CN117735486A - Method for strengthening sulfur hot melting separation by pretreatment of metal sulfur slag - Google Patents
Method for strengthening sulfur hot melting separation by pretreatment of metal sulfur slag Download PDFInfo
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- CN117735486A CN117735486A CN202311753718.3A CN202311753718A CN117735486A CN 117735486 A CN117735486 A CN 117735486A CN 202311753718 A CN202311753718 A CN 202311753718A CN 117735486 A CN117735486 A CN 117735486A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 266
- 239000011593 sulfur Substances 0.000 title claims abstract description 266
- 239000002893 slag Substances 0.000 title claims abstract description 157
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 144
- 239000002184 metal Substances 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000002844 melting Methods 0.000 title claims abstract description 46
- 230000008018 melting Effects 0.000 title claims abstract description 45
- 238000005728 strengthening Methods 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 title claims description 29
- 238000001914 filtration Methods 0.000 claims abstract description 63
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 230000001105 regulatory effect Effects 0.000 claims abstract description 20
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 19
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000005273 aeration Methods 0.000 claims abstract description 16
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 238000007781 pre-processing Methods 0.000 claims abstract description 15
- 238000011282 treatment Methods 0.000 claims abstract description 15
- 239000012943 hotmelt Substances 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 6
- 239000012265 solid product Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 20
- -1 iron ions Chemical class 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000011084 recovery Methods 0.000 abstract description 16
- 239000000047 product Substances 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 229910001385 heavy metal Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005086 pumping Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preprocessing and strengthening sulfur by hot melting, filtering and separating metal sulfur slag, which comprises the following steps: 1) Crushing and grinding the metal sulfur slag, adding water and acid to carry out slurry mixing to obtain metal sulfur slag slurry; 2) After carrying out aeration treatment on the metal sulfur slag slurry, adding a impurity removal regulating agent to remove impurities to obtain a leaching solution; the impurity removal regulating and controlling agent comprises ferric sulfate, sodium chloride and ammonium chloride; 3) Filtering the leaching solution to separate a solid product, washing and dehydrating the solid product, and separating sulfur liquid through hot melt filtration; the method can realize viscosity reduction of molten metal sulfur slag so as to improve the sulfur recovery rate in the process of hot melting and filtering the metal sulfur slag.
Description
Technical Field
The invention relates to a method for treating metal sulfur slag, in particular to a method for preprocessing and strengthening sulfur hot melting separation of metal sulfur slag, belonging to the field of comprehensive recycling of nonferrous metal smelting waste slag.
Background
Zinc smelting technology is divided into a fire method and a wet method, wherein the fire method zinc smelting has the defects of high energy consumption, harmful gas production and the like, while the wet method zinc smelting unit has relatively low energy consumption, is relatively friendly to the environment, and has high comprehensive utilization degree of resources. Currently, zinc hydrometallurgy is the mainstream of zinc metallurgy technology development, and the yield of zinc hydrometallurgy is about more than 80% of the total amount of zinc in the world. In the zinc hydrometallurgy process of zinc sulfide concentrate oxygen pressure leaching, most of sulfur enters acid leaching slag in the form of elemental sulfur, a small amount of sulfur exists in the form of sulfide, sulfate or sulfuric acid double salt, and besides sulfur, valuable metals such as zinc, iron, silicon, silver and the like are often contained in the acid leaching slag, so that the recovery value is high. If the multi-metal sulfur slag is not treated and recycled in time, the waste of the resources is extremely high, and the environmental problem of waste slag accumulation is also caused.
There are many methods for recovering elemental sulfur from sulfur slag, including chemical methods, which dissolve sulfur by adding organic/inorganic solvents and then extracting and processing to obtain sulfur products, and physical methods, which use solvents that are toxic and volatile, and cannot be applied to practical production on a large scale. The physical method mainly comprises a vacuum distillation method, a high-pressure decantation method, a floatation method, a hot filtration method and the like, and the vacuum distillation method and the high-pressure decantation method have the defects of expensive equipment, complex process and inapplicability to large-scale production; the flotation method utilizes the difference of hydrophilicity of substances in slag to separate elemental sulfur from other materials, the process is simple, the hot filtration method utilizes the low melting point property of sulfur, and the multi-metal sulfur slag is heated to a certain temperature (130-160 ℃) to filter and realize the separation of sulfur from other elements.
However, the multi-metal sulfur slag has complex components, high viscosity after direct melting, and difficult separation of liquid sulfur and other materials in the hot filtration process, so that the sulfur separation recovery rate is low and the further separation recovery of valuable metals in a filter cake is not facilitated. Currently researchers are focusing more on improvements to the melting process and less attention is paid to the raw material pretreatment process. Therefore, it is necessary to provide a method for pretreating and strengthening the hot-melting filtration separation of sulfur by using metal sulfur slag, so as to solve or at least alleviate the technical defect that the separation of sulfur and metal impurities is difficult in the prior art.
Disclosure of Invention
Aiming at the defects existing in the multi-metal sulfur slag treatment process in the prior art, the invention aims to provide a method for preprocessing and strengthening sulfur hot melting, filtering and separating metal sulfur slag, which can realize viscosity reduction of molten metal sulfur slag so as to improve the sulfur recovery rate in the metal sulfur slag hot melting, has simple operation flow, avoids adding toxic reagents and is beneficial to industrial production.
In order to achieve the technical aim, the invention provides a method for preprocessing and strengthening hot melting, filtering and separating sulfur by using metal sulfur slag, which comprises the following steps:
1) Crushing and grinding the metal sulfur slag, adding water and acid to carry out slurry mixing to obtain metal sulfur slag slurry;
2) After carrying out aeration treatment on the metal sulfur slag slurry, adding a impurity removal regulating agent to remove impurities to obtain a leaching solution; the impurity removal regulating and controlling agent comprises ferric sulfate, sodium chloride and ammonium chloride;
3) Filtering the leaching solution to separate a solid product, washing and dehydrating the solid product, and separating sulfur liquid through hot melt filtration.
The key point of the invention is that the special pretreatment process is carried out on the metal sulfur slag, and the impurity metal ions in the metal ions can be efficiently removed, thereby effectively reducing the viscosity of molten metal sulfur slag, improving the hot melting filtering effect and improving the sulfur recovery efficiency. More specifically, acid is firstly adopted for size mixing, oxygen is introduced to oxidize and leach part of metals, metal salts and the like, and a special impurity removal regulating agent is adopted on the basis, so that impurity metal sulfides (such as zinc sulfide and the like) which are difficult to leach are converted into soluble compounds through chemical reaction, and the purpose of deeply removing metal impurities is achieved. The special impurity removal regulator adopted by the invention comprises ferric sulfate, sodium chloride and ammonium chloride, wherein the ferric sulfate mainly provides iron ions for inducing insoluble metal sulfides such as zinc sulfide and the like to form soluble zinc salts, and the sodium chloride and the ammonium chloride mainly provide chloride ions and ammonium ions, which play a role in promoting the reaction between the iron ions and the insoluble metal sulfides and synergistically accelerate the process.
As a preferable scheme, the metal sulfur slag is ground to a particle size of less than or equal to 106 mu m. The metal sulfur slag is ground to proper granularity, which is beneficial to the dissolution of impurities in the metal sulfur slag.
As a preferable scheme, the solid-liquid mass ratio of the metal sulfur slag slurry is 1:2-1:5, and the ph=1-3. The pH adjustment can be achieved with dilute sulfuric acid.
As a preferable scheme, the aeration adopts a stirring auxiliary blast aeration mode, the stirring speed is 300-700 rpm, and the time is 0.5-2 hours. The temperature is room temperature, for example 20 to 35 ℃. The gas used for aeration is air or other oxygen-containing gas.
As a preferred scheme, the impurity removal regulator comprises the following components in percentage by mass: 20-80% of ferric sulfate, 2-20% of sodium chloride and 10-60% of ammonium chloride. The impurity removal regulator takes ferric sulfate as a main component, mainly provides soluble iron ions, is used for inducing insoluble metal sulfides such as zinc sulfide and the like to form soluble zinc salts, and takes chloride ions and ammonium ions as secondary components to synergistically accelerate the reaction process.
As a preferable scheme, the impurity removal regulating agent is used in an amount of 0.1-0.6M of total concentration of iron ions, chloride ions and ammonium ions in the metal sulfur slag slurry.
As a preferable scheme, the conditions for removing impurities are as follows: at normal temperature, the reaction is carried out for 10 to 24 hours.
As a preferable scheme, in the hot melt filtration process, the melting temperature is 140-150 ℃, the duration is 60-180 min, and the filtration pressure is 0.6-0.8 MPa.
As a preferable embodiment, the metal sulfur slag contains at least one of impurity metal elements such as Fe, zn, pb. More specifically, the content of sulfur element in the metal sulfur slag is more than or equal to 55wt%, the content of zinc element is less than or equal to 10wt%, the content of iron element is less than or equal to 20wt%, and the content of lead element is less than or equal to 3wt%.
As a preferable mode, the washing adopts a multi-stage washing mode, and the washing is carried out until the water washing liquid is neutral. More specific washing processes include: and carrying out suction filtration on the leaching solution, stirring and washing filter residues by using deionized water, and carrying out suction filtration again until the pH value of the filtrate is neutral.
As a preferred embodiment, the dehydration is carried out to a water content of < 10%. More specific dehydration treatments include: and dehydrating the metal sulfur slag subjected to the water washing treatment by using a belt dehydrator so that the water content of the metal sulfur slag is less than 10wt%.
As a preferred scheme, the sulfur liquid is granulated to obtain a sulfur product.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
according to the invention, through carrying out acid washing aeration treatment on the metal sulfur slag and matching with the regulation and control reagent, impurities in the metal sulfur slag can be effectively removed, so that the viscosity reduction of molten metal sulfur slag is realized, and meanwhile, the sulfur separation recovery rate is effectively improved.
The method for preprocessing and strengthening the sulfur by hot melting, filtering and separating the metal sulfur slag has simple operation flow, avoids using toxic reagents and is beneficial to industrialized application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to what is shown in the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for pretreating and strengthening sulfur by hot melting, filtering and separating metal sulfur slag.
FIG. 2 is a graph showing viscosity and separation rate of the multi-metal sulfur slag after pretreatment.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Moreover, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and to which this invention belongs, and any method, apparatus, or material of the prior art similar or equivalent to the methods, apparatus, or materials described in the examples of this invention may be used to practice the invention.
The invention further provides a method for preprocessing and strengthening sulfur by hot melting, filtering and separating metal sulfur slag, which comprises the following steps of:
(1) Crushing and grinding metal sulfur slag, wherein the size of the metal sulfur slag is less than or equal to 106 mu m; the content of sulfur element in the metal sulfur slag is more than or equal to 55wt%; the content of zinc element is less than or equal to 10wt%; the content of iron element is less than or equal to 20wt%; the content of lead element is less than or equal to 3wt%; the size of the multi-metal sulfur slag is less than or equal to 106 mu m, and can be specifically 1.3-106 mu m. It should be noted that the metal sulfur slag may be multi-metal sulfur slag, i.e., metal impurities may be various; the metal impurities can contain heavy metal elements, namely the metal elements in the metal impurities can comprise or be heavy metal elements, and the heavy metal elements can also be various; the heavy metal element can comprise or be one or more of Zn and Pb; of course, the heavy metal elements may include or be other heavy metal elements such as Hg and Cu, and are not specifically listed here.
The sulfur (S) contained in the metal sulfur slag in the invention is expressed as S 8 Form the S element existing, and the existence form of Fe comprises or is FeS 2 The Zn is in the form of ZnS and Pb is in the form of PbSO 4 The method comprises the steps of carrying out a first treatment on the surface of the In addition to the above materials, the metal sulfur slag may generally contain CaSO 4 . The metal sulfur slag comprises the following components in percentage by mass: sulfur (S) is more than or equal to 55 percent, fe is less than or equal to 20 percent, zn is less than or equal to 10 percent, and Pb is less than or equal to 3 percent. Specifically, the S content can be 55% -85%, the Fe content can be 1% -20%, the Zn content can be 1% -10%, and the Pb content can be 0.1% -3%. It is emphasized that due to FeS 2 、ZnS、PbSO 4 、CaSO 4 The S element in the S-containing substance is not present as sulfur, and the S-containing substance may not be contained in the S-containing substance.
(2) Mixing the metal sulfur slag obtained by the treatment in the step (1) with water, wherein the mass ratio of the metal sulfur slag to the water is 1:2-1:5; and dilute sulfuric acid is used for adjusting the pH value to be 1-3;
(3) Stirring (500 rpm) the slurry obtained in the step (2) and carrying out blast aeration for 0.5-2 hours; the environmental temperature of the blast aeration of the metal sulfur slag is 20-35 ℃ and the time is 0.5-2 hours, and the stirring is carried out at the same time, and the speed is 500rpm.
(4) Stopping aeration of the slurry obtained by the treatment in the step (3) under continuous stirring, adding a regulating reagent to prepare a leaching solution, and reacting for 10-24 hours at normal temperature; the regulating and controlling reagent comprises 20-80% of ferric sulfate, 2-20% of sodium chloride and 10-60% of ammonium chloride, wherein the total concentration of iron ions and ammonium ions is 0.1-0.6M;
(5) Filtering the slurry obtained in the step (4) and washing for multiple times until the pH value is neutral, and drying in vacuum until the water content is less than 10%; the water washing treatment is a conventional means, and only the metal sulfur slag needs to be washed to be neutral or close to neutral, and the details are not described herein. The dehydration treatment includes: and dehydrating the metal sulfur slag subjected to the water washing treatment so as to ensure that the water content of the metal sulfur slag is less than 10%.
The method specifically comprises the following steps: filtering and dehydrating the metal sulfur slag after the water washing treatment by a vacuum belt filter, and obtaining dehydrated sulfur slag with the water content less than 10 percent after dehydration.
(6) And (3) heating the metal sulfur slag obtained in the step (5) to 140-150 ℃ for melting, and filtering and separating the molten slag to be separated to obtain separated sulfur liquid, wherein the sulfur liquid contains sulfur.
Wherein the melting temperature can be 140-150 ℃, and the melting time can be 60-180 min
The method specifically comprises the following steps: feeding the dehydrated metal sulfur slag into a crude sulfur melting cyclone through a tape conveyor, wherein the temperature in the crude sulfur melting cyclone is 140-150 ℃, and the heat preservation time in the crude sulfur melting cyclone is 60-180 min so as to completely melt the metal sulfur slag; and after melting, filtering and separating the slag to be separated in a molten state to obtain metal filter residues and separated sulfur liquid, and granulating the sulfur liquid to obtain a sulfur product. The metal filter residue (also called as heavy metal filter residue) contains metal elements (metal impurities) and can also contain other impurities; the sulfur liquid mainly contains sulfur.
The filter diameter of the filter separation can be less than 10 mu m, and can be specifically 1-8 mu m; the filtration and separation can be pressure filtration, namely, in the process of the filtration and separation, the pressure of 0.6-0.8 MPa can be applied to the slag to be separated; in the filtering and separating process, the temperature of the slag to be separated can be kept between 140 and 150 ℃, and the slag can be filtered while the slag is hot.
The filtering and separating the slag to be separated in the molten state specifically comprises the following steps: pumping the slag to be separated in a molten state into a filter press or pumping the slag to be separated into batches; and then, delivering the sulfur liquid (high-purity sulfur liquid) obtained by pressure filtration in a filter press into a granulator for granulating to obtain a sulfur product, and packaging and piling.
It is known that, aiming at the problems of high viscosity of molten metal sulfur slag and low efficiency of hot melting filtration and sulfur recovery, the invention further removes certain metal impurities in the multi-metal sulfur slag through pretreatment, reduces the polymerization degree of sulfur in the molten multi-metal sulfur slag, thereby improving the hot filtration separation recovery rate of sulfur. The method provided by the invention has the advantages of simple process, convenient operation, no need of adding toxic and harmful chemical reagents, and capabilities of improving the recycling rate of sulfur resources in the multi-metal sulfur slag, increasing the economic benefit and reducing the environmental risk brought by the sulfur slag.
Specifically, firstly, crushing and grinding multi-metal sulfur slag, dissolving the crushed multi-metal sulfur slag in deionized water, and adjusting the pH value to be 1-3 by using concentrated sulfuric acid; then stirring (500 rpm) the obtained slurry and blasting aeration for 0.5-2 hours; after aeration is finished, adding a regulating reagent to prepare leaching solution, and reacting for 10-24 hours at normal temperature; filtering the obtained slurry, washing for a plurality of times until the pH value is neutral, and vacuum drying until the water content is less than 10%; and (3) delivering the dehydrated metal sulfur slag into a melting cyclone, maintaining the temperature in the coarse sulfur melting cyclone at 140-150 ℃, and finally filtering and separating the molten slag to be separated, and cooling filtrate or granulating to obtain the high-purity sulfur product.
The technical solutions provided by the present invention are described in detail below with reference to specific embodiments, but they should not be construed as limiting the scope of the present invention.
Example 1
The method for preprocessing and strengthening sulfur by hot melting, filtering and separating metal sulfur slag comprises the following steps:
the multi-metal sulfur slag (main components: 80wt% of S, 3.5wt% of Zn, 4wt% of Fe, 0.35wt% of Pb and 12.15wt% of other materials) is crushed, ground and sieved (200 meshes), deionized water is added into the multi-metal sulfur slag according to a mass ratio of 2:1, and the pH=1.5 is regulated by sulfuric acid. Under the condition of stirring (500 rpm), air is blown and aerated for 1h by an air pump, and then a regulating reagent A (comprising ferric sulfate, sodium chloride and ammonium chloride and Fe is added 3+ Chloride ion and NH 4 + The total concentration is 0.4M, and the components are 70% of ferric sulfate, 10% of sodium chloride and 20% of ammonium chloride in percentage by mass, and the reaction is carried out for 16 hours at normal temperature and normal pressure. Filtering the obtained slurry, washing for multiple times to pH=7, vacuum drying to water content of 8%, feeding the dehydrated metal sulfur slag into a melting cyclone, maintaining the temperature in the coarse sulfur melting cyclone at 150 ℃, preserving the temperature for 30min, and discharging molten sulfur (molten multi-metal sulfur slag) from the bottom of the coarse sulfur cyclone to a coarse sulfur cyclone with stirringIn a sulfur cell, the viscosity was measured to be 1240mpa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6MPa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the embodiment, the purity of sulfur in the sulfur product is 99.51%, the separation recovery rate of sulfur in the multi-metal sulfur slag is 65.70%, and heavy metals in the metal filter slag can be further recovered.
Comparative example 1
In this comparative example, the multi-metal sulfur slag was not pretreated as compared with example 1.
The method comprises the following steps: the multi-metal sulfur slag without any treatment is dried in vacuum until the water content is 8%, and is sent into a melting cyclone, the temperature is kept at 150 ℃ in the coarse sulfur melting cyclone, after the temperature is kept for 30min, the molten sulfur (the multi-metal sulfur slag in the molten state) is discharged from the bottom of the coarse sulfur cyclone into a coarse sulfur pool with stirring, and the viscosity is measured to be 2660mpa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6MPa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the comparative example, the purity of sulfur in the sulfur product was 99.21%, and the sulfur separation recovery rate in the multi-metal sulfur slag was 53%.
Comparative example 2
The comparative example omits the pH adjustment and aeration steps by adding acid during the pretreatment, as compared with example 1.
The method comprises the following steps: crushing, grinding and sieving (200 meshes) multi-metal sulfur slag (main components: 80wt% of S, 3.5wt% of Zn, 4wt% of Fe, 0.35wt% of Pb0.35wt% of other 12.15 wt%) to obtain a powder, adding deionized water into the multi-metal sulfur slag according to a mass ratio of 2:1, and adding a regulating and controlling reagent (comprising ferric sulfate, sodium chloride and ammonium chloride, fe) under the condition of stirring (500 rpm) 3+ Chloride ion and NH 4 + The total concentration is 0.4M, and the components are 70% of ferric sulfate, 10% of sodium chloride and 20% of ammonium chloride in percentage by mass, and the reaction is carried out for 16 hours at normal temperature and normal pressure. Filtered and dried in vacuum until the mixture containsThe water content was 8%, the dehydrated metal sulfur slag was fed into a melting cyclone, the temperature was maintained at 150℃in the crude sulfur melting cyclone, and after 30 minutes of heat preservation, molten sulfur (multi-metal sulfur slag in a molten state) was discharged from the bottom of the crude sulfur cyclone into a crude sulfur tank with stirring, and the viscosity was measured to be 1372mpa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6MPa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the comparative example, the purity of sulfur in the sulfur product is 99.22 percent, the separation recovery rate of sulfur in the multi-metal sulfur slag is 58.4 percent, and the heavy metals in the metal filter slag can be further recovered.
Comparative example 3
In this comparative example, no control reagent was added during pretreatment, as compared with example 1.
The method comprises the following steps: the multi-metal sulfur slag (main components: 80wt% of S, 3.5wt% of Zn, 4wt% of Fe, 0.35wt% of Pb0.15 wt% of other 12.15 wt%) is crushed, ground and sieved (200 meshes), deionized water is added into the multi-metal sulfur slag according to a mass ratio of 2:1, and the pH=1.5 is regulated by sulfuric acid. Under stirring (500 rpm), the slurry obtained was air-blown and aerated for 1 hour by an air pump, filtered and washed several times to ph=7, vacuum-dried to a water content of 8%, the dehydrated metal sulfur slag was fed into a melting cyclone, the temperature was kept at 150 ℃ in the crude sulfur melting cyclone, and after heat preservation for 30 minutes, molten sulfur (multi-metal sulfur slag in a molten state) was discharged from the bottom of the crude sulfur cyclone into a crude sulfur tank with stirring, and the viscosity was measured to be 1410mpa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6MPa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the comparative example, the purity of sulfur in the sulfur product is 99.33 percent, the separation recovery rate of sulfur in the multi-metal sulfur slag is 55.7 percent, and the heavy metals in the metal filter slag can be further recovered.
Comparative example 4
In this comparative example, the control reagent added during pretreatment contained only one of them, as compared with example 1.
The method comprises the following steps: crushing, grinding and sieving (200 meshes) multi-metal sulfur slag (main components: 80wt% of S, 3.5wt% of Zn, 4wt% of Fe, 0.35wt% of Pb0.35wt% of other 12.15 wt%) to obtain a powder, adding deionized water into the multi-metal sulfur slag according to a mass ratio of 2:1, and adding a regulating and controlling reagent (ferric sulfate and Fe) under the condition of stirring (500 rpm) 3 + The concentration is 0.4M, the component proportion is 100% of ferric sulfate by mass fraction, and the reaction is carried out for 16 hours at normal temperature and normal pressure. Filtering and vacuum drying until the water content is 8%, feeding the dehydrated metal sulfur slag into a melting cyclone, keeping the temperature at 150 ℃ in the coarse sulfur melting cyclone, keeping the temperature for 30min, discharging molten sulfur (molten multi-metal sulfur slag) from the bottom of the coarse sulfur cyclone into a coarse sulfur pool with stirring, and measuring the viscosity to 1658mPa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6MPa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the comparative example, the purity of sulfur in the sulfur product is 99.18 percent, the separation recovery rate of sulfur in the multi-metal sulfur slag is 58.89 percent, and the heavy metal in the metal filter slag can be further recovered.
Example 2
The method for preprocessing and strengthening sulfur by hot melting, filtering and separating metal sulfur slag comprises the following steps:
the multi-metal sulfur slag (main components: 82wt% of S, 4.1wt% of Zn, 3.8wt% of Fe, 0.52wt% of Pb and 9.58wt% of other materials) is crushed, ground and sieved (200 meshes), deionized water is added into the multi-metal sulfur slag according to a mass ratio of 2:1, and sulfuric acid is used for adjusting the pH=1.5. Under the condition of stirring (500 rpm), air is blown and aerated for 1h by an air pump, and then a regulating reagent B (comprising ferric sulfate, sodium chloride and ammonium chloride, fe 3+ Chloride ion and NH 4 + The total concentration is 0.3M, and the components are 60% of ferric sulfate, 10% of sodium chloride and 30% of ammonium chloride according to mass fraction, and the reaction is carried out for 16 hours at normal temperature and normal pressure. Filtering the obtained slurry, washing for multiple times to pH=7, vacuum drying to water content of 10%, and delivering dehydrated metal sulfur slag intoThe temperature of the melting cyclone was kept at 150 ℃ in the crude sulfur melting cyclone, and after 30min of heat preservation, molten sulfur (multi-metal sulfur slag in a molten state) was discharged from the bottom of the crude sulfur cyclone into a crude sulfur tank with stirring, and the viscosity thereof was measured as 1160mpa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6Mpa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the embodiment, the purity of sulfur in the sulfur product is 99.43%, the separation recovery rate of sulfur in the multi-metal sulfur slag is 66.1%, and heavy metals in the metal filter slag can be further recovered.
Example 3
The method for preprocessing and strengthening sulfur by hot melting, filtering and separating metal sulfur slag comprises the following steps:
the multi-metal sulfur slag (main components: 77wt% of S, 5.6wt% of Zn, 6.4wt% of Fe, 0.79wt% of Pb and 10.21wt% of other materials) is crushed, ground and sieved (200 meshes), deionized water is added into the multi-metal sulfur slag according to a mass ratio of 2:1, and sulfuric acid is used for adjusting pH=2. Under the condition of stirring (500 rpm), air is blown and aerated for 1h by an air pump, and then a regulating reagent C (comprising ferric sulfate, sodium chloride and ammonium chloride and Fe is added 3+ Chloride ion and NH 4 + The total concentration is 0.5M, and the components are 40% of ferric sulfate, 15% of sodium chloride and 45% of ammonium chloride in percentage by mass, and the reaction is carried out for 16 hours at normal temperature and normal pressure. The slurry obtained was filtered and washed several times to ph=7, dried in vacuo to a water content of 9%, the dehydrated metal sulfur slag was fed into a melting cyclone, the temperature was kept at 150 ℃ in the crude sulfur melting cyclone, and after 30 minutes of heat preservation, molten sulfur (multi-metal sulfur slag in molten state) was discharged from the bottom of the crude sulfur cyclone into a crude sulfur tank with stirring, and its viscosity was measured to be 1221mpa.s. Then pumping molten sulfur slag (slag to be separated in a molten state) into a hot filter (at 150 ℃) for filtering (the pressure is 0.6Mpa, the filtering diameter is 8 mu m) to obtain metal filter residues and high-purity sulfur liquid; granulating and packaging the high-purity sulfur liquid to obtain a sulfur product.
In the embodiment, the purity of the sulfur in the sulfur product is 99.38%, the separation recovery rate of the sulfur in the multi-metal sulfur slag is 64%, and the heavy metals in the metal filter slag can be further recovered.
In the above technical solution of the present invention, the above is only a preferred embodiment of the present invention, and therefore, the patent scope of the present invention is not limited thereto, and all the equivalent structural changes made by the description of the present invention and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present invention.
Claims (9)
1. A method for preprocessing and strengthening sulfur by hot melting, filtering and separating metal sulfur slag is characterized in that: the method comprises the following steps:
1) Crushing and grinding the metal sulfur slag, adding water and acid to carry out slurry mixing to obtain metal sulfur slag slurry;
2) After carrying out aeration treatment on the metal sulfur slag slurry, adding a impurity removal regulating agent to remove impurities to obtain a leaching solution; the impurity removal regulating and controlling agent comprises ferric sulfate, sodium chloride and ammonium chloride;
3) Filtering the leaching solution to separate a solid product, washing and dehydrating the solid product, and separating sulfur liquid through hot melt filtration.
2. The method for preprocessing and strengthening sulfur hot-melt filtration separation by using metallic sulfur slag according to claim 1, which is characterized in that: the metal sulfur slag is ground until the granularity is less than or equal to 106 mu m.
3. The method for preprocessing and strengthening sulfur hot-melt filtration separation by using metallic sulfur slag according to claim 1, which is characterized in that: the solid-liquid mass ratio of the metal sulfur slag slurry is 1:2-1:5, and the pH=1-3.
4. The method for preprocessing and strengthening sulfur hot-melt filtration separation by using metallic sulfur slag according to claim 1, which is characterized in that: the aeration adopts a stirring auxiliary blast aeration mode, the stirring speed is 300-700 rpm, and the aeration time is 0.5-2 hours.
5. The method for preprocessing and strengthening sulfur hot-melt filtration separation by using metallic sulfur slag according to claim 1, which is characterized in that: the impurity removal regulating agent comprises the following components in percentage by mass: 20-80% of ferric sulfate, 2-20% of sodium chloride and 10-60% of ammonium chloride.
6. The method for hot-melt filtration separation of the metal sulfur slag pretreatment-enhanced sulfur according to claim 1 or 5, which is characterized in that: the dosage of the impurity removal regulating agent is measured according to the total concentration of iron ions, chloride ions and ammonium ions in the metal sulfur slag slurry of 0.1-0.6M.
7. The method for hot-melt filtration separation of the metal sulfur slag pretreatment-enhanced sulfur according to claim 1 or 5, which is characterized in that: the conditions for removing impurities are as follows: at normal temperature, the reaction is carried out for 10 to 24 hours.
8. The method for preprocessing and strengthening sulfur hot-melt filtration separation by using metallic sulfur slag according to claim 1, which is characterized in that: in the hot melt filtration process, the melting temperature is 140-150 ℃, the duration is 60-180 min, and the filtration pressure is 0.6-0.8 MPa.
9. The method for pretreating and strengthening sulfur by hot melting, filtering and separating metal sulfur slag according to claim 1, 2, 3, 4, 5 or 8, wherein the method comprises the following steps: the content of sulfur element in the metal sulfur slag is more than or equal to 55wt%, the content of zinc element is less than or equal to 10wt%, the content of iron element is less than or equal to 20wt%, and the content of lead element is less than or equal to 3wt%.
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