CN113754460B

CN113754460B - Preparation method and use method of iron and manganese removal chemical reaction filler for deep bed ion reaction system

Info

Publication number: CN113754460B
Application number: CN202111051425.1A
Authority: CN
Inventors: 肖伟; 周愈尧; 刘少杰; 罗海兰; 郭小伟; 张凤英; 牛政; 董杰; 王迎祥
Original assignee: Love Soil Engineering Environmental Technology Co ltd
Current assignee: Love Soil Engineering Environmental Technology Co ltd
Priority date: 2021-09-08
Filing date: 2021-09-08
Publication date: 2022-12-13
Anticipated expiration: 2041-09-08
Also published as: CN113754460A

Abstract

The invention provides a preparation method and a use method of a chemical reaction filler for removing iron and manganese in a deep bed ion reaction system, belonging to the technical field of sewage treatment. The invention gives full play to the characteristics of each material by granulating, roasting and other processes of various raw materials, the main components of the obtained filler are iron, manganese, calcium, silicon and oxygen, the filler has good effect on removing iron and manganese, and has obvious advantages in the field of mine wastewater treatment, especially in acid mine wastewater treatment with low iron and manganese concentrations.

Description

Preparation method and use method of iron and manganese removal chemical reaction filler for deep bed ion reaction system

Technical Field

The invention relates to the technical field of sewage treatment, in particular to a preparation method and a use method of a chemical reaction filler for removing iron and manganese in a deep bed ion reaction system.

Background

In the condition that lots of closed mines exist in China and lots of slag, mine pits and mine caves are left, a large amount of wastewater overflows and is discharged everywhere under the conditions of leaching and soaking of rainwater, water burst of the mine caves and the like, so that pollution of downstream rivers, lakes, farmlands and the like can be caused, and the life safety of surrounding residents is harmed. The wastewater has the characteristics of low pH, generally containing various heavy metals such as iron, manganese, cadmium, nickel, zinc, copper and the like, complex components, relatively dispersed distribution, great treatment difficulty and the like.

At present, the main method for treating the acidic mine wastewater is an alkali-adding neutralization precipitation method, and is also the most widely applied method. However, the alkali neutralization precipitation method requires a large amount of chemicals such as lime, PAC, PAM, etc., which results in high operation cost and is likely to cause secondary pollution.

The natural manganese sand is a strong oxidant, can oxidize ferrous iron in water, is commonly used for a drinking water deironing and demanganizing filter device, and is used for removing iron and manganese in underground water to purify water, but because of the limitation of the concentration of iron-containing and manganese-containing wastewater treated by the manganese sand, the content of iron and manganese is not higher than 5mg/L generally, and the operation effect is not ideal when the acidic mine wastewater is treated.

Disclosure of Invention

In view of the above, the invention aims to provide a preparation method and a use method of a chemical reaction filler for removing iron and manganese in a deep bed ion reaction system.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of the filler comprises the following preparation steps:

and mixing the manganese sand, the steel slag, the bentonite and the pore-forming agent, and then sequentially granulating and roasting to obtain the filler.

Preferably, the mass ratio of the manganese sand to the steel slag to the bentonite to the pore-forming agent is (40 to 50): (30 to 40): (10 to 15): (5 to 10).

Preferably, the manganese dioxide content of the manganese sand is not less than 35% by mass.

Preferably, the particle size of the granulated particles is 2-4 mm.

Preferably, the baking temperature is 500 to 700 ℃.

The invention also provides the filler prepared by the preparation method.

The invention also provides application of the filler in sewage treatment, wherein the total iron concentration in the sewage is not higher than 50mg/L, and the total manganese concentration in the sewage is not higher than 5mg/L; the pH value of the sewage is 3~5.

The beneficial technical effects are as follows: the invention provides a filler, a preparation method and application thereof. The invention fully utilizes the catalytic property of manganese sand, the alkali-releasing property of steel slag, and the viscosity and the adsorbability of bentonite by granulating and roasting various raw materials. The filler obtained by the invention mainly comprises iron, manganese, calcium, silicon and oxygen, has a good effect on removing iron and manganese, and has obvious advantages in the field of mine wastewater treatment, particularly in the treatment of acid mine wastewater containing low iron and manganese.

Drawings

FIG. 1 shows different MnO in examples 1 to 8 ₂ The concentration of total iron and total manganese in the effluent of the acidic mine wastewater is treated by the filler with the content;

FIG. 2 shows the concentrations of total iron and total manganese in effluent of acidic mine wastewater treated by fillers with different raw material ratios in examples 9 to 15;

FIG. 3 is the concentrations of total iron and total manganese in effluent of acidic mine wastewater treated by fillers with different granulation particle sizes in examples 16 to 27;

FIG. 4 is the concentrations of total iron and total manganese in effluent of acidic mine wastewater treated by fillers with different roasting temperatures in examples 28 to 33;

FIG. 5 is a schematic view of a wastewater treatment tank of the deep bed ion reaction system.

Detailed Description

The invention provides a preparation method of a filler, which comprises the following preparation steps:

The manganese sand, the steel slag and the bentonite are preferably washed, dried and crushed respectively in sequence, and then are mixed with the pore-forming agent.

The washing of the invention is preferably to mix manganese sand, steel slag or bentonite with water, stir and settle the mixture, and discard the supernatant. In the present invention, the time for the standing precipitation is not particularly limited, and the solid and the liquid may be separated, and in the present invention, 10 to 15h is preferable. In the invention, the washing times are preferably 3~5, and impurities on the surface of manganese sand, steel slag or bentonite are removed by washing.

The drying of the invention is preferably to dry the manganese sand, the steel slag or the bentonite after being washed in a drying box. In the invention, the drying temperature is preferably 100 to 120 ℃, more preferably 105 to 115 ℃, and most preferably 110 ℃; the drying time is preferably 20 to 30h, and more preferably 24 to 26h.

The crushing of the invention is preferably carried out on the dried manganese sand, steel slag or bentonite. In the present invention, the method of pulverization and the particle size after pulverization are not particularly limited, and the pulverization may be carried out by a method known to those skilled in the art.

In the present invention, the manganese dioxide content in the manganese sand is preferably not less than 35% by mass, more preferably not less than 45% by mass, and most preferably not less than 60% by mass. According to the invention, the mass percentage of manganese dioxide is limited to more than 35%, so that the catalytic performance of manganese dioxide is ensured, and the removal of iron and manganese is facilitated.

In the invention, the mass ratio of the manganese sand, the steel slag, the bentonite and the pore-forming agent is preferably (40 to 50): (30 to 40): (10 to 15): (5 to 10), more preferably (42 to 45): (35 to 37): (12 to 13): (7~8). The invention gives full play to the characteristics of various materials by limiting the dosage of the manganese sand, the steel slag, the bentonite and the pore-forming agent, so that the filler achieves the optimal treatment effect.

In the present invention, the particle size of the granules is preferably 2 to 4mm, and more preferably 2 to 3mm. The invention increases the reaction contact area of the wastewater and the filler on one hand and plays a role in filtering and retaining the filler on the other hand by limiting the grain size of the granules.

In the present invention, the baking temperature is preferably 500 to 700 ℃, more preferably 550 to 650 ℃, and most preferably 600 ℃. The invention removes impurities in the material by roasting, and simultaneously increases the porosity of the filler.

The invention also provides the filler prepared by the preparation method.

In the invention, the application of the filler in sewage is preferably to apply the filler to a deep bed ion reaction system for sewage treatment, and specifically comprises the following steps: the packing is placed in a water treatment tank, preferably of organic glass tank construction. The specific method for treating the sewage by using the filler is not particularly limited, and the treatment method known to those skilled in the art can be selected.

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

Example 1

1) Manganese sand (MnO) ₂ 35 percent of mass percent), respectively mixing and stirring the steel slag and the bentonite with distilled water, standing and settling for 12 hours, skimming a supernatant, then mixing with the distilled water, and washing with water for three times;

2) Putting the cleaned manganese sand, steel slag and bentonite into a drying oven at 105 ℃ respectively for drying for 24 hours;

3) Crushing the dried manganese sand, steel slag, bentonite and pore-forming agent;

4) Mixing 50 parts of crushed manganese sand, 30 parts of steel slag, 15 parts of bentonite and 5 parts of pore-forming agent particles by weight;

5) The mixture obtained in the step 4) is processed by a granulator to obtain a filler primary finished product with the thickness of about 3 mm;

6) And (3) roasting the primary filler finished product for 2 hours at 550 ℃ in a muffle furnace, and cooling at room temperature to obtain the filler.

Examples 2 to 8

MnO in manganese Sand of example 2~8 ₂ The mass percentage content is shown in table 1, and other conditions are exactly the same as example 1.

TABLE 1 MnO in manganese Sand of example 2~8 ₂ In percentage by mass of

Examples	MnO in manganese sand ₂ In percentage by mass of
		2	30%
3	33%
		4	36%
5	37%
		6	38%
7	39%
		8	40%

The filler prepared in example 1~8 was applied to an experimental apparatus for acid mine wastewater treatment as shown in FIG. 5, and the reaction time was controlled to 6 hours at 2m under the conditions of inlet water pH of 3.6, total iron concentration of 50mg/L and total manganese concentration of 5mg/L ³ The treatment capacity is run for 60 days, and the pH value of the effluent is 6~7. The total iron and manganese contents of the effluent are shown in figure 1. As can be seen from FIG. 1, when the manganese sand MnO ₂ When the mass percentage content is more than or equal to 35 percent, the total iron concentration of the effluent is less than 0.3mg/L, the total manganese concentration of the effluent is less than 0.1mg/L, the pH value of the effluent is 6~7, and the effluent meets the national drinking water standard.

Example 9

1) Manganese sand (MnO) ₂ 38.2 percent of mass percent), steel slag, bentonite and distilled water are mixed and stirred, and then the mixture is statically settled for 12 hours, and then the mixture is mixed with the distilled water after supernatant fluid is removed, and the mixture is washed for three times;

2) Putting the cleaned manganese sand, steel slag and bentonite into a drying oven at 105 ℃ for drying for 24 hours;

4) Mixing 40 parts of crushed manganese sand, 40 parts of steel slag, 10 parts of bentonite and 10 parts of pore-forming agent particles, wherein the parts are by weight;

5) The mixture obtained in the step 4) is processed by a granulator to obtain a filler primary finished product with the thickness of about 3.5 mm;

6) And roasting the primary filler finished product for 4 hours at 650 ℃ in a muffle furnace, and cooling at room temperature to obtain the filler.

Examples 10 to 15

The mass parts of manganese sand, steel slag, bentonite and pore-forming agent in examples 10 to 15 are shown in Table 2, and the other conditions are exactly the same as those in example 9.

TABLE 2 examples 10 to 15 in which the parts by mass of manganese sand, steel slag, bentonite and pore-forming agent are

Examples	Manganese sand, steel slag, bentonite and pore-forming agent in parts by weight
		10	70 parts, 10 parts and 10 parts
11	60 parts, 20 parts, 10 parts and 10 parts
		12	50 parts, 30 parts, 10 parts and 10 parts of
13	30 parts, 50 parts, 10 parts and 10 parts
		14	10 parts, 60 parts, 10 parts and 10 parts
15	10 parts, 70 parts, 10 parts and 10 parts

The filler obtained in the examples 9 to 15 is applied to an experimental device for acid mine wastewater treatment shown in FIG. 5, the reaction time is controlled to be 4.5h under the conditions that the pH value of inlet water is 4.2, the total iron concentration is 36mg/L and the total manganese concentration is 3.3mg/L, and the reaction time is 1m ³ D, the treatment capacity is operated for 60 days, and the pH value of the obtained water is 7~8; the obtained total iron concentration and total manganese concentration of the effluent are shown in figure 2, and as can be seen from figure 2, the total iron concentration of the effluent is below 0.3mg/L, the total manganese concentration of the effluent is below 0.1mg/L, the pH of the effluent is 7~8, and the effluent meets the national drinking water standard.

Example 16

1) Manganese sand (MnO) ₂ 40 percent of mass percent), steel slag, bentonite and distillationMixing water, stirring, standing for 12h, removing supernatant, mixing with distilled water, and washing with water for three times;

4) Mixing 35 parts of crushed manganese sand, 40 parts of steel slag, 15 parts of bentonite and 10 parts of pore-forming agent particles by weight;

5) The mixture obtained in the step 4) is processed by a granulator to obtain a primary finished product of filler with the thickness of about 4 mm;

6) And roasting the primary filler product at 650 ℃ in a muffle furnace for 3 hours, and cooling at room temperature to obtain the filler.

Examples 17 to 27

The particle diameters of the mixtures obtained in step 5) in examples 17 to 27 after granulating by a granulator are shown in Table 3, and the other conditions were exactly the same as those in example 16.

TABLE 3 granulated particles for examples 17 to 27

Examples	Granulation particle size/mm
		17	0.50
18	1.00
		19	1.50
20	2.00
		21	2.50
22	3.00
		23	3.50
24	5.00
		25	6.00
26	8.00
		27	10.00

The fillers prepared in examples 17 to 27 were applied to an experimental apparatus for acid mine wastewater treatment as shown in FIG. 5, and the reaction time was controlled to 6 hours at 2m under the conditions of a feed water pH of 3.6, a total iron concentration of 50mg/L and a total manganese concentration of 5mg/L ³ The treatment capacity is run for 60 days, and the pH value of the effluent is 6~7. The total iron and manganese contents of the effluent are shown in figure 3. As can be seen from FIG. 3, when the grain size of the granules is from 2mm to 6mm, the total iron concentration of the effluent is below 0.3mg/L, the total manganese concentration of the effluent is below 0.1mg/L, the pH of the effluent is 6~7, which meets the national drinking water standard, and when the grain size of the early granules is less than 2mm or more than 6mm, the total iron concentration of the effluent is more than 0.3mg/L, the total manganese concentration of the effluent is more than 0.1mg/L, which does not meet the national drinking water standard.

Examples 28 to 33

The baking temperatures in step 6) in examples 28 to 33 are shown in Table 4, and the other conditions were exactly the same as those in example 16.

TABLE 4 baking temperatures in examples 28 to 33

Examples	Roasting temperature/. Degree.C
		28	400
29	500
		30	600
31	700
		32	800
33	900

The fillers prepared in examples 28 to 33 were applied to an experimental device for acidic mine wastewater treatment as shown in FIG. 5, and the reaction time was controlled to 6 hours at 2m under the conditions of inlet water pH of 3.6, total iron concentration of 50mg/L and total manganese concentration of 5mg/L ³ The treatment capacity is run for 60 days, and the pH value of the effluent is 6~7. The total iron and manganese contents of the effluent are shown in figure 4. As can be seen from FIG. 4, when the calcination temperature is 500 to 700 ℃, the total iron concentration of the effluent is below 0.3mg/L, the total manganese concentration of the effluent is below 0.1mg/L, the pH of the effluent is 6~7, which meets the national drinking water standard, and when the calcination temperature is less than 500 ℃ or more than 700 ℃,the concentration of the total iron in the effluent is more than 0.3mg/L, and the concentration of the total manganese in the effluent is more than 0.1mg/L, which does not meet the national drinking water standard.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of the filler is characterized by comprising the following preparation steps:

mixing manganese sand, steel slag, bentonite and a pore-forming agent, and then sequentially granulating and roasting to obtain a filler;

the mass ratio of the manganese sand to the steel slag to the bentonite to the pore-forming agent is (40 to 50): (30 to 40): (10 to 15): (5 to 10);

the roasting temperature is 500 to 700 ℃;

the mass percentage of manganese dioxide in the manganese sand is not less than 35 percent;

the grain size of the granules is 2-4 mm.

2. The filler produced by the production method according to claim 1.

3. Use of the filler of claim 2 in the treatment of wastewater, wherein the wastewater has a total iron concentration of no more than 50mg/L and a total manganese concentration of no more than 5mg/L; the pH value of the sewage is 3~5.