting the pH of the beryllium-containing wastewater to 4-9, first adding a beryllium (II) mineralizing agent with 10 times the beryllium component in the solution to carry out a mineralization reaction, and then adding a flocculant to carry out flocculation and sedimentation, thereby obtaining beryllium-free purified water. However, the process flow of the method for deep purification of beryllium-containing wastewater is relatively complicated, the properties of the solution are difficult to stably control, and the amount of the mineralizing agent used is relatively large and the cost is relatively high, which limits the cost-reduction and efficiency-enhancing treatment of beryllium in beryllium-containing wastewater.

[0005] In summary, the existing beryllium solidification technology still has the problem of incomplete beryllium dissolution and solidification, and there is still a risk of secondary beryllium pollution. Therefore, there is an urgent need for a low-cost free beryllium dissolution solidifier and a simple, efficient and green lithium smelting slag beryllium stabilization solidification method to achieve efficient dissolution and solidification of beryllium. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide a beryllium dissolution curing agent and a method for stable curing of beryllium in a beryllium-containing material, so as to solve the defects of incomplete dissolution and low curing efficiency in the current beryllium curing process.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a beryllium dissolution curing agent, which comprises, in parts by weight:

[0009] 1-5 parts of phosphorus-containing waste, 1-3 parts of fluorine-containing waste and 0.1-0.5 parts of auxiliary salt.

[0010] The beryllium dissolution curing agent provided by the present invention can provide effective matching components for beryllium components in different existence states by designing the beryllium dissolution curing agent and utilizing the synergistic effect between components to achieve efficient dissolution and curing of beryllium in the material, thereby reducing the dissolution toxicity of beryllium in the material.

[0011] As a preferred technical solution of the present invention, the phosphorus-containing waste includes any one of phosphogypsum, phosphate tailings, phosphating slag, and waste phosphating liquid, or a combination of at least two of them.

[0012] Preferably, the fluorine-containing waste material includes any one of phosphogypsum, fluorosilicic slag, and calcium fluoride sludge, or a combination of at least two of them.

[0013] Preferably, the auxiliary salt includes any one of ethylenediaminetetraacetic acid, ethylenediaminetetraacetate, potassium sulfate or potassium aluminum sulfate, or a combination of at least two thereof.

[0014] As a preferred technical solution of the present invention, the mass ratio of phosphorus-containing waste to fluorine-containing waste in the beryllium dissolution solidifying agent is 5:(2.8-3.2).

[0015] As a preferred technical solution of the present invention, the beryllium dissolution curing agent further comprises, by weight: 1-3 parts of calcium-containing waste material.

[0016] As a preferred technical solution of the present invention, the calcium-containing waste includes any one of phosphogypsum, carbide slag, blast furnace slag or steel slag, or a combination of at least two of them.

[0017] As a preferred technical solution of the present invention, the mass ratio of phosphorus-containing waste, fluorine-containing waste and calcium-containing waste in the beryllium dissolution solidifying agent is 5:(2.8-3.2):(1-3).

[0018] In a second aspect, the present invention provides a method for stabilizing and solidifying beryllium in a beryllium-containing material, the method comprising:

[0019] Wet ball milling the beryllium-containing material and the beryllium dissolution curing agent as described in the first aspect to obtain a slurry;

[0020] The obtained slurry is subjected to a curing reaction, and then a beryllium-stabilized curing material is obtained through solid-liquid separation.

[0021] As a preferred technical solution of the present invention, the beryllium-containing material includes lithium smelting slag.

[0022] As a preferred technical solution of the present invention, the amount of the beryllium dissolution curing agent used in the wet ball milling is 1-10% of the mass of the beryllium-containing material.

[0023] Preferably, the mass ratio of the grinding ball medium to the beryllium-containing material in the wet ball milling is (1-10):1.

[0024] Preferably, the mass ratio of water to beryllium-containing material used in the wet ball milling is (0.5-5):1.

[0025] Preferably, the wet ball milling time is 5-360 min.

[0026] As a preferred technical solution of the present invention, stirring is performed during the curing reaction.

[0027] Preferably, the stirring speed is 200-1000 r / min.

[0028] Preferably, the curing reaction temperature is 25-150°C.

[0029] Preferably, the curing reaction time is 15-180 min.

[0030] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0031] The beryllium dissolution solidifying agent provided by the present invention can efficiently dissolve and release beryllium components in lithium smelting slag by cooperating with the wet grinding mechanical crushing action and the beryllium dissolution solidifying agent during the dissolution process. At the same time, the beryllium dissolution solidifying agent is utilized to solidify free beryllium into stable minerals such as hydroxy beryllium phosphate, beryllium fluorophosphate and calcium fluoroberylate during the stirring and solidification reaction process, thereby realizing efficient removal and solidification of free beryllium in lithium smelting slag. The beryllium leaching toxicity of the slag obtained by the treatment can be reduced to a minimum of 4.59 ppb, which fully meets the national standard for leaching toxicity of hazardous wastes, greatly reduces the pollution of the ecological environment caused by lithium smelting slag, has good economic and environmental benefits, and has broad application prospects.

[0032] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0033] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0034] This embodiment provides a beryllium dissolution curing agent, which comprises, in parts by weight:

[0035] 1-5 parts of phosphorus-containing waste, 1-3 parts of fluorine-containing waste and 0.1-0.5 parts of auxiliary salt.

[0036] In the present invention, the phosphorus-containing waste in the beryllium dissolution curing agent is 1-5 parts by weight, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, but is not limited to the listed values. Other values ​​not listed within this range also meet the requirements.

[0037] In the present invention, the fluorine-containing waste in the beryllium dissolution curing agent is 1-3 parts by weight, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts, but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0038] In the present invention, the auxiliary salt in the beryllium dissolution curing agent is 0.1-0.5 parts by weight, for example, it can be 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts or 0.5 parts, but is not limited to the listed values, and other values ​​not listed within this range also meet the requirements.

[0039] Specifically, the phosphorus-containing waste includes any one of phosphogypsum, phosphate tailings, phosphating slag, and waste phosphating liquid, or a combination of at least two of them.

[0040] Exemplarily, the combination of the phosphorus-containing waste materials can be selected as: a combination of phosphogypsum and phosphate tailings, a combination of phosphate tailings and phosphating slag, a combination of phosphating slag and waste phosphating liquid, etc.

[0041] Specifically, the fluorine-containing waste material includes any one of phosphogypsum, fluorine silicon slag, and calcium fluoride sludge, or a combination of at least two of them.

[0042] Exemplarily, the combination of the fluorine-containing waste materials can be selected as: a combination of phosphogypsum and fluorosilicic slag, a combination of fluorosilicic slag and calcium fluoride sludge, a combination of phosphogypsum, fluorosilicic slag and calcium fluoride sludge, and the like.

[0043] Specifically, the auxiliary salt includes any one of ethylenediaminetetraacetic acid, ethylenediaminetetraacetate, potassium sulfate or potassium aluminum sulfate, or a combination of at least two thereof.

[0044] Exemplarily, the combination of the auxiliary agents can be selected as: a combination of ethylenediaminetetraacetic acid and ethylenediaminetetraacetate, a combination of potassium sulfate and potassium aluminum sulfate, a combination of ethylenediaminetetraacetate and potassium sulfate, a combination of ethylenediaminetetraacetate, potassium sulfate and potassium aluminum sulfate, etc., preferably a combination of ethylenediaminetetraacetic acid and potassium aluminum sulfate.

[0045] Specifically, the mass ratio of phosphorus-containing waste and fluorine-containing waste in the beryllium dissolution curing agent is 5:(2.8-3.2), for example, it can be 5:2.8, 5:2.85, 5:2.9, 5:2.95, 5:3, 5:3.05, 5:3.1, 5:3.15 or 5:3.2, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0046] Specifically, the beryllium dissolution curing agent further comprises, by weight: 1-3 parts of calcium-containing waste material.

[0047] In the present invention, the calcium-containing waste in the beryllium dissolution curing agent is 1-3 parts by weight, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts, but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0048] Specifically, the calcium-containing waste includes any one of phosphogypsum, carbide slag, blast furnace slag or steel slag, or a combination of at least two of them.

[0049] Exemplarily, the combination of the calcium-containing waste materials can be selected as: a combination of phosphogypsum and carbide slag, a combination of carbide slag and blast furnace slag, a combination of blast furnace slag and steel slag, a combination of phosphogypsum, carbide slag and blast furnace slag, etc.

[0050] Specifically, the mass ratio of phosphorus-containing waste, fluorine-containing waste and calcium-containing waste in the beryllium dissolution solidifying agent is 5:(2.8-3.2):(1-3), for example, it can be 5:2.8:1, 5:2.9:1, 5:3:1, 5:3.1:1.5, 5:3.2:2, 5:3:2, 5:3:3 or 5:3.2:1, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0051] Furthermore, this embodiment provides a method for stabilizing the solidification of beryllium in a beryllium-containing material, the method comprising:

[0052] Wet ball milling the beryllium-containing material and the beryllium dissolving curing agent to obtain a slurry;

[0053] The obtained slurry is subjected to a curing reaction, and then a beryllium-stabilized curing material is obtained through solid-liquid separation.

[0054] Specifically, the beryllium-containing material includes lithium smelting slag.

[0055] Specifically, the amount of beryllium dissolution curing agent used in the wet ball milling is 1-10% of the mass of the beryllium-containing material, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0056] In the present invention, when the beryllium dissolution curing agent used does not contain calcium-containing waste, the amount of the beryllium dissolution curing agent used is 3-8% of the mass of the beryllium-containing material, for example, it can be 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%, etc., but is not limited to the listed values, and other values ​​not listed within this range also meet the requirements.

[0057] Specifically, the mass ratio of the grinding ball medium to the beryllium-containing material in the wet ball mill is (1-10):1, for example, it can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but is not limited to the listed values, and other unlisted values ​​within this range also meet the requirements.

[0058] Specifically, the mass ratio of water to beryllium-containing material used in the wet ball milling is (0.5-5):1, for example, it can be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0059] Specifically, the wet ball milling time is 5-360 min, for example, it can be 5 min, 10 min, 20 min, 40 min, 60 min, 80 min, 100 min, 150 min, 200 min, 250 min, 300 min, 350 min or 360 min, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0060] Specifically, stirring is performed during the curing reaction.

[0061] Specifically, the stirring speed is 200-1000r / min, for example, it can be 200r / min, 250r / min, 300r / min, 350r / min, 400r / min, 450r / min, 500r / min, 550r / min, 600r / min, 650r / min, 700r / min, 750r / min, 800r / min, 850r / min, 900r / min, 950r / min or 1000r / min, but is not limited to the listed values, and other values ​​not listed in this range also meet the requirements.

[0062] Specifically, the temperature of the curing reaction is 25-150°C, for example, it can be 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0063] Specifically, the curing reaction time is 15-180 min, for example, it can be 15 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min or 180 min, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0064] Further, in order to illustrate the good dissolution curing effect that can be achieved by the beryllium dissolution curing agent provided by the present invention, actual examples are used for illustration, as follows:

[0065] Example 1

[0066] This embodiment provides a beryllium dissolution solidifying agent and a method for stabilizing and solidifying beryllium in lithium smelting slag, the method comprising the following steps:

[0067] Lithium smelting slag, beryllium dissolution curing agent and water are placed in a ball mill for wet grinding, wherein the mass of the beryllium dissolution curing agent used in the wet grinding is 8% of the mass of the lithium smelting slag; the beryllium dissolution curing agent is composed of 5 parts of phosphorus-containing waste (phosphating slag), 3 parts of fluorine-containing waste (fluorosilicon slag), and 0.3 parts of auxiliary salt (sodium ethylenediaminetetraacetate);

[0068] The main components of the phosphating slag used are as follows in terms of mass percentage: FePO 4 82.18%, Zn 3 (PO 4 ) 2 11.7%;

[0069] The main components of the fluorine silicon slag (dried material from a fluorine chemical plant in Guizhou) used are as follows in terms of mass percentage: SiO 2 86.12%, F 10.73%, SO 3 1.68%, MgO 0.62%, Na 2 O 0.28%, P 2 O 5 0.26%, others 0.31%;

[0070] At this time, the mass ratio of phosphorus-containing waste to fluorine-containing waste is 5:3, the mass ratio of grinding ball medium to lithium smelting slag is 5:1, and the mass ratio of water to lithium smelting slag is 5:1. After wet grinding for 60 minutes, the ball mill medium is separated from the slurry to obtain a primary mixed slurry;

[0071] The obtained primary mixed slurry was pumped into a stirring tank for curing reaction, the curing reaction temperature was controlled to be 60°C, the stirring speed was controlled to be 400r / min, and the secondary mixed slurry was obtained after the curing reaction for 60 minutes;

[0072] The obtained secondary mixed slurry is pumped into a solid-liquid separation device, filtered and separated to obtain stable solidified lithium smelting slag, and the leaching toxicity of the obtained stable solidified lithium smelting slag is tested.

[0073] Example 2

[0074] This embodiment provides a beryllium dissolution solidifying agent and a method for stabilizing and solidifying beryllium in lithium smelting slag, the method comprising the following steps:

[0075] The lithium smelting slag, the beryllium dissolving solidifying agent and water are placed in a ball mill for wet grinding, wherein the mass of the beryllium dissolving solidifying agent used in the wet grinding is 8% of the mass of the lithium smelting slag, and the composition of the beryllium dissolving solidifying agent is 5 parts of phosphorus-containing waste (phosphate tailings), 3 parts of fluorine-containing waste (calcium fluoride sludge), and 1 part of calcium-containing waste (blast furnace slag);

[0076] The main components of the phosphorus tailings used are as follows in terms of mass percentage: MgO 16.73%, CaO 34.42%, SiO 2 3.96%, P 2 O 5 3.08%, SO 3 1.07%,Al 2 O 3 0.10%,Fe 2 O 3 0.80%, F 0.56%;

[0077] The main composition of the calcium fluoride sludge used is as follows in terms of mass percentage: Ca 15.2%, F 33.7%, Al1.2%, C 30.8%, S 0.5%, Si 0.5%, Cl 0.1%, Na 0.5%, O 17.3%;

[0078] The main components of the blast furnace slag used are as follows in terms of mass percentage: CaO 37.81%, SiO 2 31.26%, Al 2 O 3 17.91, MgO 8.4%, SO 3 1.47%, TiO 2 0.99%,Fe 2 O 3 0.83%, K 2 O 0.66%, Na 2 O 0.42%, MnO 0.25%;

[0079] At this time, the mass ratio of phosphorus-containing waste, fluorine-containing waste and calcium-containing waste is 5:3:1, the auxiliary salt (potassium sulfate) is 0.1 part, the mass ratio of grinding ball medium to lithium smelting slag is 1:1, the mass ratio of water to lithium smelting slag is 3:1, and after wet grinding for 30 minutes, the ball milling medium is separated from the slurry to obtain a primary mixed slurry;

[0080] The obtained primary mixed slurry was pumped into a stirring tank for curing reaction, the curing reaction temperature was controlled to be 40°C, the stirring speed was controlled to be 300r / min, and the secondary mixed slurry was obtained after the curing reaction for 90min;

[0081] The obtained secondary mixed slurry is pumped into a solid-liquid separation device, filtered and separated to obtain stable solidified lithium smelting slag, and the leaching toxicity of the obtained stable solidified lithium smelting slag is tested.

[0082] Example 3

[0083] This embodiment provides a beryllium dissolution solidifying agent and a method for stabilizing and solidifying beryllium in lithium smelting slag, the method comprising the following steps:

[0084] Lithium smelting slag, beryllium dissolution curing agent and water are placed in a ball mill for wet grinding, wherein the mass of the beryllium dissolution curing agent used in the wet grinding is 6% of the mass of the lithium smelting slag, and the beryllium dissolution curing agent is composed of 5 parts of phosphorus-containing waste (phosphate tailings), 3 parts of fluorine-containing waste (phosphogypsum), and 3 parts of calcium-containing waste (steel slag);

[0085] The main components of the phosphorus tailings used are as follows in terms of mass percentage: MgO 20.83%, CaO 59.04%, SiO 2 7.17%, P 2 O 56.14%, SO 3 1.14%,Al 2 O 3 1.33%,Fe 2 O 3 1.93%, F 0.74%, K 2 O 0.73%;

[0086] The main components of the phosphogypsum used are as follows in terms of mass percentage: CaO 26.62%, MgO 0.08%, SO 3 37.45%, SiO 2 6.26%, P 2 O 5 1.65%,Fe 2 O 3 0.31%,Al 2 O 3 0.46%, F 1.7%, K 2 O, 0.62%, Na 2 O 0.21%, BaO 0.16%, TiO 2 0.09%, SrO 0.05%, ZrO 2 0.01%, I 0.01%;

[0087] The main components of the steel slag used are as follows in terms of mass percentage: CaO 53.749%, SO 3 0.498%,MgO3.368%,P 2 O 5 0.776%,Fe 2 O 3 23.379%, SiO 2 11.94%,Al 2 O 3 1.249%, others 5.041%;

[0088] The corresponding mass ratio is 5:3:3, the auxiliary salt (potassium aluminum sulfate) is 0.5 parts, the mass ratio of the grinding ball medium to the lithium smelting slag is 10:1, the mass ratio of water to the lithium smelting slag is 7:1, and the ball mill medium is separated from the slurry after wet grinding for 120 minutes to obtain a primary mixed slurry;

[0089] The obtained primary mixed slurry was pumped into a stirring tank for curing reaction, the curing reaction temperature was controlled to be 80°C, the stirring speed was controlled to be 500r / min, and the secondary mixed slurry was obtained after curing reaction for 30min;

[0090] The obtained secondary mixed slurry is pumped into a solid-liquid separation device, filtered and separated to obtain stable solidified lithium smelting slag, and the leaching toxicity of the obtained stable solidified lithium smelting slag is tested.

[0091] Example 4

[0092] This embodiment provides a beryllium dissolution solidifying agent and a method for stabilizing and solidifying beryllium in lithium smelting slag, the method comprising the following steps:

[0093] Lithium smelting slag, beryllium dissolution curing agent and water are placed in a ball mill for wet grinding, wherein the mass of the beryllium dissolution curing agent used in the wet grinding is 8% of the mass of the lithium smelting slag, and the beryllium dissolution curing agent is composed of 5 parts of phosphorus-containing waste (phosphating slag), 3 parts of fluorine-containing waste (calcium fluoride sludge), and 3 parts of calcium-containing waste (steel slag);

[0094] The main composition of the phosphating slag used is as follows in terms of mass percentage: Fe 66.448%, P 16.077%, Zn15.922%, Ca 1.388%, Mn 0.165%;

[0095] The main components of the calcium fluoride sludge used are as follows in terms of mass percentage: Ca 35.505%, F23.79%, Al0.064%, C 2.1%, S1.209%, Si 10.684%, O 26.018%, Mg 0.52%, Fe 0.11%

[0096] The main components of the steel slag used are as follows in terms of mass percentage: CaO 46.72%, MgO 4.01%, P 2 O 5 2.76%,Fe 2 O 3 26.43%, SiO 2 13.28%,Al 2 O 3 2.20%, MnO 2.13%, TiO 2 1.34%;

[0097] The corresponding mass ratio is 5:3:3, the auxiliary salt (mass ratio is ethylenediaminetetraacetic acid: potassium aluminum sulfate = 1:1) is 0.5 parts, the mass ratio of the grinding ball medium to the lithium smelting slag is 5:1, the mass ratio of water to the lithium smelting slag is 3:1, and the ball mill medium is separated from the slurry after wet grinding for 30 minutes to obtain a primary mixed slurry;

[0098] The obtained primary mixed slurry was pumped into a stirring tank for curing reaction, the curing reaction temperature was controlled to be 70°C, the stirring speed was controlled to be 300r / min, and the secondary mixed slurry was obtained after curing reaction for 30 minutes;

[0099] The obtained secondary mixed slurry is pumped into a solid-liquid separation device, filtered and separated to obtain stable solidified lithium smelting slag, and the leaching toxicity of the obtained stable solidified lithium smelting slag is tested.

[0100] Example 5

[0101] The difference from Example 4 is that the mass ratio of the phosphorus-containing waste, the fluorine-containing waste and the calcium-containing waste in the beryllium dissolution solidifying agent is adjusted to 5:3:1.

[0102] Example 6

[0103] The only difference from Example 1 is that the mass of the beryllium dissolving solidifying agent used in the wet grinding is 3% of the mass of the lithium smelting slag, and the temperature of the solidification reaction is 25°C.

[0104] Example 7

[0105] The only difference from Example 3 is that the mass of the beryllium dissolving solidifying agent used in the wet grinding is 2% of the mass of the lithium smelting slag, and the temperature of the solidification reaction is 25°C.

[0106] Example 8

[0107] The only difference from Example 1 is that the auxiliary salt is ethylenediaminetetraacetic acid and potassium aluminum sulfate in a mass ratio of 1:1.

[0108] Example 9

[0109] The only difference from Example 3 is that the auxiliary salt is ethylenediaminetetraacetic acid and potassium aluminum sulfate in a mass ratio of 1:1.

[0110] Comparative Example 1

[0111] The only difference from Example 1 is that no beryllium dissolution curing agent is added during the ball milling process, and the rest is the same as Example 1.

[0112] Comparative Example 2

[0113] The difference from Example 1 is that the fluorine-containing waste in the beryllium dissolution curing agent is replaced with an equal amount of calcium-containing waste, and the rest is the same as Example 1.

[0114] Comparative Example 3

[0115] The difference from Example 1 is that the beryllium dissolution curing agent used does not contain fluorine-containing waste materials, and the rest is the same as Example 1.

[0116] Comparative Example 4

[0117] The only difference from Example 1 is that the beryllium dissolution curing agent used does not contain auxiliary salt.

[0118] Comparative Example 5

[0119] The only difference from Example 1 is that the auxiliary salt in the beryllium dissolution curing agent is replaced by an equal amount of alanine.

[0120] Comparative Example 6

[0121] The only difference from Example 4 is that the mass ratio of phosphorus-containing waste, fluorine-containing waste and calcium-containing waste in the beryllium dissolution solidifying agent is adjusted to 5:1:3, and the rest is the same as Example 1.

[0122] Comparative Example 8

[0123] The only difference from Example 4 is that the beryllium dissolution curing agent used does not contain auxiliary salt.

[0124] Comparative Example 10

[0125] The only difference from Example 4 is that the auxiliary salt in the beryllium dissolution curing agent is replaced by an equal amount of alanine.

[0126] Comparative Example 11

[0127] The only difference from Example 1 is that wet ball milling is not performed, but the curing reaction is directly performed after mixing with water.

[0128] Comparative Example 12

[0129] The only difference from Example 4 is that wet ball milling is not performed, but the curing reaction is directly carried out after mixing with water.

[0130] The stabilized solidified lithium smelting slag obtained by the beryllium dissolution solidifying agent and the lithium smelting slag beryllium stabilization solidification method provided in the embodiments and comparative examples was tested for beryllium leaching toxicity using the standard "Solid Waste Leaching Toxicity Leaching Method Sulfuric Acid and Nitric Acid Method (HJ / T299-2007)". The test results are shown in Table 1.

[0131] Table 1

[0132]

[0133]

[0134] It can be seen from Table 1 that the agent and method provided by the present invention utilize mechanical ball milling and the action of beryllium dissolution and solidification agent to dissolve, release and stably solidify beryllium in lithium smelting slag, effectively reducing the leaching toxicity of beryllium components in lithium smelting slag and achieving efficient and stable solidification of lithium smelting slag.

[0135] By comparing Example 1 with Examples 2, 3, and 4, it can be seen that adding the calcium-containing waste to lithium smelting slag helps reduce the leaching toxicity of beryllium, because the beryllium component exists in two main forms in the solution system, not only in the form of beryllium ions, but also in the form of part of beryllium ions, and the addition of the calcium component helps to solidify the beryllium anion; by comparing Example 4 with Example 5, it can be seen that after adjusting the mass ratio of phosphorus-containing waste, fluorine-containing waste, and calcium-containing waste, the leaching toxicity of the beryllium component is significantly increased; by comparing Examples 1 and 4 with Examples 6 and 7, it can be seen that when the content of the dissolution curing agent added during the treatment in lithium smelting slag is reduced and the curing reaction temperature is reduced, the leaching toxicity of the beryllium component is significantly increased. By comparing the results of Examples 1 and 3 with Examples 8 and 9, it can be seen that the leaching toxicity of thallium is significantly reduced under the preferred combined auxiliary salt of ethylenediaminetetraacetic acid and potassium aluminum sulfate.

[0136] From the comparison between Example 1 and Comparative Example 1, it can be seen that no beryllium dissolution solidifying agent is added during the treatment of lithium smelting slag, and the leaching toxicity of the beryllium component in the slag after treatment is significantly improved. From the comparison between Example 1 and Comparative Examples 2, 3, 4, 5, 6, 11 and Example 4 and Comparative Examples 7, 8, 9, 10, 12, it can be seen that when the lithium smelting slag is not wet-milled, the leaching toxicity of the beryllium component is significantly improved. The reason is that the particle size of the lithium smelting slag is relatively large, and the beryllium component is easily present in the form of a package, which makes it difficult for the beryllium component in the coarse particles to be effectively dissolved and solidified; in addition, when the addition of fluorine-containing waste and additives is reduced, the beryllium component is difficult to efficiently dissolve and release and form a stable beryllium-containing substance, resulting in a significant increase in the leaching toxicity of the beryllium component in the slag after treatment, which significantly exceeds the limit specified by the national standard.

[0137] In summary, the beryllium dissolution curing agent and the method for stable solidification of beryllium in lithium smelting slag provided by the present invention can efficiently dissolve and release the beryllium component in the lithium smelting slag by using the wet grinding mechanical crushing effect and the beryllium dissolution curing agent, and at the same time, the beryllium dissolution curing agent is used to solidify the free beryllium into stable minerals such as hydroxy beryllium phosphate, beryllium fluorophosphate and calcium fluoroberylate during the stirring and solidification reaction, thereby achieving efficient removal and solidification of free beryllium in the lithium smelting slag, and the beryllium leaching toxicity of the treated slag is reduced to 4.59 ppb, which fully meets the national standard for leaching toxicity of hazardous waste, greatly reduces the pollution of the ecological environment caused by lithium smelting slag, and improves economic and environmental benefits.

[0138] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0139] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0140] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A beryllium dissolution curing agent, characterized in that: In parts by weight, the beryllium dissolution curing agent comprises: 1-5 parts of phosphorus-containing waste, 1-3 parts of fluorine-containing waste and 0.1-0.5 parts of auxiliary salt.

2. The beryllium dissolution curing agent according to claim 1, characterized in that: The phosphorus-containing waste material includes any one of phosphogypsum, phosphorus tailings, phosphating slag, and waste phosphating liquid, or a combination of at least two thereof; The fluorine-containing waste material includes any one of phosphogypsum, fluorine silicon slag, and calcium fluoride sludge, or a combination of at least two thereof; The auxiliary salt includes any one of ethylenediaminetetraacetic acid, ethylenediaminetetraacetate, potassium sulfate or potassium aluminum sulfate, or a combination of at least two thereof.

3. The beryllium dissolution curing agent according to claim 1, characterized in that: The mass ratio of phosphorus-containing waste to fluorine-containing waste in the beryllium dissolution curing agent is 5:(2.8-3.2).

4. The beryllium dissolution curing agent according to claim 1, characterized in that: In parts by weight, the beryllium dissolution curing agent further comprises: 1-3 parts of calcium-containing waste material.

5. The beryllium dissolution curing agent according to claim 4, characterized in that: The calcium-containing waste material includes any one of phosphogypsum, carbide slag, blast furnace slag or steel slag, or a combination of at least two of them.

6. The beryllium dissolution curing agent according to claim 4, characterized in that: The mass ratio of phosphorus-containing waste, fluorine-containing waste and calcium-containing waste in the beryllium dissolution curing agent is 5:(2.8-3.2):(1-3).

7. A method for stabilizing and solidifying beryllium in a beryllium-containing material, characterized in that: The stable curing method comprises: Wet ball milling the beryllium-containing material and the beryllium dissolution curing agent according to any one of claims 1 to 6 to obtain a slurry; The obtained slurry is subjected to a curing reaction, and then a beryllium-stabilized curing material is obtained through solid-liquid separation.

8. The stable curing method according to claim 7, characterized in that: The beryllium-containing material includes lithium smelting slag.

9. The stable curing method according to claim 7, characterized in that: The amount of the beryllium dissolution curing agent used in the wet ball milling is 1-10% of the mass of the beryllium-containing material; The mass ratio of the grinding ball medium to the beryllium-containing material in the wet ball mill is (1-10):1; The mass ratio of water to beryllium-containing material used in the wet ball milling is (0.5-5):1; The wet ball milling time is 5-360 min.

10. The stable curing method according to claim 7, characterized in that: Stirring during the curing reaction; The stirring speed of the stirring is 200-1000r / min; The curing reaction temperature is 25-150°C; The curing reaction time is 15-180 minutes.

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