CN109019666B - Method and device for removing fluorine, chlorine and organic matters in secondary zinc oxide - Google Patents
Method and device for removing fluorine, chlorine and organic matters in secondary zinc oxide Download PDFInfo
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Abstract
The invention provides a method and a device for removing fluorine, chlorine and organic matters in secondary zinc oxide. Adding concentrated sulfuric acid into zinc hypoxide powder according to the mass ratio of 1:0.8-1.6 for acidification reaction, so that the zinc oxide, the components capable of chemically reacting with the concentrated sulfuric acid and the concentrated sulfuric acid are subjected to chemical reaction to generate corresponding sulfate and hydrogen fluoride and hydrogen chloride gases simultaneously; collecting gas by using alkaline absorption liquid to generate corresponding fluorine salt precipitate and chlorine salt liquid; the sulfate is sent into a roasting device and roasted at the temperature of 930-2And water, and finally obtaining the corresponding oxide with fluorine, chlorine and organic matters removed. Thoroughly remove fluorine, chlorine, realize resource utilization, production efficiency is high, and the energy consumption is low, environmental protection.
Description
Technical Field
The invention relates to the technical field of metallurgy and chemical industry, in particular to a method and equipment for efficiently and thoroughly removing fluorine, chlorine and organic matters in secondary zinc oxide and realizing effective recycling of the fluorine and chlorine.
Background
The main component of the zinc hypoxide is ZnO, and the zinc content is generally 35 to 70 percent. The main sources are as follows: the method is characterized in that zinc-containing dust removal ash smoke dust of a steel plant, lead-zinc ore smelting slag, leaching slag of zinc hydrometallurgy, zinc-containing by-products of copper-tin smelting, lean zinc oxide ore and other products enriched by a rotary kiln are obtained. The main application is as follows: used as raw materials for producing electrolytic zinc, active zinc oxide, zinc sulfate and basic zinc carbonate. Because the secondary zinc oxide source is extensive, and the composition is very complicated, wherein there are: fluorine, chlorine, acid-soluble silicon, organic matter, etc., and some of these components are still quite high in the zinc hypoxide. Due to the existence of fluorine, chlorine, acid-soluble silicon, organic matters and the like, the negative effect on the use is large, and the negative effect is more serious when the content is higher. Therefore, the method has great practical value for reducing the contents of fluorine, chlorine, acid-soluble silicon, organic matters and the like in the zinc hypoxide.
In the prior art, fluorine and chlorine removal in secondary zinc oxide is mainly divided into two categories: firstly, roasting by a fire method and secondly, washing by alkali. Wherein:
first, the fire roasting mainly comprises the roasting in a multi-hearth furnace and the roasting in a rotary kiln. The multi-hearth furnace is mostly used for treating zinc oxide smoke dust of a rotary kiln of an electrolytic zinc plant with low fluorine and chlorine content (lower than 1%), the fluorine and chlorine removal rate of the method is 40% -65%, but the method cannot treat secondary zinc oxide with high fluorine content and high chlorine content; the rotary kiln is mostly used for treating materials with high fluorine and chlorine content, and has a defluorination rate of 60-80% and a dechlorination rate of 50-70%. But the content of fluorine and chlorine in the removed product is still higher (F is more than or equal to 0.1 percent and Cl is more than or equal to 0.3 percent), and the process requirements of electrolytic zinc production cannot be met, because the F is less than or equal to 0.03 percent and the Cl is less than or equal to 0.1 percent in the process of preparing the electrolytic zinc liquid, otherwise, the process for removing fluorine and chlorine is required to be added in the process of preparing the electrolytic zinc liquid. For example, chinese patent CN101649396B discloses a method for efficiently removing F, Cl from secondary zinc oxide soot and producing electrolytic zinc, which adopts a rotary kiln roasting mode, and adds a small amount of sulfuric acid before granulating secondary zinc oxide. The method has five defects: firstly, fluorine and chlorine are not thoroughly removed, the content of fluorine and chlorine in the removed product is still high (F is more than or equal to 0.1 percent, Cl is more than or equal to 0.3 percent), and the process requirements of electrolytic zinc production are difficult to meet; secondly, fluorine and chlorine can not be well recycled as byproducts; thirdly, the higher the fluorine-chlorine content in the secondary zinc oxide is, the lower the direct zinc yield is, a large amount of gaseous zinc chloride can enter tail gas to corrode equipment and cause the equipment to be seriously scaled, and the utilization value of zinc recovered from the tail gas is lower; fourthly, the high-lead zinc hypoxide is difficult to process; and fifthly, the rotary kiln is used as roasting equipment, the problem of environmental pollution is difficult to really solve thoroughly due to the limitation of the working operation mode of the equipment, and particularly, when high fluorine-chlorine and high lead materials are treated, the pollution and the system scaling and corrosion are more serious. For another example, chinese patent CN 104773751 a discloses a method for removing fluorine, chlorine and valuable metals from secondary zinc oxide, which uses a granulation rotary kiln for calcination. The method has three disadvantages: firstly, the removal of fluorine and chlorine is not thorough, and the three disclosed embodiments ensure that the fluorine and chlorine content of the roasted product after treatment still cannot meet the process requirements of electrolytic zinc production, and the fluorine and chlorine need to be further removed in the liquid preparation process; secondly, the higher the fluorine and chlorine in the secondary zinc oxide is, the lower the direct yield of zinc is, a large amount of gaseous zinc chloride enters the tail gas, the corrosion and the scaling are serious, and the value of the zinc collected from the tail gas is greatly devalued; thirdly, the rotary kiln is used as roasting equipment, the problem of environmental pollution is difficult to really solve thoroughly due to the limitation of the working and running mode of the equipment, and particularly, when high fluorine, chlorine and lead materials are treated, the pollution is serious, and the system is seriously scaled and corroded.
The above pyro-roasting has the common disadvantages that:
1. the removal of fluorine and chlorine is not thorough enough and can not meet the requirements of the electrolytic zinc production process.
2. Fluorine and chlorine enter tail gas smoke dust in a high-temperature volatilization mode of lead and zinc salts of the fluorine and chlorine, the components are complex, and the fluorine and chlorine are difficult to be effectively recycled.
3. The problem of environmental pollution is difficult to really solve completely, especially when high fluorine chlorine and high lead zinc hypoxide are treated.
Secondly, the fluorine and chlorine are removed by an alkali washing method, only the fluorine and chlorine in the water-soluble fluorine and chlorine salt can be removed, and the high fluorine and chlorine secondary zinc oxide material after alkali washing treatment still has high fluorine content of 0.1-0.3 percent and chlorine content of 0.3-0.6 percent and cannot meet the requirements of electrolytic zinc production process.
The alkaline washing method has the following disadvantages:
1. the removal of fluorine and chlorine is not thorough enough, the requirements of electrolytic zinc production process cannot be met, and the fluorine and chlorine are further removed in the liquid preparation process;
2. the fluorine and the chlorine are not recycled;
3. the content of Na and K in the zinc material after alkali washing is high, and negative influence is caused due to accumulation in an electrolytic zinc production system.
4. A large amount of washed concentrated brine neutralized by acid waste liquid of a factory is evaporated and concentrated to obtain salt, the components of the salt are very complex and difficult to utilize, and the salt is piled up in a factory to form a hill, which becomes a new environmental protection problem.
In addition, chinese patent CN 104593586A discloses a method for removing fluorine and chlorine from zinc oxide smoke by microwave low-temperature roasting and alkali washing, which adds microwave low-temperature activation before alkali washing, although the effect of removing fluorine and chlorine is slightly better than that of removing fluorine and chlorine by pure alkali washing, but still belongs to alkali washing, and still has a plurality of defects of alkali washing, and the chlorine content of the material before treatment disclosed in the third embodiment is only 2.4% and is not high, while the chlorine content in most of zinc hypoxide on the market is more than 6%, the fluorine content in the treated material is 0.088% and the chlorine content in the treated material is 0.14%, which cannot meet the requirements of electrolytic zinc production process, and further remove fluorine and chlorine in the process of liquid preparation.
Therefore, there is a need for improvements in the prior art.
Disclosure of Invention
In order to solve the problems of the removal of fluorine and chlorine by the pyrogenic roasting and alkaline washing methods, in particular to a hypozinc oxide raw material with high fluorine and chlorine content (fluorine + chlorine is more than or equal to 6%) and ultrahigh fluorine and chlorine content (fluorine + chlorine is more than or equal to 15%), the invention solves the problems from two aspects of a removal method and matched equipment.
The invention provides a method for removing fluorine, chlorine and organic matters in secondary zinc oxide, which is characterized by comprising the following steps:
A. adding concentrated sulfuric acid into zinc hypoxide powder according to the mass ratio of 1:0.8-1.6 for acidification reaction, so that the zinc oxide, the components capable of chemically reacting with the concentrated sulfuric acid and the concentrated sulfuric acid are subjected to chemical reaction to generate corresponding sulfate and hydrogen fluoride and hydrogen chloride gases simultaneously;
B. introducing hydrogen fluoride and hydrogen chloride gas into alkaline absorption liquid with the mass concentration of 20-30% to generate corresponding fluorine salt precipitate and chlorine salt liquid, and filtering and separating to obtain the fluorine salt precipitate and the chlorine salt liquid;
C. b, conveying the sulfate obtained in the step A into a roasting device, conveying natural gas or liquefied gas fuel into the roasting device, roasting the sulfate at the temperature of 930 ℃ plus 1200 ℃ formed by fuel combustion, so that main zinc sulfate, iron sulfate and lead sulfate in the sulfate are thermally decomposed, and organic matters in the sulfate are oxidized into CO2And water, finally obtaining the corresponding oxide with fluorine, chlorine and organic matters removed;
D. and C, conveying the gas containing sulfur trioxide generated in the roasting process in the step C into a sulfuric acid absorption tower, conveying concentrated sulfuric acid into the sulfuric acid absorption tower, enabling the concentrated sulfuric acid after absorbing the sulfur trioxide to become fuming sulfuric acid, diluting to obtain the concentrated sulfuric acid, returning to the acidification reaction in the step A for recycling, washing tail gas with water to obtain dilute sulfuric acid, using the dilute sulfuric acid to dilute the fuming sulfuric acid to prepare the concentrated sulfuric acid, and absorbing the tail gas after washing with lime milk and then discharging.
And the alkaline absorption liquid in the step B is alkali or alkaline oxide, preferably one or more of calcium aluminate slurry, lime milk, alumina, magnesia, caustic soda and lime milk, and is used for respectively generating corresponding fluorine salt precipitate and chlorine salt liquid after reacting with hydrogen fluoride and hydrogen chloride gas generated in the introduced acidification reaction process, so as to realize the separation of fluorine and chlorine.
And B, washing, dehydrating and drying the fluoride salt precipitate obtained in the step B in a conventional manner to obtain a fluoride product, and returning the generated water to the alkaline absorption liquid in the step B.
And B, performing conventional curing treatment and drying on the chloride liquid obtained in the step B to obtain polyaluminium chloride or other chloride products.
And D, cooling the oxide obtained in the step C to obtain the treated zinc calcine.
The sulfuric acid absorption tower of the step D is conventional equipment.
And the roasting device in the step C is conventional equipment.
The roasting device of the step C is preferably the following device: including one and have the feed inlet on it, the gas vent, the fuel inlet, the horizontal barrel of bin outlet, the rotatory horizontal axis of setting on horizontal barrel axis, the interval sets up on rotatory horizontal axis, and with a plurality of connecting rods of rotatory horizontal axis vertically, set up the shovel flitch at a plurality of connecting rod both ends respectively, dislocation set on the circumferencial direction between the shovel flitch at adjacent connecting rod and both ends, and each shovel flitch is established to the hang plate, so that after the material gets into horizontal barrel, when carrying out the calcination under the high temperature gas effect, shovel flitch through a plurality of slopes is along with the rotation of rotatory horizontal axis, the solid material propelling movement after the calcination discharges to the bin outlet, sulfur trioxide gas that the calcination in-process produced is through the gas vent, the blast pipe that links to each other with the gas vent, send into in the sulfuric acid absorption tower that links to each other with the.
The horizontal cylinder body comprises an outer metal cylinder, and a heat preservation layer, a fire-resistant layer and a high-temperature and acid corrosion resistant layer which are sequentially arranged on the inner wall of the metal cylinder, so that the cylinder body has the functions of heat preservation, fire resistance, high-temperature resistance and acid corrosion resistance in the high-temperature roasting process.
The heat-insulating layer is made of the following materials: rock wool, aluminum silicate fiber cotton, aluminum chlorate fiber cotton and expanded perlite powder; the refractory layer is made of the following materials: high-alumina bricks, magnesium-chromium refractory bricks and clay refractory bricks; the high-temperature and acid corrosion resistant layer is made of the following materials: one or more of corundum, silicon carbide and high-silicon cast stone.
The inclination angle of the shoveling plate is 2-5 degrees, and the shoveling plate is used for single-furnace roasting with single inlet and single outlet; when the temperature is more than 5-20 ℃, the method is used for continuous roasting with continuous feeding and continuous discharging.
The shovel flitch is established to the arc, and the work pot head of this arc is equipped with the arc pottery shovel, makes the work end of shovel flitch have fire-resistant, high temperature resistant, acidproof effect of corroding.
A material baffle plate is arranged on the horizontal cylinder body at the position of the discharge opening, is a semi-circular arc plate and is fixed on the horizontal cylinder body for stopping the material and prolonging the roasting time,
the lower end of the striker plate is provided with a through hole, the through hole is provided with a plug cover which is adaptive to the shape and size of the through hole, the outer end of the plug cover is provided with a push-pull rod, and the outer end of the push-pull rod penetrates through the wall of the corresponding horizontal cylinder body to extend outwards and then is connected with a handle, so that the plug cover can be opened as required to clean roasted materials.
Two ends of the rotating horizontal shaft are fixed at two ends of the horizontal cylinder body through bearings and bearing seats respectively, one end of the rotating horizontal shaft extends outwards to be connected with the speed reducer and the power machine, so that the rotating horizontal shaft is driven by the power machine to rotate, the connecting rod and the shoveling plates at two ends of the connecting rod rotate along with the rotating horizontal shaft to shovel materials and mix the materials, and roasting of the materials is completed efficiently.
The corresponding main chemical reactions in the acidification process of the step A are as follows:
MX2+ H2SO4= MSO4+ 2HX↑
2AX + H2SO4= A2SO4+ 2HX↑
MSiO3+ H2SO4= MSO4+ H2SiO3
A2SiO3+ H2SO4=A2SO4+ H2SiO3
m represents: pb, Zn, etc. +2 valent elements; a represents: K. na and the like + 1-valent elements;
x represents: F. and (4) Cl.
In the process of alkaline absorption of hydrogen fluoride and hydrogen chloride gas in the step B, the following chemical reactions occur:
mCaO·nAl2O3+xHCl=yCaCl2+ zAlCl3+ wH2O
mCaO·nAl2O3+xHF=yCaF2↓+ zAlF3↓ + wH2O
Ca Cl2+ 2HF=CaF2↓ +H2O
AlCl3+3 HF=AlF3↓ +3HCl
the corresponding main chemical reactions in the roasting process of the step C are as follows:
ZnSO4= ZnO + SO3↑
PbSO4= PbO + SO3↑
Fe2(SO4)3= Fe2O3+ 3SO3↑
H2SiO3=SiO2+ H2O↑
HnCm+ xO2= yH2O ↑+ zCO2↑
the method provided by the invention has the following advantages:
1. the method can efficiently and thoroughly remove fluorine and chlorine, and even if the ultrahigh fluorine-chlorine zinc hypoxide is treated, the F content in the material is less than or equal to 0.03 percent and the Cl content in the material is less than or equal to 0.1 percent, so that the requirements of electrolytic zinc production processes are completely met, which cannot be met by any other conventional method;
2. the removed fluorine and chlorine are effectively separated, resource utilization is realized, and the harm is really changed into the benefit;
3. the direct yield of zinc is more than or equal to 98 percent, and no loss exists;
4. the production process is environment-friendly and green, no toxic or harmful gas is discharged, and the environmental protection problem is solved;
5. oxidizing organic matters in the secondary zinc oxide to prevent zinc electrodeposition and burning caused by the organic matters;
6. high-efficiency utilization of energy and cyclic utilization of sulfuric acid.
Generally, the industrial production can be formed by multistage cascade connection of the roasting devices, continuous feeding and continuous discharging are realized, the production efficiency is high, and the energy consumption is low.
The roasting device provided by the invention has the following advantages and effects:
1) the heat utilization rate is high, the contact area of the materials and the high-temperature gas is large, the heat exchange is sufficient, and particularly after the materials are serially connected into a multi-stage working device, the heat utilization rate is obviously improved compared with that of a rotary kiln and a multi-hearth furnace;
2) for treating high-lead secondary zinc oxide, the normal operation of equipment is influenced by the scaling phenomenon easily generated in a rotary kiln and a multi-hearth furnace, but the normal operation of the equipment cannot be influenced by scaling due to the arrangement of a plurality of groups of rotary shoveling plates of the roasting device disclosed by the invention;
3) the equipment investment is low and is only 50-60% of that of a multi-hearth furnace;
4) the power consumption is lower than that of the rotary kiln and is only 30-40 percent of that of the rotary kiln;
5) the device has good sealing performance, is easy to realize negative pressure operation, and has important significance for capturing tail gas and preventing untreated tail gas from leaking to pollute the environment.
In the exhaust gas of the roasting device of the method, the smoke content is very low because: 1) the materials after acid mixing have certain viscosity and cannot fly upwards in the roasting process, and 2) most of volatile lead-zinc halides at the temperature of 1000 ℃ in the secondary zinc oxide are acidified by concentrated sulfuric acid to become non-volatile sulfate and cannot volatilize to enter roasting tail gas, so that the direct recovery rate of zinc is very high, and the tail gas smoke dust is very little. The tail gas can be collected by the smoke without a dust removal device (of course, the dust removal device can be arranged), the smoke in the tail gas can enter the sulfuric acid in the sulfuric acid absorption tower, and the smoke is pumped back to the mixed acid process no matter in an ionic state or a precipitation state, so that the smoke is not lost. Therefore, the metal recovery rate is very high with almost no loss.
And after the gas generated by roasting is discharged, the gas is extracted by a corrosion-resistant and high-temperature-resistant exhaust fan, is mixed with cold air and cooled to a sulfur trioxide absorption tower, and is prepared into concentrated sulfuric acid for recycling. The tail gas of the absorption tower is subjected to primary washing (washing water is used for preparing concentrated sulfuric acid), is absorbed by primary lime milk, and is discharged after secondary washing. The discharged gas completely reaches the national discharge standard.
The residual zinc sulfate, lead sulfate, ferric sulfate and sulfate which are not decomposed completely by heat in the roasting process, and the sulfate which is not decomposed completely by heat under the roasting condition, the sulfuric acid consumed in the acid mixing process can not be recycled by heat decomposition, but the acid consumption of the material for producing electrolytic zinc can not be increased, because the sulfuric acid is already sulfate and the acid is not consumed in the leaching process, which is equivalent to that the part of the acid consumption of the leaching process is advanced to the roasting process.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic structural view of a roasting apparatus according to the present invention;
FIG. 3 is a view taken from the side A of FIG. 2;
FIG. 4 is a block diagram of the scraper plate of FIG. 2;
fig. 5 is a right side view of fig. 4.
Detailed Description
The invention is further illustrated by the following examples in connection with the accompanying drawings.
Example 1
The roasting device provided by the invention comprises: the device comprises a horizontal cylinder 4 with a feeding port 2, an exhaust port 3, a fuel feeding port 12 and a discharging port 16, a rotating horizontal shaft 8 arranged on the central axis of the horizontal cylinder 4, five connecting rods 10 which are arranged on the rotating horizontal shaft 8 at intervals and are vertical to the rotating horizontal shaft 8, shoveling plates 9 respectively arranged at two ends of the five connecting rods 10, wherein adjacent connecting rods 10 and shoveling plates 9 at two ends of the adjacent connecting rods are arranged in a staggered manner in the circumferential direction, and each shoveling plate 9 is arranged as an inclined plate; the horizontal cylinder body 4 comprises an outer-layer metal cylinder, and an insulating layer 5, a fire-resistant layer 6 and a high-temperature and acid-corrosion resistant layer 7 which are sequentially arranged on the inner wall of the metal cylinder, so that the horizontal cylinder body 4 has the functions of heat insulation, fire resistance, high-temperature resistance and acid-corrosion resistance in the high-temperature roasting process; the heat-insulating layer is made of the following materials: rock wool, aluminum silicate fiber cotton, aluminum chlorate fiber cotton salt and expanded perlite powder; the refractory layer is made of the following materials: high-alumina bricks, magnesium-chromium refractory bricks and clay refractory bricks; the high-temperature and acid corrosion resistant layer is made of the following materials: one or more of corundum, silicon carbide and high-silicon cast stone; the inclination angle of the shoveling plate 9 is more than 5-20 degrees, and the shoveling plate is used for continuous feeding, continuous discharging and continuous roasting; obviously, the temperature can also be 2-5 degrees and is used for single-furnace roasting with single inlet and single outlet; the shoveling plate 9 is sleeved with an arc-shaped ceramic shoveling plate 18, so that the working end of the shoveling plate 9 has the functions of fire resistance, high temperature resistance and acid corrosion resistance; a material baffle plate 11 is arranged on the horizontal cylinder 4 at the discharge port 16, and the material baffle plate 11 is a semi-circular arc plate and is fixed on the horizontal cylinder 4 for stopping materials and prolonging the roasting time; the lower end of the striker plate 11 is provided with a through hole, the through hole is provided with a blocking cover 17 which is adaptive to the shape and size of the through hole, the outer end of the blocking cover 17 is provided with a push-pull rod 15, the outer end of the push-pull rod 15 penetrates through the wall of the corresponding horizontal cylinder 4 and extends outwards and then is connected with a handle 14, so that the blocking cover 17 can be opened as required to clean roasted materials; two ends of the rotating horizontal shaft 8 are respectively fixed at two ends of the horizontal cylinder 4 through bearings and bearing seats 13, wherein the left end extends outwards to be connected with the speed reducer and the power machine 1, so that the rotating horizontal shaft 8 is driven by the power machine 1 to rotate, and the connecting rod 10 and the shoveling plates 9 at two ends of the connecting rod rotate along with the rotating horizontal shaft to shovel and mix materials, and roasting of the materials is efficiently completed.
The whole material of the device is preferably prepared from conventional alloy materials or ceramic materials with high temperature resistance and corrosion resistance.
Example 2
The method for removing fluorine, chlorine and organic matters in the secondary zinc oxide provided by the invention comprises the following steps:
the zinc suboxide is taken from a company of Dali of Yunnan as a raw material, and the components are shown in Table 1.
Table 1 units: wt.%
A. Adding concentrated sulfuric acid into the zinc hypoxide powder according to the mass ratio of 1:0.8 to carry out an acidification reaction, so that the zinc hypoxide and components capable of carrying out a chemical reaction with the concentrated sulfuric acid generate corresponding sulfates, and hydrogen fluoride and hydrogen chloride gas are generated at the same time;
B. introducing hydrogen fluoride and hydrogen chloride gas into 20 mass percent calcium aluminate slurry to generate corresponding calcium fluoride precipitate and aluminum chloride liquid, and filtering and separating to obtain the calcium fluoride precipitate and the aluminum chloride liquid; the calcium fluoride precipitate is washed, dehydrated and dried conventionally to obtain a calcium fluoride product, and the generated water is returned to the calcium aluminate serous fluid; after the aluminum chloride liquid is subjected to conventional curing treatment and drying, a polyaluminum chloride product is obtained;
C. b, conveying the sulfate obtained in the step A into a roasting device, simultaneously conveying natural gas fuel into the roasting device, roasting the sulfate at 930 ℃ formed by fuel combustion and under countercurrent fluidization, so that main zinc sulfate, iron sulfate and lead sulfate in the sulfate are thermally decomposed, and organic matters in the sulfate are oxidized into CO2And water, finally obtaining the corresponding oxide with fluorine, chlorine and organic matters removed, and cooling to obtain the treated zinc calcine;
D. and C, conveying the gas containing sulfur trioxide generated in the roasting process in the step C into a conventional sulfuric acid absorption tower, conveying sulfuric acid into the sulfuric acid absorption tower, generating gas and liquid fuming sulfuric acid after the gas is absorbed by the conventional sulfuric acid, diluting the liquid to prepare concentrated sulfuric acid, returning the concentrated sulfuric acid to the acidification reaction in the step A for recycling, washing the gas with water to obtain dilute sulfuric acid, using the dilute sulfuric acid to dilute the fuming sulfuric acid, and washing the tail gas with water with lime emulsion to discharge.
The calcine composition obtained is shown in Table 2.
Table 2 units: wt.%
Example 3
Zinc suboxide from some old Yunnan company is used as raw material, and the components are shown in Table 3.
Table 3 units: wt.%
The method for removing fluorine, chlorine and organic matters in the secondary zinc oxide provided by the invention comprises the following steps:
A. adding concentrated sulfuric acid into the zinc hypoxide powder according to the mass ratio of 1: 1.6 to carry out an acidification reaction, so that the zinc hypoxide and components capable of carrying out a chemical reaction with the concentrated sulfuric acid generate corresponding sulfates, and hydrogen fluoride and hydrogen chloride gas are generated at the same time;
B. introducing hydrogen fluoride and hydrogen chloride gas into lime milk with the mass concentration of 30% to generate corresponding calcium fluoride precipitate and calcium chloride liquid, and filtering and separating to obtain the calcium fluoride precipitate and the calcium chloride liquid; the calcium fluoride precipitate is washed, dehydrated and dried conventionally to obtain a calcium fluoride product, and the generated water is returned to prepare lime emulsion; conventionally concentrating and drying the calcium chloride liquid to obtain a calcium chloride product;
C. b, conveying the sulfate obtained in the step A into a roasting device, conveying natural gas or liquefied gas fuel into the roasting device, roasting the sulfate at 1200 ℃ formed by fuel combustion and under countercurrent fluidization, so that main zinc sulfate, iron sulfate and lead sulfate in the sulfate are thermally decomposed, and organic matters in the sulfate are oxidized into CO2And water, finally obtaining the corresponding oxide with fluorine, chlorine and organic matters removed, and cooling to obtain the treated zinc calcine;
D. and C, conveying the gas containing sulfur trioxide generated in the roasting process in the step C into a conventional sulfuric acid absorption tower, conveying sulfuric acid into the sulfuric acid absorption tower, generating gas and liquid fuming sulfuric acid after the gas is absorbed by the conventional sulfuric acid, diluting the liquid to prepare concentrated sulfuric acid, returning the concentrated sulfuric acid to the acidification reaction in the step A for recycling, washing the gas with water to obtain dilute sulfuric acid, using the dilute sulfuric acid to dilute the fuming sulfuric acid, and washing the tail gas with water with lime emulsion to discharge.
The calcine composition obtained is shown in Table 4.
Table 4 units: wt.%
Example 4
The raw materials are mixed by taking a secondary zinc oxide from a certain company of Ji Chi of Hunan, a secondary zinc oxide from a certain company of Qujing of Yunnan and ultrahigh fluorine chlorine secondary zinc oxide from a certain company of river basin of Guangxi, and the components are shown in Table 5.
Table 5 units: wt.%
The method for removing fluorine, chlorine and organic matters in the secondary zinc oxide provided by the invention comprises the following steps:
A. adding concentrated sulfuric acid into the zinc hypoxide powder according to the mass ratio of 1: 1 to carry out an acidification reaction, so that the zinc hypoxide and components capable of carrying out a chemical reaction with the concentrated sulfuric acid generate corresponding sulfates, and hydrogen fluoride and hydrogen chloride gas are generated at the same time;
B. introducing hydrogen fluoride and hydrogen chloride gas into 25 mass percent calcium aluminate slurry to generate corresponding calcium fluoride precipitate and aluminum chloride liquid, and filtering and separating to obtain the calcium fluoride precipitate and the aluminum chloride liquid; the calcium fluoride precipitate is washed, dehydrated and dried conventionally to obtain a calcium fluoride product, and the generated water is returned to the calcium aluminate serous fluid; after the aluminum chloride liquid is subjected to conventional curing treatment and drying, a polyaluminum chloride product is obtained;
C. b, conveying the sulfate obtained in the step A into a roasting device, conveying natural gas or liquefied gas fuel into the roasting device, roasting the sulfate at 1100 ℃ formed by fuel combustion and under countercurrent fluidization, so that main zinc sulfate, iron sulfate and lead sulfate in the sulfate are thermally decomposed, and organic matters in the sulfate are oxidized into CO2And water, finally obtaining the corresponding oxide with fluorine, chlorine and organic matters removed, and cooling to obtain the treated zinc calcine;
D. and C, conveying the gas containing sulfur trioxide generated in the roasting process in the step C into a conventional sulfuric acid absorption tower, conveying sulfuric acid into the sulfuric acid absorption tower, generating gas and liquid fuming sulfuric acid after the gas is absorbed by the conventional sulfuric acid, diluting the liquid to prepare concentrated sulfuric acid, returning the concentrated sulfuric acid to the acidification reaction in the step A for recycling, washing the gas with water to obtain dilute sulfuric acid, using the dilute sulfuric acid to dilute the fuming sulfuric acid to prepare the concentrated sulfuric acid, and washing tail gas with the water to be washed with lime emulsion and then discharged.
The ingredients of the obtained calcine are shown in Table 6.
Table 6 units: wt.%
Claims (9)
1. The method for removing fluorine, chlorine and organic matters in the secondary zinc oxide is characterized by comprising the following steps:
A. adding concentrated sulfuric acid into zinc hypoxide powder according to the mass ratio of 1:0.8-1.6 for acidification reaction, so that the zinc oxide, the components capable of chemically reacting with the concentrated sulfuric acid and the concentrated sulfuric acid are subjected to chemical reaction to generate corresponding sulfate and hydrogen fluoride and hydrogen chloride gases simultaneously;
B. introducing hydrogen fluoride and hydrogen chloride gas into alkaline absorption liquid with the mass concentration of 20-30% to generate corresponding fluorine salt precipitate and chlorine salt liquid, and filtering and separating to obtain the fluorine salt precipitate and the chlorine salt liquid;
C. b, conveying the sulfate obtained in the step A into a roasting device, conveying natural gas or liquefied gas fuel into the roasting device, roasting the sulfate at the temperature of 930 ℃ plus 1200 ℃ formed by fuel combustion, so that main zinc sulfate, iron sulfate and lead sulfate in the sulfate are thermally decomposed, and organic matters in the sulfate are oxidized into CO2And water, finally obtaining the corresponding oxide with fluorine, chlorine and organic matters removed;
the roasting device comprises a horizontal cylinder body with a feed inlet, an exhaust outlet, a fuel feed inlet and a discharge outlet, a rotating horizontal shaft is arranged on the central axis of the horizontal cylinder, a plurality of connecting rods which are arranged on the rotating horizontal shaft at intervals and are vertical to the rotating horizontal shaft, shoveling plates which are respectively arranged at the two ends of the plurality of connecting rods, adjacent connecting rods and shoveling plates at the two ends of the adjacent connecting rods are arranged in a staggered way in the circumferential direction, each shoveling plate is arranged as an inclined plate, so that after materials enter the horizontal cylinder, when roasting is carried out under the action of high-temperature fuel gas, a plurality of inclined shovel plates rotate along with a rotating horizontal shaft, roasted solid materials are pushed to a discharge port to be discharged, sulfur trioxide gas generated in the roasting process is sent into a sulfuric acid absorption tower connected with the exhaust pipe through the exhaust port and an exhaust pipe connected with the exhaust port, and the preparation of sulfuric acid is completed;
D. and C, conveying the gas containing sulfur trioxide generated in the roasting process in the step C into a sulfuric acid absorption tower, conveying concentrated sulfuric acid into the sulfuric acid absorption tower, enabling the concentrated sulfuric acid after absorbing the sulfur trioxide to become fuming sulfuric acid, diluting to obtain the concentrated sulfuric acid, returning to the acidification reaction in the step A for recycling, washing tail gas with water to obtain dilute sulfuric acid, using the dilute sulfuric acid to dilute the fuming sulfuric acid to prepare the concentrated sulfuric acid, and absorbing the tail gas after washing with lime milk and then discharging.
2. The method according to claim 1, wherein the alkaline absorption liquid in step B is one or more of alkali or alkaline oxide, i.e. calcium aluminate slurry, lime milk, alumina, magnesia, caustic soda + lime milk, and is used for reacting with hydrogen fluoride and hydrogen chloride gas generated in the introduced acidification reaction process to respectively generate corresponding fluorine salt precipitate and chlorine salt liquid, thereby realizing the separation of fluorine and chlorine.
3. The method according to claim 1, wherein the fluoride salt precipitate obtained in step B is subjected to conventional washing, dehydration and drying to obtain a fluoride product, and the produced water is returned to the alkaline absorption solution in step B.
4. The method of claim 1, wherein the chloride solution obtained in step B is subjected to conventional aging treatment and drying to obtain polyaluminum chloride or other chloride products; and D, cooling the oxide obtained in the step C to obtain the treated zinc calcine.
5. The process according to claim 1, characterized in that the sulfuric acid absorption column of step D is a conventional plant; and the roasting device in the step C is conventional equipment.
6. The method as claimed in claim 1, wherein the horizontal cylinder comprises an outer metal cylinder, and an insulating layer, a fire-resistant layer and a high temperature and acid corrosion resistant layer sequentially arranged on the inner wall of the metal cylinder, so that the cylinder has the functions of insulating heat, fire resistance, high temperature and acid corrosion resistance during the high temperature roasting process; the heat-insulating layer is made of the following materials: one or more of rock wool, aluminum silicate fiber cotton, aluminum chlorate fiber cotton and expanded perlite powder; the refractory layer is made of the following materials: one or more of high-alumina bricks, magnesium-chromium refractory bricks and clay refractory bricks; the high-temperature and acid corrosion resistant layer is made of the following materials: one or more of corundum, silicon carbide and high-silicon cast stone.
7. The method according to claim 1, wherein the angle of inclination of the shoveling plate is 2-5 ° for single-in, single-out single-furnace roasting; when the inclination angle of the shoveling plate is more than 5 degrees, the shoveling plate is used for continuous roasting of continuous feeding and continuous discharging; the shovel flitch is established to the arc, and the work pot head of this arc is equipped with the arc pottery shovel, makes the work end of shovel flitch have fire-resistant, high temperature resistant, acidproof effect of corroding.
8. The method as claimed in claim 1, wherein a material baffle plate is arranged on the horizontal cylinder body at the discharge opening, and the material baffle plate is a semi-circular arc plate and is fixed on the horizontal cylinder body for stopping materials and prolonging the roasting time; the lower end of the striker plate is provided with a through hole, the through hole is provided with a plug cover which is adaptive to the shape and size of the through hole, the outer end of the plug cover is provided with a push-pull rod, and the outer end of the push-pull rod penetrates through the wall of the corresponding horizontal cylinder body to extend outwards and then is connected with a handle, so that the plug cover can be opened as required to clean roasted materials.
9. The method as claimed in claim 1, wherein two ends of the horizontal rotating shaft are fixed to two ends of the horizontal cylinder through bearings and bearing seats, respectively, and one end of the horizontal rotating shaft extends outward and is connected to the speed reducer and the power machine, so that the horizontal rotating shaft is rotated by the power machine, and the connecting rod and the shoveling plates at the two ends of the connecting rod rotate accordingly to shovel and mix the materials, thereby efficiently completing the roasting of the materials.
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