CN113122734B - Smelting method for removing fluorine and chlorine from secondary zinc oxide - Google Patents
Smelting method for removing fluorine and chlorine from secondary zinc oxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
The invention provides a smelting method for removing fluorine and chlorine from secondary zinc oxide, which relates to the technical field of metallurgy of nonferrous metals and comprises the following steps: firstly, feeding secondary zinc oxide into a rotary kiln for roasting, collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filtrate; and (3) separating the primary filtrate in four steps, sequentially utilizing sodium hydroxide, sodium carbonate, sodium sulfide, polymeric ferric chloride, ferrous sulfate and calcium hydroxide to continue to react, comprehensively recovering valuable metals in the solution, putting the filtrate into a multi-effect evaporator to concentrate to obtain an industrial salt product, and returning evaporated condensate water for recycling. The method for removing fluorine and chlorine from zinc hypoxide can comprehensively recover various metals, fluorine and chlorine ions, has low energy consumption and low water consumption, achieves no water discharge, and has the effects of environmental protection, high efficiency and rapid impurity removal.
Description
Technical Field
The invention belongs to the technical field of metallurgy of nonferrous metals, and particularly relates to a smelting method for removing fluorine and chlorine from zinc hypoxide.
Background
The chemical composition of the secondary zinc oxide is greatly changed along with different mineral sources, and valuable metals such as zinc, indium, arsenic, antimony, tin, silver, lead, cadmium, germanium, bismuth and the like contained in the secondary zinc oxide have high recovery value, so that the research on comprehensive recovery and utilization of the secondary zinc oxide in the zinc smelting industry is developed, the secondary resources are fully utilized, the environmental protection is facilitated, and the economic value and the social benefit are obvious.
The zinc hypoxide is referred to in the invention as a generalized zinc-containing oxide, and comprises smoke dust produced by roasting zinc-containing smelting waste residues through reduction kilns such as a rotary kiln, a fuming furnace, a blast furnace and the like; dust collection zinc ash and waste steel recycling dust collection through iron ore smelting blast furnace, sintering and other processes; dust collecting zinc ash and the like generated by hot galvanizing and zinc alloy.
Foreign attention is paid to the recycling of the secondary zinc oxide. As early as 1995, the capacity of japan, western europe and usa to treat zinc-containing fumes from steel plants has reached 36.5 ten thousand, 40.5 ten thousand tons/year and 53.3 ten thousand tons/year, respectively; respectively accounting for 73 percent, 87 percent and 97 percent of the total amount of the produced smoke dust, so that the zinc recovery and regeneration are the primary tasks facing the zinc recovery in China.
In recent years, domestic zinc smelting enterprises take zinc hypoxide as a zinc smelting raw material for recycling, but compared with the traditional zinc smelting process adopting zinc concentrate, the zinc smelting process adopting zinc hypoxide has obvious defects, the zinc hypoxide contains fluorine and chlorine elements, and the sources and components are complicated, so that the production process cannot be unified, the production cost is high, and the environmental pollution is great. In the actual production process, the common method for removing fluorine and chlorine from the secondary zinc oxide is to wash the secondary zinc oxide with water and alkali for multiple times, deeply remove chlorine by matching with ion exchange, and then enter the traditional hydrometallurgy process to produce zinc metal, so that the maximum washing fluorine and chlorine ion removal water is produced, and not only is the water consumption per ton of zinc metal huge, but also the sewage treatment and discharge amount are large, and the production cost is high. Meanwhile, the change of fluorine, chlorine and other impurities of the secondary zinc oxide is complex, so that the corresponding impurity removal process is complex, and the uniform treatment process cannot be realized, so that the problems of low production efficiency, high pollution, high investment and technical improvement cost, high metal loss, high energy consumption and the like exist.
The inventor firstly discloses a Chinese patent application with publication number CN103924091A, provides a smelting method for removing fluorine and chlorine from fluorine-and chlorine-containing zinc hypoxide and enriching valuable metals, and can better remove fluorine and chlorine and enrich valuable metals. In order to further save energy consumption, process improvement is also needed, and further cost reduction and capacity improvement are expected.
Disclosure of Invention
In order to solve the technical problems, the invention provides a smelting method for removing fluorine and chlorine from zinc hypoxide, which can reduce the combustion temperature and the combustion time in the roasting process, has the effects of energy saving and environmental protection, and can concentrate the final filtrate by four times of step-by-step defluorination and chlorine recovery treatment and multi-step heavy metal separation to achieve no sewage discharge.
In order to achieve the purpose, the invention provides the following technical scheme:
a smelting method for removing fluorine and chlorine from zinc hypoxide comprises the following steps:
(1) Roasting: feeding the secondary zinc oxide into a rotary kiln, and roasting by adopting high-temperature roasting fuel; the high-temperature roasting fuel comprises any one of natural gas, heavy oil, tar and water gas or the combination of the natural gas, the heavy oil, the tar and the water gas;
(2) Collecting dust: collecting roasting flue gas, spraying water to purify the roasting flue gas by using a spraying system, collecting dust sludge, filtering and squeezing the dust sludge to respectively obtain primary filter sludge and primary filter liquor;
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 5.5-6, reacting at 63-65 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 7.5-8, reacting for a certain time, filtering and squeezing again to obtain third filter mud and third filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polymeric ferric chloride, ferrous sulfate and calcium hydroxide into the third filtrate, adjusting the pH value to 11.5-12, reacting for a certain time, filtering and squeezing again to obtain fourth filter mud and fourth filtrate;
(6) And (4) putting the filtrate of the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensate water can be recycled.
Furthermore, the high-temperature roasting fuel is a combination of heavy oil and tar according to the weight ratio of 1-4:1-2.
Further, the mass ratio of the secondary zinc oxide high-temperature roasting fuel is 3-15.
Furthermore, the roasting temperature is 1100-1150 ℃ and the time is 1.0-1.5 h.
Further, the mass ratio of the sodium sulfide, the polymeric ferric chloride, the ferrous sulfate and the calcium hydroxide is 0.5-1.5: 0.1 to 0.5: 1.
Further, the spraying speed of the spraying system is 250-280 m 3 /h。
Further, the heat value of the high-temperature roasting fuel required by roasting the zinc hypoxide is as follows: gas 8000-12000 cal/m 3 (ii) a The liquid is 8000-12000 cal/kg.
Further, the contents of main elements in the fourth filtrate are as follows: the total zinc is less than or equal to 1.2mg/L, the total lead is less than or equal to 0.05mg/L, the total chlorine is less than or equal to 0.5mg/L, the total fluorine is less than or equal to 0.1mg/L, and the content of other elements is less than 0.01mg/L.
The invention has the following beneficial effects:
1. in the roasting process, natural gas, heavy oil, tar and water gas are used as fuels, so that the secondary zinc oxide can be fully combusted, the combustion temperature and the combustion time are reduced, and the method has the effects of energy conservation and environmental friendliness.
2. After the secondary zinc oxide is roasted, the produced solid residue is zinc-containing oxide containing little fluorine and chlorine, and zinc metal can be directly recycled in all the existing zinc smelting systems; and (3) spraying and recovering the roasted flue gas, wherein substances such as fluorine, chlorine, a small amount of metal impurities, precious metal precipitates and the like contained in the flue gas can be collected, filtering and squeezing are carried out, solid matters in the primary filter mud are recovered, and the fluorine, the chlorine and the small amount of metal impurities contained in the primary filter mud can be continuously recovered and treated.
3. The method comprises the steps of carrying out four times of stepwise recovery treatment on primary filtrate, adjusting the pH to 5.5-6 by using sodium hydroxide for the first time, removing a large amount of lead, tin, silver, indium, iron and bismuth ions in the solution, adding sodium carbonate for continuous reaction, further removing zinc ions in the solution, and simultaneously enriching a small amount of metal impurities in the solution in filter residues for secondary extraction and recovery; adding sodium sulfide, poly ferric chloride, ferrous sulfate and calcium hydroxide into the filtrate step by step to remove arsenic and cadmium impurities, adjusting the pH to 11.5-12, reacting for a certain time, filtering and squeezing again to obtain filter mud for four times and filter liquor for four times; and (4) putting the filtrate obtained in the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensed water can be recycled.
Detailed Description
The present invention will be further described with reference to the following examples. The following raw materials used in the present invention were purchased from chemical raw materials corporation.
Example 1
A smelting method for removing fluorine and chlorine from zinc hypoxide comprises the following steps:
(1) Roasting: feeding the zinc hypoxide into a rotary kiln, roasting by using natural gas, mixing the zinc hypoxide with high-temperature roasting fuel in a mass ratio of 8:1, and roasting at 1100 ℃ for 1.5h;
(2) Collecting dust: collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filter liquor; the spraying speed is 250m 3 /h；
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 5.5, reacting at 63 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 7.5, reacting for a certain time, filtering and squeezing again to obtain tertiary filter mud and tertiary filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polyferric chloride, ferrous sulfate and calcium hydroxide (in a mass ratio of 0.5; and (4) putting the filtrate obtained in the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensed water can be recycled.
According to the method of example 1, the secondary zinc oxide of a certain factory is subjected to defluorination and chlorine smelting, and the experimental raw material secondary zinc oxide contains the chemical components shown in the following table 1.
TABLE 1
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/% | 0.45 | 4.82 | 55.43 | 1.8 | 3.31 | 0.32 | 0.12 | 3.62 |
The solid residue produced after the treatment of example 1 is zinc-containing oxide containing little fluorine and chlorine, and the contents of main elements are shown in the following table 2.
TABLE 2
As can be seen from the data in tables 1 and 2, after the solid residue is treated by the method in the embodiment 1, the content of each element in the finally obtained solid residue is low, the index requirements of zinc oxide-containing raw materials in the traditional zinc smelting process are met, and defluorination and dechlorination are effectively realized.
Example 2
A smelting method for removing fluorine and chlorine from zinc hypoxide comprises the following steps:
(1) Roasting: feeding secondary zinc oxide into a rotary kiln, roasting by adopting heavy oil, mixing the secondary zinc oxide with a high-temperature roasting fuel in a mass ratio of 15;
(2) Collecting dust: collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filter liquor; the spraying speed is 280m 3 /h；
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 6, reacting at 65 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 8, reacting for a certain time, filtering and squeezing again to obtain tertiary filter mud and tertiary filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polyferric chloride, ferrous sulfate and calcium hydroxide (in a mass ratio of 1.5; and (4) putting the filtrate of the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensate water can be recycled.
According to the method of example 2, the secondary zinc oxide of a certain factory is subjected to defluorination and chlorine smelting, and the experimental raw material secondary zinc oxide contains the chemical components shown in the following table 3.
TABLE 3
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/% | 0.44 | 4.84 | 55.13 | 1.6 | 3.32 | 0.28 | 0.13 | 3.60 |
The solid residue produced after the treatment of example 2 is a zinc-containing oxide containing little fluorine and chlorine, and the contents of main elements are shown in the following table 4:
TABLE 4
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/% | 0.01 | 0.04 | 65.5 | 0.1 | 0.1 | 0.25 | 0.14 | 5.11 |
As can be seen from the data in tables 3 and 4, after the solid residue is treated in the embodiment 2 of the invention, the finally obtained solid residue has low content of each element, meets the index requirements of zinc oxide-containing raw materials in the traditional zinc smelting process, and effectively realizes defluorination and dechlorination.
Example 3
A smelting method for removing fluorine and chlorine from zinc hypoxide comprises the following steps:
(1) Roasting: feeding secondary zinc oxide into a rotary kiln, roasting by adopting tar, mixing the secondary zinc oxide with a high-temperature roasting fuel in a mass ratio of 7.5;
(2) Collecting dust: collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filter liquor; the spraying speed is 260m 3 /h；
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 5.7, reacting at the temperature of 64 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 7.6, reacting for a certain time, filtering and squeezing again to obtain tertiary filter mud and tertiary filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polyferric chloride, ferrous sulfate and calcium hydroxide (in a mass ratio of 1 to 0.2; and (4) putting the filtrate of the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensate water can be recycled.
According to the method of example 3, the secondary zinc oxide of a certain factory is subjected to defluorination and chlorine smelting, and the experimental raw material secondary zinc oxide contains the chemical components shown in the following table 5.
TABLE 5
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/%) | 0.47 | 4.88 | 55.37 | 1.7 | 3.35 | 0.26 | 0.11 | 3.58 |
The solid residue produced after the treatment of example 3 is a zinc-containing oxide containing little fluorine and chlorine, and the contents of main elements are shown in the following table 6:
TABLE 6
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/% | 0.01 | 0.03 | 65.9 | 0.4 | 0.2 | 0.24 | 0.12 | 5.07 |
As can be seen from the data in tables 5 and 6, after the solid residue is treated in the embodiment 3 of the invention, the finally obtained solid residue has low content of each element, meets the index requirements of zinc oxide-containing raw materials in the traditional zinc smelting process, and effectively realizes defluorination and dechlorination.
Example 4
A smelting method for removing fluorine and chlorine from zinc hypoxide comprises the following steps:
(1) Roasting: feeding zinc hypoxide into a rotary kiln, roasting by using water gas, mixing the zinc hypoxide with high-temperature roasting fuel in a mass ratio of 3:1, and roasting at the temperature of 1130 ℃ for 1.2 hours;
(2) Collecting dust: collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filter liquor; the spraying speed is 270m 3 /h；
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 5.8, reacting at the temperature of 64 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 7.7, reacting for a certain time, filtering and squeezing again to obtain tertiary filter mud and tertiary filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polymeric ferric chloride, ferrous sulfate and calcium hydroxide (in a mass ratio of 0.5; and (4) putting the filtrate of the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensate water can be recycled.
According to the method of example 4, the secondary zinc oxide of a certain factory is subjected to defluorination and chlorine smelting, and the experimental raw material secondary zinc oxide contains the chemical components shown in the following table 7.
TABLE 7
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/% | 0.47 | 4.81 | 55.26 | 1.9 | 3.35 | 0.36 | 0.17 | 3.59 |
The solid residue produced after the treatment of example 4 is an oxide containing zinc with little fluorine and chlorine, and the content of main elements is shown in the following table 8:
TABLE 8
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/% | 0.01 | 0.04 | 65.8 | 0.4 | 0.1 | 0.27 | 0.12 | 5.09 |
As can be seen from the data in tables 7 and 8, after the solid residue is treated in the embodiment 4 of the invention, the finally obtained solid residue has lower content of each element, meets the index requirements of zinc oxide-containing raw materials in the traditional zinc smelting process, and effectively realizes defluorination and dechlorination.
Example 5
A smelting method for removing fluorine and chlorine from zinc hypoxide comprises the following steps:
(1) Roasting: feeding zinc hypoxide into a rotary kiln, roasting by adopting heavy oil and tar (the mass ratio is 2:1), mixing the zinc hypoxide with high-temperature roasting fuel at the mass ratio of 10;
(2) Collecting dust: collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filter liquor; the spraying speed is 270m 3 /h；
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 5.8, reacting at the temperature of 64 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 7.7, reacting for a certain time, filtering and squeezing again to obtain tertiary filter mud and tertiary filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polyferric chloride, ferrous sulfate and calcium hydroxide (in a mass ratio of 1.5; and (4) putting the filtrate of the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensate water can be recycled.
The method of example 5 was used to perform defluorination and chlorination of crude zinc hypoxide from a factory, and the experimental raw material zinc hypoxide contained the chemical compositions as shown in table 9 below.
TABLE 9
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/%) | 0.47 | 4.95 | 55.72 | 1.6 | 3.38 | 0.31 | 0.15 | 3.68 |
The solid residue produced after the treatment of example 5 is a zinc-containing oxide containing little fluorine and chlorine, and the contents of main elements are shown in the following table 10:
TABLE 10
| Element(s) | F | Cl | Zn | Pb | S | Co | Ni | Fe |
| Content/%) | 0.01 | 0.04 | 65.8 | 0.4 | 0.2 | 0.27 | 0.12 | 5.09 |
As can be seen from the data in tables 9 and 10, after the solid residue is treated in the embodiment 5 of the invention, the finally obtained solid residue has low content of each element, meets the index requirements of zinc oxide-containing raw materials in the traditional zinc smelting process, and effectively realizes defluorination and dechlorination.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made thereto by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should be considered as falling within the scope of the present invention.
Claims (5)
1. A smelting method for removing fluorine and chlorine from zinc hypoxide is characterized by comprising the following steps:
(1) Roasting: feeding the secondary zinc oxide into a rotary kiln, and roasting by adopting high-temperature roasting fuel; the high-temperature roasting fuel comprises any one of natural gas, heavy oil, tar and water gas or the combination of the natural gas, the heavy oil, the tar and the water gas; the mass ratio of the secondary zinc oxide to the high-temperature roasting fuel is 3-15; the roasting temperature is 1100-1150 ℃ and the time is 1.0-1.5 h;
(2) Collecting dust: collecting roasting flue gas, purifying water sprayed by a spraying system, collecting dust mud, filtering and squeezing the dust mud to respectively obtain primary filter mud and primary filter liquor;
(3) Primary recovery: adding sodium hydroxide into the primary filtrate, adjusting the pH to 5.5-6, reacting at 63-65 ℃ for a certain time, filtering and squeezing again to obtain secondary filter mud and secondary filtrate;
(4) Secondary recovery: adding sodium carbonate into the secondary filtrate, adjusting the pH value to 7.5-8, reacting for a certain time, filtering and squeezing again to obtain third filter mud and third filtrate;
(5) And (3) recovering for the third time: adding sodium sulfide, polymeric ferric chloride, ferrous sulfate and calcium hydroxide into the third filtrate, adjusting the pH value to 11.5-12, reacting for a certain time, filtering and squeezing again to obtain fourth filter mud and fourth filtrate; the mass ratio of the sodium sulfide to the polymeric ferric chloride to the ferrous sulfate to the calcium hydroxide is 0.5-1.5: 0.1 to 0.5:1: 10-30;
(6) And (4) putting the filtrate of the fourth time into a multi-effect evaporator for concentration to obtain an industrial salt product, wherein the evaporated condensate water can be recycled.
2. The smelting method of zinc hypoxide defluorination chlorine as claimed in claim 1, wherein said high temperature roasting fuel is a combination of heavy oil and tar in weight ratio of 1-4:1-2.
3. The smelting method of zinc hypoxide defluorination chlorine as claimed in claim 1, wherein the spraying rate of said spraying system is 250-280 m 3 /h。
4. The smelting method for removing fluorine and chlorine from zinc hypoxide according to claim 1, wherein the heat value of the high-temperature roasting fuel required by roasting the zinc hypoxide is as follows: gas 8000-12000 cal/m ethanol; liquid 8000-12000 cal/kg.
5. The smelting method of zinc hypoxide defluorination chlorine as claimed in claim 1, wherein the content of main elements in the four filtrates is as follows: the total zinc is less than or equal to 1.2mg/L, the total lead is less than or equal to 0.05mg/L, the total chlorine is less than or equal to 0.5mg/L, the total fluorine is less than or equal to 0.1mg/L, and the content of other elements is less than 0.01mg/L.
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