CN115197867B - A kind of biological adjustment agent and its method of sorting aluminum electrolytic carbon slag - Google Patents

Abstract

The invention provides a biological regulator and a method for sorting aluminum electrolytic carbon slag by using it, belonging to the technical field of aluminum electrolytic carbon slag separation. The biological adjustment agent is composed of a main bacterial agent, a secondary bacterial agent and an auxiliary bacterial agent. Each bacterial agent is subjected to expanded culture, centrifugation, freeze-drying, and the biological regulator is obtained after weighing and proportioning. The biological regulator is used for the flotation and separation of fine particles in the aluminum electrolytic carbon slag, the method is as follows: After the aluminum electrolytic carbon slag is crushed, ball milled, and sieved, the ‑200 mesh fine particles enter the adjustment tank, and the pH regulator and biological adjustment are added The agent is inflated and stirred, the biologically adjusted fine particles are separated by flotation, and then dehydrated and dried to obtain high-quality toner products and electrolyte products. The bioregulator of the present invention is combined with fine particles and surface modified to efficiently improve the selective adsorption of fine particles and collectors and improve the sorting efficiency; the bioregulator is a natural biological preparation, which is green, efficient, and easy to degrade The advantages.

Description

A kind of biological adjustment agent and its method of sorting aluminum electrolytic carbon slag

technical field

The invention relates to the technical field of aluminum electrolysis carbon slag treatment, in particular to a biological conditioner and a method for sorting aluminum electrolysis carbon slag using it.

Background technique

Aluminum electrolytic carbon slag is a subsidiary product of the aluminum production process. It must be removed from the electrolytic cell in time because it will deteriorate the technical and economic indicators of aluminum electrolytic production. It has leaching toxicity and is a hazardous waste. "National Hazardous Waste List (2021 Edition)" Medium code is "321-025-48".

Aluminum electrolytic carbon residue is mainly composed of carbon and electrolyte. The flotation method utilizes the difference in surface properties between carbon and electrolyte to recover carbon powder and regenerate electrolyte by adding a specific collector and then aerating and sorting. Due to the low separation efficiency of fine particles, the overall separation efficiency of the existing flotation method is low: the carbon content in the recycled electrolyte is high, which limits its reuse in the production of electrolytic aluminum; there are still electrolyte inclusions in the carbon powder According to the "Identification of Hazardous Waste Identification Standard for Leaching Toxicity" (GB5085.3-2007), it is still a hazardous waste with leaching toxicity. Although the flotation method has the advantages of normal temperature and pressure in the recovery process, no secondary pollution, comprehensive resource recovery, and low processing costs, the low product quality caused by the low efficiency of fine particle sorting has become a bottleneck that limits the large-scale industrial application of this method.

Compared with physical separation, biopharmaceuticals have a unique mechanism of action, which can significantly change the surface characteristics of specific components, or use specific carriers for targeted adsorption; and the particle size of biopharmaceuticals is closer to that of fine-grained minerals, which is beneficial to the strengthening of fine-grained minerals. Sorting granular minerals and reducing impurities have natural advantages; in addition, biopharmaceuticals are environmentally friendly and low in cost, and have great application prospects in the efficient utilization of refractory minerals.

Contents of the invention

The purpose of the present invention is to: aim at the above-mentioned problems, to provide a biological regulator and a method for sorting aluminum electrolytic carbon slag by using it. The separation efficiency of slag fine particles improves the separation efficiency of carbon and electrolyte.

In order to achieve the above object, the technical scheme adopted in the present invention is as follows:

A biological adjustment agent is composed of a main bacterial agent, a secondary bacterial agent and an auxiliary bacterial agent, wherein the main bacterial agent is Rhodobacteraceae sp., accounting for 54-70% by weight, and the secondary bacterial agent is composed of Paracoccus pantotrophus and Planktosalinus lacus, Among them, Paracoccus pantotrophus accounted for 8-15%, and Planktosalinus lacus accounted for 8-15%. The auxiliary bacterial agent was composed of Gemmobacter aquaticus and Novosphingobium aerophilum, among which Gemmobacter aquaticus accounted for 3-8%, and Novosphingobium aerophilum accounted for 3-8%. .

The method for sorting aluminum electrolytic carbon slag by using the above-mentioned biological regulator comprises the following steps:

(1) Carry out expanded culture of each bacterial strain respectively; Centrifuge and freeze-dry the bacterial liquid after expanded culture to obtain powdery biological bacterial agent, and the effective number of viable bacteria of a single bacterial species in the powdery biological bacterial agent is ≥10 billion/g;

(2) mixing the main bacterial agent, the secondary bacterial agent and the auxiliary bacterial agent according to the proportion to obtain the biological regulator;

(3) Crushing and ball milling the aluminum electrolytic carbon slag, sieving and separating to obtain unqualified coarse particles of +80 mesh, qualified particle size above +200 mesh, and fine particles of -200 mesh, among which the unqualified coarse particles are returned to the ball mill for 200 mesh The ore pulp with qualified particle size above mesh enters the original flotation separation process, and the ore pulp with fine particles of -200 mesh enters the next step;

(4) Transfer the pulp of -200 mesh fine particles into the adjustment tank, add pH adjuster and biological adjuster, and inflate and stir for 10-20 minutes;

(5) Add collectors to the pulp, and mechanically stir for 1 to 5 minutes;

(6) The pulp enters the flotation equipment for flotation;

(7) The flotation product is dehydrated in three stages of sedimentation, filtration and drying to obtain the final product.

In the above method, preferably, in step (4), the mass concentration of the pulp is controlled at 10-20%, and the pulp is controlled at 20-40°C.

In the above method, preferably, the pH regulator in step (4) is K ₂ HPO ₄ , KH ₂ PO ₄ , Na ₂ CO ₃ or NaHCO ₃ , and the pH value is adjusted to be 8.5-9.5.

In the above method, preferably, the added amount of the bioregulator in step (4) is 10-50 g/t.

In the above method, preferably, the collector described in step (5) is kerosene, and the amount of the collector is 0.3-1 kg/t.

In summary, owing to adopting above-mentioned technical scheme, the beneficial effect of the present invention is:

1. The present invention separately separates the fine particles of aluminum electrolytic carbon slag, avoids the inclusion of fine particles in conventional flotation, solves the problem of low product quality caused by the inclusion of fine particles, and improves the flotation efficiency of conventional particles.

2. In the present invention, a biological regulator is also added during sorting. The biological regulator is close to the particle size of the fine particles, and it is easier to combine with the fine particles and modify the surface, improve the surface characteristics of the fine particles of aluminum electrolytic carbon slag, and effectively improve the fine particle size. The selective adsorption of particles and collectors greatly improves the sorting efficiency of fine particles.

3. The biological regulator is a natural biological agent, which has the advantages of green, high efficiency and easy degradation.

Description of drawings

Fig. 1 is the process flow diagram of the preparation process of the biological regulator according to the present invention and the separation of aluminum electrolytic carbon slag by using it.

Fig. 2 is the micrograph of the flotation product of embodiment 2.

Detailed ways

Below in conjunction with specific embodiment, the present invention is described in further detail, but the implementation mode of the present invention is not limited to the scope that embodiment shows. These examples are only used to illustrate the present invention, not to limit the scope of the present invention. In addition, after reading the contents of the present invention, those skilled in the art can make various modifications to the present invention, and these equivalent changes also fall within the scope defined by the appended claims of the present invention.

In the present invention, the main bacterial agent Rhodobacteraceae sp. is purchased from Guangdong Microbial Culture Collection Center, and the culture preservation number is: GDMCC 1.1153. Paracoccus pantotrophus and Planktosalinus lacus are composed of Paracoccus pantotrophus and Planktosalinus lacus, wherein: Paracoccus pantotrophus was purchased from Guangdong Microbial Culture Collection Center, the culture preservation number is: GDMCC 1.432; No.: CGMCC 1.12924. The auxiliary bacterial agent is composed of Gemmobacter aquaticus and Novosphingobium aerophilum, wherein: Gemmobacter aquaticus was purchased from Guangdong Microbial Culture Collection Center, the strain preservation number is: GDMCC 1.1790; Novosphingobium aerophilum was purchased from Guangdong Microbial Culture Collection Center, and the strain preservation number was : GDMCC 1.1828.

When expanding the culture, the medium number used by Rhodobacteraceae sp. is 108, and the formula is as follows: 0.50 g of yeast powder, 0.50 g of peptone, 0.50 g of casamino acids, 0.50 g of glucose, 0.50 g of soluble starch, and pyruvic acid Sodium 0.30g, K ₂ HPO ₄ 0.30g, MgSO ₄ 7H ₂ O 0.05g, agar 15.00g, distilled water 1000.00ml, adjust to final pH 7.2 with K ₂ HPO ₄ or KH ₂ PO ₄ , culture temperature: 30°C, Culture time: 24-48h.

The medium number used by the pantotrophic Paracoccus pantotrophus is 104, and the formula is as follows: polypeptone 10.0g, yeast powder 2.0g, MgSO ₄ ·7H ₂ O 1.0g, distilled water 1.0L, agar 15.0g. Cultivation temperature: 30°C Cultivation time: 24-48h.

The medium number used by the lake salt bacterium Planktosalinus lacus is 0223, and the formula is as follows: 55.1g of seawater 2216 agar, 1.0L of distilled water, pH7.4. Culture temperature: 30°C, culture time: 24-48h.

The medium number used by Gemmobacter aquaticus is 2108, and the formula is as follows: peptone 10.0g, yeast extract 5.0g, glucose 1.0g, agar 15.0g, distilled water 1.0L, pH 6.8-7.0, culture temperature: 30°C culture time: 24- 48h.

The medium number used by the aerobic neosphingobium Novosphingobium aerophilum is 108, the culture temperature: 28° C. and the culture time: 24-48 hours.

The following takes the carbon slag of an electrolytic aluminum plant in Baise, Guangxi as the raw material, and performs flotation separation as an example to illustrate. The main process of flotation separation is: carbon slag crushing → ball milling → screening → flotation → three-stage dehydration of flotation products, in which the unqualified coarse particles of +80 mesh are screened out and returned to the ball milling process, and the qualified particles of +200 mesh and -200 mesh qualified particles enter the flotation process, and the flotation adopts a flotation process of one roughing, two selections, and two sweeping; +200 mesh qualified particles and -200 mesh qualified particles are flotationed separately, The final toner products, medium mineral products (in-process circulation in actual production), and electrolyte products are combined separately.

Example 1

A biological adjustment agent is composed of a main bacterial agent, a secondary bacterial agent and an auxiliary bacterial agent, wherein the main bacterial agent is Rhodobacteraceae sp., accounting for 70% by weight, and the secondary bacterial agent is composed of Paracoccus pantotrophus and Planktosalinus lacus, wherein, Paracoccus pantotrophus accounted for 10%, Planktosalinus lacus accounted for 10%; auxiliary bacterial agents consisted of Gemmobacter aquaticus and Novosphingobium aerophilum, of which Gemmobacter aquaticus accounted for 3% and Novosphingobium aerophilum accounted for 7%.

Utilize this bioregulator to carry out the method for sorting aluminum electrolysis carbon slag, its flow chart is referring to Fig. 1, comprises the following steps:

(1) Carry out expanded culture of each strain respectively; Centrifuge and freeze-dry the bacterial liquid after expanded culture to obtain powdery biological bacterial agent, the effective number of viable bacteria of a single strain ≥ 1 billion/g;

(2) mixing the main bacterial agent, the secondary bacterial agent and the auxiliary bacterial agent according to the proportion to obtain the biological regulator;

(3) Crushing and ball milling the aluminum electrolytic carbon slag, sieving and separating to obtain unqualified coarse particles of +80 mesh, qualified particle size above 200 mesh, and fine particles of -200 mesh, among which the unqualified coarse particles are returned to the ball mill for 200 mesh The ore pulp of the above qualified particle size enters the original flotation separation process, and the ore pulp with -200 mesh fine particles enters the next step;

(4) Transfer the ore pulp of -200 mesh fine particles into the adjustment tank, control the mass concentration of the ore pulp at 10%, and control the ore pulp at 20°C; add pH regulator NaHCO ₃ to adjust the pH value to 8.5, and the addition amount is 10g /t add bioregulator, inflate and stir for 10 minutes;

(5) Add collector kerosene to the pulp according to the addition amount of 0.3kg/t, and mechanically stir for 1min;

(6) The pulp enters the flotation equipment for flotation, adopting a flotation process of one roughing, two selections, and two sweeps;

(7) The flotation product is dehydrated in three stages of sedimentation, filtration and drying to obtain the final product.

Example 2

A biological adjustment agent is composed of a main bacterial agent, a secondary bacterial agent and an auxiliary bacterial agent, wherein the main bacterial agent is Rhodobacteraceae sp., and the weight ratio is 68%, and the secondary bacterial agent is composed of Paracoccus pantotrophus and Planktosalinus lacus, wherein, Paracoccus pantotrophus accounted for 10%, Planktosalinus lacus accounted for 12%; auxiliary bacterial agents consisted of Gemmobacter aquaticus and Novosphingobium aerophilum, of which Gemmobacter aquaticus accounted for 7% and Novosphingobium aerophilum accounted for 3%.

Utilize this bioregulator to carry out the method for sorting aluminum electrolysis carbon slag, its flow chart is referring to Fig. 1, comprises the following steps:

(1) Carry out expanded culture of each strain respectively; Centrifuge and freeze-dry the bacterial liquid after expanded culture to obtain powdery biological bacterial agent, the effective number of viable bacteria of a single strain ≥ 1 billion/g;

(2) mixing the main bacterial agent, the secondary bacterial agent and the auxiliary bacterial agent according to the proportion to obtain the biological regulator;

(3) Crushing and ball milling the aluminum electrolytic carbon slag, sieving and separating to obtain unqualified coarse particles of +80 mesh, qualified particle size above 200 mesh, and fine particles of -200 mesh, among which the unqualified coarse particles are returned to the ball mill for 200 mesh The ore pulp of the above qualified particle size enters the original flotation separation process, and the ore pulp with -200 mesh fine particles enters the next step;

(4) Transfer the pulp of -200 mesh fine particles into the adjustment tank, control the mass concentration of the pulp at 15%, and control the pulp at 30°C; add pH regulator K ₂ HPO ₄ to adjust the pH value to 9.0, according to the amount added Add bioregulator to 30g/t, inflate and stir for 15min;

(5) Add collector kerosene to the pulp according to the addition amount of 0.8kg/t, and mechanically stir for 3 minutes;

(6) The pulp enters the flotation equipment for flotation;

(7) The flotation product is dehydrated in three stages of sedimentation, filtration and drying to obtain the final product.

Example 3

A biological adjustment agent is composed of a main bacterial agent, a secondary bacterial agent and an auxiliary bacterial agent, wherein the main bacterial agent is Rhodobacteraceae sp., and the weight ratio is 54%, and the secondary bacterial agent is composed of Paracoccus pantotrophus and Planktosalinus lacus, wherein, Paracoccus pantotrophus accounted for 15%, Planktosalinus lacus accounted for 15%; auxiliary bacterial agents consisted of Gemmobacter aquaticus and Novosphingobium aerophilum, of which Gemmobacter aquaticus accounted for 8% and Novosphingobium aerophilum accounted for 8%.

Utilize this bioregulator to carry out the method for sorting aluminum electrolysis carbon slag, its flow chart is referring to Fig. 1, comprises the following steps:

(1) Carry out expanded culture of each strain respectively; Centrifuge and freeze-dry the bacterial liquid after expanded culture to obtain powdery biological bacterial agent, the effective number of viable bacteria of a single strain ≥ 1 billion/g;

(2) mixing the main bacterial agent, the secondary bacterial agent and the auxiliary bacterial agent according to the proportion to obtain the biological regulator;

(3) Crushing and ball milling the aluminum electrolytic carbon slag, sieving and separating to obtain unqualified coarse particles of +80 mesh, qualified particle size above 200 mesh, and fine particles of -200 mesh, among which the unqualified coarse particles are returned to the ball mill for 200 mesh The ore pulp of the above qualified particle size enters the original flotation separation process, and the ore pulp with -200 mesh fine particles enters the next step;

(4) Transfer the pulp of -200 mesh fine particles into the adjustment tank, control the mass concentration of the pulp at 20%, and control the pulp at 40°C; add pH regulator Na ₂ CO ₃ to adjust the pH value to 9.5, according to the amount added Add bioregulator at 50g/t, inflate and stir for 20min;

(5) Add collector kerosene to the ore slurry according to the addition amount of 1kg/t, and mechanically stir for 5 minutes;

(6) The pulp enters the flotation equipment for flotation;

(7) The flotation product is dehydrated in three stages of sedimentation, filtration and drying to obtain the final product.

Comparative example 1

This comparative example is blank comparative example 1, adopts conventional flotation process, and its process is specifically:

(1) Crushing and ball milling the aluminum electrolytic carbon slag;

(2) Transfer the ore pulp after ball milling into the adjustment tank, control the mass concentration of the ore pulp at 15%, and control the ore pulp at 30°C; add pH regulator K ₂ HPO ₄ to adjust the pH value to 9.0; do not add biological regulator;

(3) Add collector kerosene to the pulp according to the addition amount of 0.8kg/t, and mechanically stir for 3 minutes;

(4) The pulp enters the flotation equipment for flotation;

(5) The flotation product is dehydrated in three stages of sedimentation, filtration and drying to obtain the final product.

Comparative example 2

This comparative example is blank comparative example 2, does not add biological adjustment agent when carrying out the flotation of -200 mesh fine particles, and its technology is:

(1) Crushing and ball milling the aluminum electrolytic carbon slag, and screening and separating to obtain unqualified coarse particles of +80 mesh, qualified particle size above 200 mesh, and fine particles of -200 mesh, among which the unqualified coarse particles are returned to the ball mill for 200 mesh The ore pulp of the above qualified particle size enters the original flotation separation process, and the ore pulp with -200 mesh fine particles enters the next step;

(2) Transfer the pulp of -200 mesh fine particles into the adjustment tank, control the mass concentration of the pulp at 15%, and control the pulp at 30°C; add pH regulator K ₂ HPO ₄ to adjust the pH value to 9.0, and aerate and stir for 15 minutes ;

(3) Add collector kerosene to the pulp according to the addition amount of 0.8kg/t, and mechanically stir for 3 minutes;

(4) The pulp enters the flotation equipment for flotation;

(5) The flotation product is dehydrated in three stages of sedimentation, filtration and drying to obtain the final product.

Comparative example 3-4

The weight proportion of bioregulator in Comparative Examples 3 and 4 is referring to Table 2, adopts the proportioning of bioregulator in Table 2 to replace the proportioning in Example 2 in step (2), and other steps are all the same as Example 2.

Table 2 Bioregulator formula table

After the methods of Examples 1-3 and Comparative Examples 1-4 were used for flotation of the same batch of electrolytic aluminum plant carbon slag, the flotation results are shown in Table 3.

Table 3 carbon slag flotation example results

The flotation results show that the product quality of +200 mesh qualified particles and -200 mesh qualified particles separated by flotation (comparative example 2 groups) has a certain improvement when not separated (comparative example 1 group), after adding the main bacterial agent (to Proportion 3 and Comparative Example 4) The product quality is obviously improved again. The product quality of (embodiment 2) is the best after adding main bacterium agent, secondary bacterium agent and auxiliary bacterium agent simultaneously, and Fig. 2 is the micromorphology of embodiment 2 flotation products, the carbon powder product (Fig. 2-a) The carbon content reaches more than 95%, and the carbon impurity content in the electrolyte product (Fig. 2-b) drops below 3%.

The above description is a detailed description of the preferred feasible embodiments of the present invention, but the embodiments are not used to limit the scope of the patent application of the present invention. All equivalent changes or modifications completed under the technical spirit suggested by the present invention shall belong to The scope of patents covered by the present invention.

Claims (7)

1. a bioregulator, is characterized in that, described bioregulator is made up of main bacterium agent, secondary bacterium agent and auxiliary bacterium agent, and wherein main bacterium agent is Rhodobacteraceae sp. , and weight ratio is 54～70%, The auxiliary bacterial agent is composed of Paracoccus pantotrophus and Planktosalinus lacus , of which, Paracoccus pantotrophus accounts for 8~15%, and Planktosalinus lacus accounts for 8~15% . 8%, Novosphingobium aerophilum accounted for 3~8%; the main bacterial agent Rhodobacteraceae sp. was purchased from the Guangdong Microbial Culture Collection Center, and the culture preservation number was: GDMCC 1.1153; the secondary bacterial agent Paracoccus pantotrophus was purchased from the Guangdong Microbial Culture Collection Center, strain preservation number: GDMCC 1.432; Planktosalinus lacus was purchased from China General Microorganism Strain Collection Management Center, strain preservation number: CGMCC 1.12924; auxiliary bacterial agent Gemmobacter aquaticus was purchased from Guangdong Microbial Culture Collection Center, strain The preservation number is: GDMCC 1.1790; Novosphingobium aerophilum was purchased from Guangdong Microbial Culture Collection Center, and the culture preservation number is GDMCC 1.1828. 2. The application of the biological regulator according to claim 1 in the separation of aluminum electrolytic carbon slag. 3. The method for sorting aluminum electrolytic carbon slag by using the biological regulator as claimed in claim 1, is characterized in that: comprising the following steps: Expand the culture of each strain separately; centrifuge and freeze-dry the cultured bacteria solution to obtain a powdered biological agent. The effective number of viable bacteria of a single strain in the powdered biological agent is ≥ 1 billion/g ; Mix the main bacterial agent, secondary bacterial agent and auxiliary bacterial agent according to the proportion to obtain the biological regulator; The aluminum electrolytic carbon slag is crushed, ball milled, screened and separated to obtain unqualified coarse particles of +80 mesh, qualified particle size of +200 mesh, and fine particles of -200 mesh. The unqualified coarse particles are returned to the ball mill, and the qualified particles above 200 mesh The ore pulp of particle size enters the original flotation separation process, and the ore pulp of -200 mesh fine particles enters the next step; Transfer the pulp of -200 mesh fine particles into the adjustment tank, add pH adjuster and biological adjuster, aerate and stir for 10~20min; Add collector to the pulp, and mechanically stir for 1-5 minutes; The pulp enters the flotation equipment for flotation; Flotation products are dehydrated in three stages of sedimentation, filtration and drying to obtain flotation products. 4. The method according to claim 3, characterized in that: in step (4), the mass concentration of the pulp is controlled at 10-20%, and the pulp is controlled at 20-40°C. 5. The method according to claim 3, characterized in that: in step (4), the pH regulator is K ₂ HPO ₄ , KH ₂ PO ₄ , Na ₂ CO ₃ or NaHCO ₃ , and the pH value is adjusted to 8.5-9.5. 6 . The method according to claim 3 , characterized in that: the amount of bioregulator added in step (4) is 10-50 g/t. 7. The method according to claim 3, characterized in that: the collector described in step (5) is kerosene, and the amount of collector is 0.3-1kg/t.

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