A system and method for preparing an oxygen pressure leach dispersant using herbivore excrement

Abstract

The application belongs to the technical field of oxygen pressure leaching dispersant preparation, and discloses a system and method for preparing oxygen pressure leaching dispersant from herbivorous animal excrement. The herbivorous animal digests, decomposes and absorbs nutrients such as protein, fat, starch and crude fiber in plants, and only lignin and insoluble residual substances after the nutrients are absorbed are left to form excrement, so that the excrement becomes a carrier for naturally enriching and purifying lignin, and the total amount of organic matters such as protein, fat, starch and crude fiber entering the zinc hydrometallurgy process can be reduced to the maximum. Due to the increase of lignin content in the raw material, the processing turnover is reduced, the processing cost is directly reduced, and the unit output of the oxygen pressure leaching dispersant is improved. Meanwhile, the process of enriching and purifying lignin from herbivorous animal excrement to prepare oxygen pressure leaching dispersant is smoothly connected with the oxygen pressure leaching zinc smelting process, and the two processes can be continuously and stably operated.

Description

Technical Field

[0001] This invention belongs to the field of oxygen pressure leaching dispersant preparation technology, specifically relating to a system and method for preparing oxygen pressure leaching dispersants using herbivorous animal excrement. Background Technology

[0002] The oxygen pressure leaching process for wet zinc smelting, developed in the 1980s, is a revolutionary zinc smelting method. Its key feature is the elimination of roasting, acid production, and atmospheric leaching of zinc sulfide concentrate. Instead, it employs a specially designed pressure reactor (high-pressure vessel) to leach zinc sulfide in a high-temperature, high-pressure, and oxygen-rich environment. In the presence of ferric ions, oxygen pressure leaching can dissolve zinc sulfide that would not dissolve under normal leaching conditions. Because the reaction products include sulfates, elemental sulfur, and alum compounds, and the reaction temperature exceeds the melting point of sulfur (119°C), without additives, the hydrophobic surface of the sulfides makes them difficult to wet with water but easily wetted by molten sulfur. This causes the molten sulfur to preferentially wet and encapsulate unreacted sulfides, penetrating into the pores, thus significantly increasing diffusion resistance and severely hindering the leaching rate of valuable metals. Extensive research on various oxygen pressure leaching dispersants, such as lignin sulfonates, tannin from white oak (expensive), and lignite (poor dispersion and low leaching rate), has revealed that only lignin sulfonates (commonly sodium lignin sulfonate or calcium lignin sulfonate) are truly suitable for large-scale application in production.

[0003] Lignosulfonates are complex polycyclic derivatives of sulfonates containing phenolic hydroxyl groups, ether methyl groups, and aldehyde groups. The molecules contain a network of multiple groups and polysulfonic acid groups. When adsorbed onto the surface of concentrates or sulfur, they still retain polar groups extending into the solution, exhibiting hydrophilicity and reducing the surface tension between the surface and water. Adding an appropriate amount of lignin sulfonate lowers the surface tension of liquid sulfur, allowing it to be wiped off the sulfide surface under stirring, exposing the reaction surface and improving the leaching process. Simultaneously, the resulting leaching residue is easier to flotate. Lignosulfonates are mainly found in acid pulping wastewater in the paper industry and are one of the major byproducts of the paper industry. Acid pulping involves acid hydrolysis, where sulfite ions replace the functional groups on the phenylpropane side chains, thereby enhancing their solubility and accelerating separation from cellulose. The lignin obtained after removing cellulose is called lignin sulfonate.

[0004] As a byproduct of the papermaking industry, lignin sulfonate products lack unified quality standards. For zinc refining enterprises using pressure leaching, the procurement of lignin sulfonates lacks direction and focus, and the suitability of the lignin sulfonate products currently in use is questionable. From a production perspective, lignin sulfonate products from different manufacturers, or even different batches from the same manufacturer, exhibit certain differences. In the oxygen leaching zinc refining process of various enterprises, the following problems have arisen when using these lignin sulfonate products without clear quality standards:

[0005] (1) Insufficient sulfur dispersion capacity, molten sulfur encapsulates unreacted zinc concentrate, affecting element leaching rate and element sulfur conversion rate, and even affecting subsequent flotation treatment of leaching residue;

[0006] (2) During use, it was found that the oxygen pressure vessel was not discharging smoothly, and even the oxygen pressure vessel, flash tank and other equipment were clumping, which affected safe production.

[0007] (3) Quality issues: The chlorine content of purchased lignin sulfonate fluctuates (3-10%), which leads to a rise and large fluctuation in chlorine content in the production process, and aggravates the corrosion of equipment and pipelines. In particular, oxygen pressure leaching involves three highs: high temperature, high pressure and high acid, which poses a high risk to process safety. The zinc electrowinning anode plate (Pb-Ag alloy plate) is severely corroded, and the quality of zinc ingots and lead fluctuates.

[0008] Given the above situation, lignin sulfonates, a byproduct of the papermaking industry, can no longer meet the requirements of the oxygen pressure leaching process in wet zinc refining, and have significantly hampered safe, continuous, and stable production. Therefore, providing a system and method for preparing oxygen pressure leaching dispersants using herbivore excrement is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0009] In view of this, the present invention provides a system and method for preparing oxygen pressure leaching dispersants using herbivorous animal excrement. Through the digestion, decomposition, and absorption of nutrients (organic matter) such as protein, fat, starch, and crude fiber from plants by herbivorous animals, only lignin and insoluble residues of absorbed nutrients remain in the excrement. This excrement becomes a natural carrier for enriching and purifying lignin. Using this as raw material, the total amount of organic matter such as protein, fat, starch, and crude fiber entering the hydrometallurgical zinc smelting process can be minimized. Due to the increased lignin content in the raw material, the processing turnover is reduced, directly lowering processing costs and increasing the unit yield of oxygen pressure leaching dispersants (i.e., lignin sulfonates). Simultaneously, the process of enriching and purifying lignin from herbivorous animal excrement to prepare oxygen pressure leaching dispersants is smoothly integrated with the oxygen pressure leaching zinc smelting process, ensuring continuous and stable operation of both processes.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] A system for preparing an oxygen pressure leaching dispersant using herbivore excrement, the system comprising: a pulverizer, a mixing tank, and a delivery pump;

[0012] The excrement from the herbivorous animals passes sequentially through a pulverizer, a mixing tank, and a delivery pump.

[0013] Furthermore, it also includes a heat source device; the heat source device is connected to the stirring tank.

[0014] A method for preparing an oxygen pressure leaching dispersant using herbivore excrement, comprising the steps described above:

[0015] (1) Herbivorous animal excrement is pulverized using a pulverizer, with a 30-mesh passing rate of >90%;

[0016] (2) The crushed excrement of herbivorous animals is placed in a mixing tank, an alkaline substance is added, the temperature is raised and heated to prepare alkali lignin.

[0017] (3) After the alkali lignin is prepared, a sulfonating agent is added to the stirring tank for sulfonation treatment to obtain an oxygen pressure leaching dispersant.

[0018] (4) Use a delivery pump to pump the oxygen pressure leaching dispersant to the point of use.

[0019] Furthermore, the alkaline substance is selected from one or more of CaO, Ca(OH)2, NaOH, NH3·H2O, and Na2CO3.

[0020] The beneficial effects of the above technical solution are as follows: This invention uses chemical treatment, which has the advantages of lower equipment requirements and shorter processing time compared to physical and biological treatment. Among them, alkali treatment is gentler than acid treatment and has a higher lignin degradation rate. Through alkali treatment, chemical bonds such as ether bonds and ester bonds in lignin are broken, resulting in the partial degradation of a large number of chemical bonds and the generation of a large number of active groups such as phenolic hydroxyl groups, forming alkali lignin.

[0021] Furthermore, the alkaline substance accounts for 5-15% of the weight of the herbivore's excrement.

[0022] Furthermore, in step (2), the alkaline boiling process is controlled with a liquid-to-solid ratio of 8 to 15:1 and a temperature of 70 to 90°C. The reaction endpoint is reached when the pH reaches 12 to 13.

[0023] Furthermore, the sulfonating agent is Na2SO3, accounting for 5-15% of the weight of herbivore excrement.

[0024] Furthermore, in step (3), the sulfonation treatment is controlled with a liquid-to-solid ratio of 8 to 15:1, a temperature of 70 to 90°C, and a reaction time of 2 to 4 hours.

[0025] Furthermore, in step (3), a catalyst is added at the same time as the sulfonating agent, wherein the catalyst is ferric sulfate or copper sulfate.

[0026] The beneficial effects of the above technical solution are as follows: Alkali lignin containing a large number of active groups such as phenolic hydroxyl groups can be modified by sulfonation with sulfonating agents to introduce sulfonic acid groups (-SO3H) into the lignin molecules, thereby increasing the hydrophilicity of the lignin molecules. At the same time, the steric hindrance between lignin molecules increases, which is beneficial to the improvement of the system's dispersibility. Meanwhile, under the action of a catalyst, sulfite can form sulfite free radicals, which initiate free radical reactions and are beneficial to the sulfonation reaction of lignin.

[0027] Furthermore, Fe in the catalyst 3+ or Cu 2+ The dosage is 1–3 mg / g lignin.

[0028] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The plants involved in this invention are wide-ranging, and the excrement of herbivorous animals can meet the requirements of the oxygen pressure leaching zinc smelting process, enabling normal production.

[0030] 2. This invention solves the problem that traditional plants generally have low lignin content, which leads to high direct preparation and processing costs, and the problem that all nutrients (organic matter) in plants, such as protein, fat, starch, and crude fiber, enter the wet zinc smelting process.

[0031] 3. This invention overcomes the limitations imposed by plant species, plant parts, and seasonal plant selection. It eliminates the need to specifically select plants with high lignin content (overcoming plant species limitations), parts of lignin-rich plants (overcoming plant part limitations), or lignin-rich plants in their dry season (overcoming plant growth stage limitations). Through the digestion, decomposition, and absorption of nutrients (organic matter) such as protein, fat, starch, and crude fiber from plants by herbivores, only lignin and insoluble residues of absorbed nutrients remain in the excrement. This significantly increases the lignin content of the excrement. Using this as raw material, the total amount of organic matter such as protein, fat, starch, and crude fiber entering the hydrometallurgical zinc refining system can be minimized. The increased lignin content in the raw material reduces processing turnover, directly lowering processing costs, while simultaneously increasing the unit output of the oxygen pressure leaching dispersant (i.e., lignin sulfonate). Attached Figure Description

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0033] Figure 1 This is a process flow diagram of the method of the present invention. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] This invention provides a system for preparing oxygen pressure leaching dispersants using herbivorous animal excrement, the system comprising: a pulverizer, a mixing tank, and a delivery pump;

[0036] The excrement from the herbivorous animals passes sequentially through a pulverizer, a mixing tank, and a delivery pump.

[0037] Furthermore, it also includes a heat source device; the heat source device is connected to the stirring tank.

[0038] Example 1

[0039] A method for preparing an oxygen pressure leaching dispersant using herbivore excrement, comprising the steps described above:

[0040] (1) Herbivorous animal excrement (lignin content 45.58%, water content 15.66%) was pulverized by a pulverizer, with a 30-mesh pass rate of >90%;

[0041] (2) The crushed excrement of herbivorous animals is placed in a mixing tank, an alkaline substance is added, the temperature is raised and heated to prepare alkali lignin.

[0042] (3) After the alkali lignin is prepared, a sulfonating agent is added to the stirring tank for sulfonation treatment to obtain an oxygen pressure leaching dispersant.

[0043] (4) Use a delivery pump to pump the oxygen pressure leaching dispersant to the point of use.

[0044] Furthermore, the alkaline substance is selected from Ca(OH)2.

[0045] Furthermore, the alkaline substance accounts for 10% of the weight of the herbivore's excrement.

[0046] Furthermore, in step (2), the alkaline boiling process is controlled with a liquid-to-solid ratio of 12:1 and a temperature of 85°C. The reaction endpoint is reached when the pH reaches 12-13.

[0047] Furthermore, the sulfonating agent is Na2SO3, accounting for 10% of the weight of herbivore excrement.

[0048] Furthermore, in step (3), the sulfonation treatment is controlled with a liquid-to-solid ratio of 12:1, a temperature of 85°C, and a reaction time of 2.5 h.

[0049] After alkali boiling and sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 12.57 g / L, which meets the requirements of oxygen pressure leaching production (lignin content ≥ 4 g / L).

[0050] Example 2

[0051] A method for preparing an oxygen pressure leaching dispersant using herbivore excrement, comprising the steps described above:

[0052] (1) Herbivorous animal excrement (lignin content 53.62%, water content 12.71%) was pulverized by a pulverizer, with a 30-mesh pass rate of >90%;

[0053] (2) The crushed excrement of herbivorous animals is placed in a mixing tank, an alkaline substance is added, the temperature is raised and heated to prepare alkali lignin.

[0054] (3) After the alkali lignin is prepared, a sulfonating agent is added to the stirring tank for sulfonation treatment to obtain an oxygen pressure leaching dispersant.

[0055] (4) Use a delivery pump to pump the oxygen pressure leaching dispersant to the point of use.

[0056] Furthermore, the alkaline substance is selected from Ca(OH)2.

[0057] Furthermore, the alkaline substance accounts for 10% of the weight of the herbivore's excrement.

[0058] Furthermore, in step (2), the alkaline boiling process is controlled with a liquid-to-solid ratio of 12:1 and a temperature of 85°C. The reaction endpoint is reached when the pH reaches 12-13.

[0059] Furthermore, the sulfonating agent is Na2SO3, accounting for 10% of the weight of herbivore excrement.

[0060] Furthermore, in step (3), the sulfonation treatment is controlled with a liquid-to-solid ratio of 12:1, a temperature of 85°C, and a reaction time of 2.5 h.

[0061] After alkali boiling-sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 15.13 g / L.

[0062] Example 3

[0063] The difference from Example 1 is that the temperature of both the alkali boiling and sulfonation treatments is controlled at 75°C.

[0064] After alkali boiling-sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 10.41 g / L.

[0065] Example 4

[0066] The difference from Example 1 is that Ca(OH)2 accounts for 5% of the weight of the herbivore's excrement.

[0067] After alkali boiling-sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 9.34 g / L.

[0068] Example 5

[0069] The difference from Example 1 is that the alkaline substance is selected from NaOH and accounts for 10% of the weight of the herbivore excrement.

[0070] After alkali boiling-sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 12.06 g / L.

[0071] Example 6

[0072] The difference from Example 1 is that the sulfonating agent accounts for 5% of the weight of the herbivore excrement.

[0073] After alkali boiling and sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 8.05 g / L.

[0074] Example 7

[0075] The difference from Example 1 is that the reaction time is controlled at 3.5 hours.

[0076] After alkali boiling and sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 12.99 g / L.

[0077] Example 8

[0078] The difference from Example 1 is that in step (3), a catalyst is added simultaneously with the sulfonating agent. The catalyst is ferric sulfate (iron content 20.5%), and the Fe in the catalyst is... 3+ The dosage was 1.33 mg / g lignin, and the sulfonation treatment time was 2 hours, which improved the reaction rate and reduced the reaction time.

[0079] After alkali boiling-sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 12.53 g / L.

[0080] Example 9

[0081] The difference from Example 1 is that in step (3), a catalyst is added simultaneously with the sulfonating agent. The catalyst is copper sulfate (copper content 25.09%), and the Cu in the catalyst... 2+ The dosage was 1.28 mg / g lignin, and the sulfonation time was 2 hours, which improved the reaction rate and reduced the reaction time.

[0082] After alkali boiling-sulfonation treatment, the lignin content of the oxygen pressure leaching dispersant solution was 13.04 g / L.

[0083] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. For the apparatus disclosed in the embodiments, since it corresponds to the method disclosed in the embodiments, the description is relatively simple; relevant parts can be referred to the method section.

[0084] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an oxygen pressure leaching dispersant using herbivore excreta, characterized by, The preparation is carried out using a system comprising: a pulverizer, a mixing tank, and a delivery pump; the herbivore excrement is sequentially passed through the pulverizer, the mixing tank, and the delivery pump. The method includes the following steps: (1) Herbivore excrement is pulverized using a pulverizer, with a 30-mesh pass rate >90%; (2) The crushed excrement of herbivorous animals is placed in a mixing tank, an alkaline substance is added, the temperature is raised and heated to prepare alkali lignin. (3) After the alkali lignin is prepared, a sulfonating agent is added to the stirring tank for sulfonation treatment to obtain an oxygen pressure leaching dispersant; (4) Use a delivery pump to pump the oxygen pressure leaching dispersant to the point of use; The alkaline substance accounts for 5-15% of the weight of herbivore excrement; In step (2), the alkaline boiling process is controlled with a liquid-to-solid ratio of 8-15:1 and a temperature of 70-90°C. The reaction endpoint is reached when the pH reaches 12-13. The sulfonating agent is Na2SO3, accounting for 5-15% of the weight of herbivore excrement; In step (3), the sulfonation treatment is controlled with a liquid-to-solid ratio of 8-15:1, a temperature of 70-90℃, and a reaction time of 2-4 h.

2. A method of preparing an oxygen pressure leaching dispersant using herbivore excreta according to claim 1, characterized in that, It also includes a heat source device; the heat source device is connected to the stirring tank.

3. A method of preparing an oxygen pressure leaching dispersant using herbivore excreta according to claim 1, characterized in that, The alkaline substance is selected from one or more of CaO, Ca(OH)2, NaOH, NH3·H2O, and Na2CO3.

4. A method of preparing an oxygen pressure leaching dispersant using herbivore excreta according to claim 1, characterized in that, In step (3), a catalyst is added at the same time as the sulfonating agent. The catalyst is ferric sulfate or copper sulfate.

5. A method of preparing an oxypresso leaching dispersant using herbivore excreta according to claim 4, characterized in that, The amount of Fe 3+ or Cu 2+ in the catalyst is 1-3 mg / g of lignin.

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