CN118619220B - System and method for producing yellow phosphorus by smelting phosphorite - Google Patents
System and method for producing yellow phosphorus by smelting phosphorite Download PDFInfo
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Abstract
本发明公开了一种磷矿熔炼生产黄磷的系统和方法，其中，一种磷矿熔炼生产黄磷的方法，包括：获取液态高磷渣，向液态高磷渣中加入还原剂进行还原获得含磷烟气，含磷烟气冷凝获取黄磷；所述液态高磷渣的获取在氧化熔炼炉中进行，所述还原剂的添加以及黄磷的获取在还原炉中进行；液态高磷渣的获取过程为：将磷矿石、造渣熔剂混合后获得酸度系数0.65~0.85的混合物料，混合物料在氧化熔炼炉中进行氧化熔炼获得熔融的液态高磷渣。本发明提高了磷矿源的忍耐度并拓宽利用边界，实现了连续热法熔炼生产黄磷目的，大幅降低黄磷冶炼单位能耗，降低泥磷产量，降低烟气中酸性气相组分提高收磷尾气的利用率，降低生产成本。
The invention discloses a system and method for producing yellow phosphorus by smelting phosphate ore, wherein a method for producing yellow phosphorus by smelting phosphate ore comprises: obtaining liquid high-phosphorus slag, adding a reducing agent to the liquid high-phosphorus slag for reduction to obtain phosphorus-containing flue gas, and condensing the phosphorus-containing flue gas to obtain yellow phosphorus; the liquid high-phosphorus slag is obtained in an oxidation smelting furnace, and the adding of the reducing agent and the obtaining of yellow phosphorus are carried out in a reduction furnace; the liquid high-phosphorus slag is obtained by mixing phosphate ore and slag-making flux to obtain a mixed material with an acidity coefficient of 0.65 to 0.85, and the mixed material is oxidized and smelted in an oxidation smelting furnace to obtain molten liquid high-phosphorus slag. The invention improves the tolerance of phosphate ore sources and broadens the utilization boundary, realizes the purpose of continuous thermal smelting to produce yellow phosphorus, greatly reduces the unit energy consumption of yellow phosphorus smelting, reduces the output of mud phosphorus, reduces the acidic gas phase components in flue gas, improves the utilization rate of phosphorus tail gas, and reduces production costs.
Description
Technical Field
The invention relates to the field of phosphorite smelting, in particular to a system and a method for producing yellow phosphorus by phosphorite smelting.
Background
The existing yellow phosphorus production main process technology is an electric furnace yellow phosphorus method, and is generally characterized in that phosphate ore and silica are mixed in proportion and added into a reaction furnace for melting, after the melt reaches a certain height, the mixed material of the phosphate ore, the silica and carbon is directly added into the high-temperature melt of the reaction furnace, excessive carbon is maintained, the melt is subjected to reduction reaction to obtain flue gas and phosphorus mud respectively, the flue gas mainly contains gasified yellow phosphorus and CO, and the flue gas is separated and purified to obtain yellow phosphorus products and yellow phosphorus tail gas rich in CO respectively. The whole heat required for producing yellow phosphorus is provided by electric energy, the electricity consumption per ton of yellow phosphorus is about 14000-16000 kWh, and the energy consumption is higher.
The traditional electric furnace yellow phosphorus tail gas contains phosphorus, sulfur, arsenic, fluorine and other impurities, and practice proves that the untreated yellow phosphorus tail gas is burnt, and the combustion gas has stronger corrosiveness because the untreated yellow phosphorus tail gas contains a plurality of harmful elements and has highly corrosive substances. If used as the synthesis gas, various catalysts of the synthesis gas have more severe requirements on impurities and also have to be subjected to deep purification; therefore, the yellow phosphorus tail gas has difficult problem of difficult utilization. In addition, in the electric furnace smelting process, a part of solid dust is always carried out, the dust content of furnace gas is 20-50 g/Nm 3, if phosphate ore meeting high carbonate is decomposed and crushed at high temperature, the dust is carried out more seriously, and the dust content in the furnace gas is up to more than 100 g/Nm 3, so that the yellow phosphorus quality is greatly influenced.
Meanwhile, in the traditional yellow phosphorus method of the electric furnace, the excessive water content of furnace burden often worsens the operation, blocks a material pipe, makes the blanking unsmooth, and causes material collapse due to caking bridging in the electric furnace, so that flame spraying and even explosion accidents occur; in addition, a large amount of free water enters the furnace, the side reaction is increased, the tail gas amount is increased, the content of impurities such as PH 3、H2 S in yellow phosphorus tail gas is also increased, and especially when the water content of the raw material is increased in rainy season, the content of H 2 S in the yellow phosphorus tail gas is obviously increased, thus causing adverse effects on desulfurization. As the side reaction is increased, the consumption of raw material carbon and electrodes is increased, the recovery rate of elemental phosphorus is reduced, and the yield of phosphorus is reduced.
Therefore, conventionally, high-quality yellow phosphorus is required to be obtained, the material fed into the furnace needs to be dried until the water content is lower than 2%, and the powder ore needs to be granulated and pelletized and then fed into the furnace, namely, the phosphorite needs to be pretreated such as drying, granulating and the like before entering into an electric furnace for reduction smelting. For example: the equipment and the method for producing the yellow phosphorus by utilizing the middle-low grade phosphate ore disclosed in the Chinese patent application CN107686099A are characterized in that a grinding unit and a ball-making drying unit are adopted to treat the phosphate ore firstly so as to prepare the granular material with low water content and a certain particle size, and then the granular material is put into a furnace to carry out reduction reaction to produce the yellow phosphorus.
Phosphorus mud is a byproduct produced by producing phosphorus by an electric furnace, and belongs to dangerous solid wastes. Sludge phosphorus disposal is an important component of yellow phosphorus production, not only affects the yield and production cost of yellow phosphorus, but also causes pollution to the surrounding environment. In order to realize energy conservation, emission reduction, environmental protection and resource conservation, the sludge phosphorus must be effectively recycled and subjected to source reduction treatment. At present, the treatment of the sludge phosphorus is carried out by adopting a phosphorus steaming method, and the treatment of the sludge phosphorus is carried out by directly returning the sludge phosphorus to an electric furnace for smelting to form high-phosphorus slag. In the process of returning the phosphorus mud to the electric furnace for disposal, the elemental phosphorus and water are subjected to interactive reaction at high temperature, the products are hypophosphorous acid (H 3PO2), a small amount of phosphine gas (H 3 P) and hydrogen (H 2), so that elemental phosphorus is lost, the hypophosphorous acid and dust react, the normal production is influenced by the damage to the air permeability of raw materials, and the phosphine gas and the hydrogen have lower explosion lower limit, so that certain potential safety hazards exist.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the electric furnace yellow phosphorus method has high requirements on furnace materials, yellow phosphorus tail gas is difficult to use and phosphorus mud recycling affects normal production in the prior art, thereby providing a system and a method for producing yellow phosphorus by smelting phosphorite.
A method for producing yellow phosphorus by smelting phosphorite comprises the following steps: obtaining liquid high-phosphorus slag, adding a reducing agent into the liquid high-phosphorus slag for reduction to obtain phosphorus-containing flue gas, and condensing the phosphorus-containing flue gas to obtain yellow phosphorus;
The liquid high-phosphorus slag is obtained in an oxidation smelting furnace, and the addition of the reducing agent and the obtaining of yellow phosphorus are carried out in the reduction furnace;
the liquid high phosphorus slag is obtained by the following steps: and mixing the phosphate ore and the slag-forming flux to obtain a mixed material with an acidity coefficient of 0.65-0.85, and carrying out oxidation smelting on the mixed material in an oxidation smelting furnace to obtain molten liquid high-phosphorus slag.
The acidity coefficient is the mass ratio of SiO 2/CaO. Too low and too high acid degree, high slag melting point and high viscosity, influence the fluidity of metallurgical slag and influence the reduction behavior of phosphorus in the reduction period; in addition, the too high acidity causes too large flux proportion, so that the phosphorus grade of the mixed phosphorus ore is reduced, and the unit production cost of phosphorus is increased; therefore, the acidity coefficient of the mixed material obtained after mixing the phosphate ore and the slag-forming flux is set to be 0.65-0.85.
In the oxidation smelting and reduction steps, if the temperature is too low, the fluidity of slag is reduced, the subsequent reduction of phosphorus is affected, the emission of slag is not facilitated, and the process is difficult to run smoothly; if the temperature is too high, the unit energy consumption of smelting is improved, the production cost is increased, and the service life of the refractory material of the oxidation furnace is influenced. Therefore, the temperature of the oxidation smelting and reduction in the present invention is preferably 1350 ℃ to 1500 ℃.
The traditional electric furnace process requires that the water content of the raw materials fed into the furnace is required to be less than 2 percent, and for the raw materials with the water content higher than 2 percent, the drying and granulating procedures of the raw materials are required, so that the application of the raw materials is limited. After the operation flow is optimized, the invention has wider application range of the water content of the raw materials, can meet the requirement that the raw materials with the water content of more than 2 percent are directly fed into the furnace, shortens the working procedure and reduces the production cost. However, when the water content is too high, a large amount of heat is taken away in the form of water vapor, so that the energy consumption for smelting yellow phosphorus is high, and the water content of the mixed material in the invention is preferably below 12%, more preferably 2% -5%.
The particle size is too large, and the time required for complete melting of the material is long; the particle size of the mixture in the invention is preferably less than or equal to 50mm.
The addition amount of the reducing agent in the liquid high-phosphorus slag may be 1 to 2 times, preferably 1 to 1.3 times, the theoretical amount.
The reducing agent comprises at least one of anthracite, semi-coke, graphite powder and coke;
the slag-forming flux is silica, quartz stone, etc.; the fuel is pulverized coal or natural gas, etc.
The reducing agent particles are too large, the contact interface of the reaction medium is small, and the reaction time is long; the particles are too small and the dust rate is too high. According to the invention, the particle size of the reducing agent is preferably 15-35 mm, and the reducing agent is ensured to participate in the reduction reaction to the greatest extent.
A system for a method for producing yellow phosphorus by smelting phosphate ore, comprising:
The oxidation smelting furnace is used for oxidizing and smelting the phosphate ore and the slag-forming flux into molten liquid high-phosphorus slag;
The reducing furnace comprises a liquid high-phosphorus slag input port, a reducing material input port and a phosphorus-containing flue gas outlet, and is used for reducing the liquid high-phosphorus slag to obtain phosphorus-containing flue gas;
and the water spraying tower is communicated with the phosphorus-containing flue gas outlet and is used for condensing and recycling yellow phosphorus products from the phosphorus-containing flue gas.
The oxidation smelting furnace is a side-blowing furnace, a top-blowing furnace, a bottom-blowing furnace, a top-side combined-blowing furnace and a top-bottom combined-blowing furnace; wherein, the phosphorite powder, fuel and the like can be selectively sprayed into the molten pool directly by adopting a material-carrying side-blowing spray gun, so that the direct utilization rate of the powder phosphorite can be improved; and (3) when the liquid level of the Gao Linzha melt in the side-blowing furnace reaches the discharge height, periodically discharging, and transferring the liquid high-phosphorus slag into a closed reduction furnace.
The reduction furnace is an electric furnace, preferably a side-blown electric furnace.
The technical scheme of the invention has the following advantages:
1. The invention provides a method for producing yellow phosphorus by smelting phosphorite, which is used for preparing molten liquid high-phosphorus slag by rapidly oxidizing and melting phosphorite mixture by an oxidizing smelting furnace, so that the requirements on the particle size and the water content of furnace charge are not needed, the applicable furnace charge range is widened, and the influence of phosphorus mud recycling is avoided; meanwhile, the acidity coefficient of a mixed material formed by mixing the phosphate ore and the slag-forming flux is controlled to be 0.65-0.85, so that the loss of phosphorus element caused by volatilization of phosphorus element in the process of preparing the molten liquid high-phosphorus slag can be reduced; in addition, harmful elements and water can be effectively removed in the step, the problem that the quality of phosphorus-containing flue gas is low when the molten liquid high-phosphorus slag enters a reduction furnace to carry out reduction and volatilization of phosphorus so as to volatilize the phosphorus into the flue gas to obtain phosphorus-containing flue gas is avoided, the problem that yellow phosphorus tail gas is difficult to utilize is further solved, and finally, the high-quality phosphorus-containing flue gas is condensed and recovered through a multi-stage water leaching tower to obtain a yellow phosphorus product, so that the purposes of efficiently, low-carbon and cleanly disposing the phosphorus ore are realized.
Wherein, phosphorite is directly subjected to oxidation smelting treatment, and the smelting process is controlled to be oxidation smelting under a specific acidity coefficient, so that the oxygen potential in the furnace is higher, and the phosphorus simple substance in phosphorite is not easy to volatilize and enters slag to form high-phosphorus slag, thereby avoiding the loss of phosphorus element; the oxidation smelting furnace is used for smelting in a molten pool, and a raw material layer does not exist, so that the requirements on the material state and the water content of phosphorite are not high, and the application range is wider. Meanwhile, in the melting process of returning the sludge phosphorus to the oxidation smelting furnace, explosive gases such as phosphine, hydrogen and the like similar to an electric furnace are not generated, so that the oxidation smelting furnace has potential technical advantages for comprehensive treatment of the sludge phosphorus. In addition, in the melting process of the oxidation smelting furnace, sulfur, arsenic, fluorine, chlorine (S, as, F, cl) and other harmful elements in phosphorite can be removed by utilizing oxidation smelting, and meanwhile, water (H 2 O) carried by the material fed into the furnace is removed, so that the quality of the volatilized phosphorus-containing flue gas of the reduction furnace is improved, the corrosiveness of the furnace gas is reduced, the emission of the furnace gas is reduced, the CO content in the furnace gas of the reduction furnace is higher, the phosphorus concentration is high, the impurity content is low, the subsequent flue gas purification treatment load and the corresponding cost are reduced, and the subsequent high-quality yellow phosphorus is acquired.
Specifically, the oxidation smelting furnace mainly completes smelting of furnace burden, phosphorus element still remains in slag to form liquid high-phosphorus slag, and in the smelting process, harmful elements (S, as, F, cl, I, na and the like) and water content (H 2 O) of materials entering the reduction furnace can be effectively removed, so that the impurity removal effect is provided for the reduction and volatilization of phosphorus in the subsequent reduction furnace, the purity of phosphorus-containing flue gas of the reduction furnace is improved, the smoke dust rate is reduced, the phosphorus yield of phosphorus-containing sludge in the phosphorus-collecting process is reduced, and the phosphorus yield is improved. Meanwhile, as moisture can be removed in the melting process of the oxidation smelting furnace, the oxidation smelting furnace has wide application range on the moisture content and granularity (powder ore, lump ore and pellets) of the furnace burden, the moisture content of the furnace burden is less than 12%, the processes of material drying and powder granulating can be reduced, or the flue gas waste heat of the melting furnace can be adopted for carrying out raw material drying treatment, so that the investment of a separate drying system is avoided. In addition, the bed energy rate of the oxidation smelting furnace adopted by the invention is 27-50 t/(d.m 2), which is far higher than the bed energy rate of an electric furnace commonly used in yellow phosphorus production at present by 5-12 t/(d.m 2), the heat source can be anthracite, natural gas, kerosene and the like, the oxidation smelting furnace adopts oxidation smelting, the content of tail gas CO is lower, and the utilization efficiency of combustion heat is high; meanwhile, the reduction furnace only completes the reduction volatilization of the liquid high-phosphorus slag and maintains the heat preservation function of smelting temperature, and effectively reduces the influence of the diffusion speed of solute atoms on the phosphorus reduction chemical reaction rate, thereby improving the phosphorus reduction volatilization reaction kinetics, shortening the reaction time and improving the treatment capacity and efficiency of the electric furnace; compared with the traditional electric furnace for smelting yellow phosphorus, the method has the advantages of lower smoke dust rate, high smelting reduction reaction efficiency, shortened reduction reaction time of the reduction furnace, improved volatilization phosphorus smelting bed energy rate of the reduction furnace, reduced equipment investment, greatly reduced electric energy consumption and cost saving.
In conclusion, the invention improves the tolerance of the phosphorite source and widens the utilization boundary, achieves the purpose of producing yellow phosphorus by continuous hot smelting, thoroughly solves the problem of phosphogypsum emission from the phosphorite source, and further achieves the energy-saving, circulating and clean production of the phosphorite.
2. Under the same capacity condition, the invention greatly reduces equipment investment and occupied area, improves on-site operation environment and reduces labor intensity; meanwhile, the electrode can be not used as a heat source any more, so that the problems of difficult electrode operation, easy electrode breakage, electric furnace burden bridging and material collapse and the like can be effectively avoided.
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 needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is a schematic diagram showing the state of the system smelting process for producing yellow phosphorus in accordance with example 1 of the present invention;
fig. 3 is a schematic view showing a state in the process of producing yellow phosphorus by smelting a system according to example 5 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
A method for producing yellow phosphorus by smelting phosphorite, as shown in fig. 1 and 2, comprises the following steps:
(1) Liquid high phosphorus slag acquisition
Mixing phosphate ore and slag-forming flux to obtain a mixed material with an acidity coefficient of 0.8, wherein the phosphate ore adopted in the embodiment is middle-grade and low-grade phosphate ore, and the components of the phosphate ore are shown in the following table 1;
TABLE 1 phosphorus ore composition (wt%)
Specifically, adding a slag-forming flux quartz stone into the phosphate ore, controlling the mass ratio of an acidity coefficient SiO 2/CaO to be 0.8, crushing to obtain a mixed material with the grain size less than or equal to 50mm, adding the mixed material with the water content of 2.5% through a charging port of an oxygen-enriched side-blowing furnace, spraying pulverized coal into the melt by using a spraying mode, controlling the back pressure of a spray gun to be 0.2-0.35 Mpa, controlling the oxygen combustion excess coefficient to be 1.2, controlling the temperature of a melt to be 1400 ℃ and controlling the oxygen-enriched concentration to be 75%. The excess coefficient of oxygen combustion in oxidation smelting refers to the ratio of the amount of air actually supplied to the fuel during combustion to the theoretical amount of air.
The smelting products of the oxygen-enriched side-blown furnace comprise liquid high-phosphorus slag, melting smoke dust and melting smoke gas, wherein the melting smoke dust and the melting smoke gas are obtained by filtering and separating furnace gas obtained by oxidizing and melting the oxygen-enriched side-blown furnace.
After pulverized coal is sprayed into the melt, the phosphorus grade P 2O5 in the side-blown slag (liquid high-phosphorus slag) is 24.67%. The melting flue gas mainly comprises CO 2 due to complete combustion, the volume fraction of CO 2 is 62.79%, and the volume fraction of partial P 2O5,P2O5 is only 0.1%; the defluorination rate of slag can reach 99 percent by side blowing enhanced oxidation combustion, specifically, the volume fraction of SiF 4 in the melting smoke reaches 1.52 percent, the melting smoke contains CaF 4 with the mass percentage of 7.08 percent, and the content of F substances CaF 4 in the liquid high-phosphorus slag is only 0.06 percent. Meanwhile, the melting flue gas also comprises H 2 S with the volume fraction of 0.01 percent and SO 2 with the volume fraction of 0.26 percent. The melting dust contained 13.50% P 2O5, 7.08% CaF 2, 0.2% I,1.66% Cl.
The side blowing stage input conditions are as follows: coal consumption per ton of ore is 0.21t, oxygen consumption per ton of ore is 279.61Nm 3, compressed air consumption per ton of ore is 125.83Nm 3, and quartz stone consumption per ton of ore is 0.32t; the output condition is that the slag rate is 80.51 percent, the ton phosphorus side-blown melting smoke is 180.46kg, the smoke rate is 1.50 percent, and the ton ore smoke amount is 491.39Nm 3.
(2) Reduction of
Transferring the high-phosphorus slag of the side-blown converter into an electric furnace, maintaining the temperature of the melt at 1400 ℃ by utilizing electric heat, and adding reducing agent coke with the particle size of 15-35 mm, wherein the addition amount of the coke is 1.2 times of the theoretical amount. The products of the reduction and volatilization phosphorus smelting stage in the electric furnace comprise dephosphorization slag, phosphorus-containing flue gas, ferrophosphorus and volatile smoke dust.
Wherein the P 2O5 content in dephosphorization slag is only 0.46%, and the FeO content is 0.04%; the phosphorus-containing flue gas mainly comprises CO, the volume fraction of the CO is 84.32%, the volume fraction of the P 4 is 8.23%, the volume fraction of H 2 S is only 0.16%, the volume fraction of HF is only 0.01%, and the volume fraction of SO 2 is only 0.16%; the iron content in the ferrophosphorus is 77.25 percent, and the P content is 18 percent; the content of P 2O5 in the volatilized smoke is 24.48%, and the content of Fe 2O3 is 1.57%.
In the stage of reducing, volatilizing and smelting phosphorus by the electric furnace, the power consumption per ton of phosphorus is 3958.20 kW.h, the coke consumption per ton of phosphorus is 1.17t, the flue gas quantity of the electric furnace per ton of phosphorus is 2023.00Nm 3, the phosphorus yield per ton of phosphorus is 0.14t, and the volatilizing smoke dust per ton of phosphorus is 4.88kg.
(3) Yellow phosphorus acquisition
The main component volume fraction of the phosphorus-containing flue gas is P 4: 8.23%, CO:84.32%. Obtaining yellow phosphorus and yellow phosphorus tail gas after phosphorus is recovered by a water leaching tower, wherein the volume fraction of CO in the yellow phosphorus tail gas reaches 91.86%, HF is 0.01%, and P 4 is 0.02%; the estimated heat value is about 12323.50KJ/Nm 3 according to the smoke component, and the yield of yellow phosphorus in the step after conversion is 93%.
Example 2
A method for producing yellow phosphorus by smelting phosphorite comprises the following steps:
(1) Liquid high phosphorus slag acquisition
Mixing phosphate ore and silica in the embodiment 1 to obtain a mixed material with the particle size less than or equal to 50mm and the acidity coefficient SiO 2/CaO of 0.65, adding the mixed material with the water content of 3.0% through a charging port of an oxygen-enriched side-blowing furnace, spraying pulverized coal into a melt by using a spraying mode, wherein the back pressure of a spray gun is 0.2-0.35 Mpa, the oxygen combustion excess coefficient is 1.2, and controlling the temperature of the melt to 1500 ℃ and the oxygen concentration to 75%.
After the pulverized coal is added, the phosphorus grade P 2O5 in the side-blown slag (liquid high-phosphorus slag) is 28%. The flue gas is mainly CO 2 due to complete combustion, and the volume fraction of CO 2 is 65%. The side blowing enhanced oxidation combustion has slag defluorination rate up to 95%, and the volume fraction of SiF 4 in the flue gas is 1.4%.
The side blowing stage input conditions are as follows: coal consumption per ton of ore is 0.23t, oxygen consumption per ton of ore is 290 Nm 3, compressed air consumption per ton of ore is 140: 140 Nm 3, quartz stone consumption per ton of ore is 0.28: 0.28 t; the output condition is that the slag rate is 75%, the smoke rate of 160kg of ton phosphorus side blown melting smoke is 1.45%, and the smoke amount of ton ore is 512Nm 3.
(2) Reduction of
Transferring the high-phosphorus slag of the side-blown converter into an electric furnace, maintaining the temperature of the melt at 1500 ℃ by utilizing electric heat, adding anthracite serving as a reducing agent, wherein the addition amount of the anthracite is 1.3 times of the theoretical amount, and the particle size of the anthracite is 15-35 mm. In the stage of electric furnace reduction and volatilization phosphorus smelting, the power consumption per ton of phosphorus is 4050 kW.h, the power consumption per ton of phosphorus is 1.20t of anthracite, the smoke volume of the electric furnace per ton of phosphorus is 2100Nm 3, the phosphorus production per ton of phosphorus is 0.15t, and the phosphorus volatilization smoke is 4.50kg.
(3) Yellow phosphorus acquisition
The main component volume fraction of the phosphorus-containing flue gas is P 4: 8.5%, CO:83%. And (3) collecting phosphorus by a water leaching tower to obtain yellow phosphorus tail gas, wherein the volume fraction of CO in the yellow phosphorus tail gas reaches 90%, the HF is 0.015%, the estimated heat value of the yellow phosphorus tail gas is about 12200KJ/Nm 3 according to the smoke component, and the yield of the yellow phosphorus is 94%.
Example 3
A method for producing yellow phosphorus by smelting phosphorite comprises the following steps:
(1) Liquid high phosphorus slag acquisition
Mixing phosphate ore and silica in the embodiment 1 to obtain a mixed material with the particle size less than or equal to 50mm and the acidity coefficient SiO 2/CaO of 0.85, adding the mixed material with the water content of 2.8% through a charging port of an oxygen-enriched side-blowing furnace, spraying pulverized coal into a melt by using a spraying mode, wherein the back pressure of a spray gun is 0.2-0.35 Mpa, the oxygen combustion excess coefficient is 1.2, and controlling the temperature of the melt to 1350 ℃ and the oxygen concentration to 75%.
After the pulverized coal is added, the phosphorus grade P 2O5 in the side-blown slag (liquid high-phosphorus slag) is 23.80%. The flue gas is mainly CO 2 due to complete combustion, and the volume fraction of CO 2 is 65%. The side blowing enhanced oxidation combustion has slag defluorination rate up to 96%, and the volume fraction of SiF 4 in the flue gas is 1.6%.
The side blowing stage input conditions are as follows: coal consumption per ton of ore is 0.22t, oxygen consumption per ton of ore is 280 Nm 3, compressed air consumption per ton of ore is 130: 130 Nm 3, quartz stone consumption per ton of ore is 0.35: 0.35 t; the output condition is that the slag rate is 82%, the ton phosphorus side blowing melting smoke dust is 190kg, the smoke dust rate is 1.55%, and the ton ore smoke gas amount is 510Nm 3.
(2) Reduction of
Transferring the high-phosphorus slag of the side-blown converter into an electric furnace, maintaining the temperature of the melt at 1350 ℃ by utilizing electric heat, adding anthracite serving as a reducing agent, wherein the addition amount of the anthracite is 1.25 times of the theoretical amount, and the particle size of the anthracite is 15-35 mm. In the electric furnace reduction and volatilization phosphorus smelting stage, the power consumption per ton of phosphorus is 3850 kW.h, the power consumption per ton of phosphorus is 1.15t of anthracite, the smoke volume of the electric furnace per ton of phosphorus is 1980Nm 3, the phosphorus production per ton of phosphorus is 0.13t, and the phosphorus volatilization smoke is 4.50kg.
(3) Yellow phosphorus acquisition
The main component volume fraction of the phosphorus-containing flue gas is P 4: 7.5%, CO:86%. And (3) collecting phosphorus by a water leaching tower to obtain yellow phosphorus tail gas, wherein the volume fraction of CO in the yellow phosphorus tail gas reaches 92%, the HF is 0.01%, the estimated heat value of the yellow phosphorus tail gas is about 12500KJ/Nm 3 according to the smoke component, and the yield of the yellow phosphorus is 95%.
Example 4
A method for producing yellow phosphorus by smelting phosphorite comprises the following steps:
(1) Liquid high phosphorus slag acquisition
Mixing phosphate ore and silica in the embodiment 1 to obtain a mixed material with the particle size less than or equal to 50mm and the acidity coefficient SiO 2/CaO of 0.80, adjusting the water content of the mixed material to 10%, adding the mixed material through a charging port of an oxygen-enriched side-blown furnace, spraying pulverized coal into a melt by using a spraying mode, wherein the back pressure of a spray gun is 0.2-0.35 Mpa, the oxygen combustion excess coefficient is 1.2, and controlling the temperature of the melt to 1400 ℃ and the oxygen enrichment concentration to 75%.
After the pulverized coal is added, the phosphorus grade P 2O5 in the side-blown slag (liquid high-phosphorus slag) is 25.50%. The flue gas is mainly CO 2 due to complete combustion, and the volume fraction of CO 2 is 68%. The side blowing enhanced oxidation combustion has slag defluorination rate up to 96%, and the volume fraction of SiF 4 in the flue gas is 1.78%.
The side blowing stage input conditions are as follows: coal consumption per ton of ore is 0.20t, oxygen consumption per ton of ore is 270 Nm 3, compressed air consumption per ton of ore is 120 Nm 3, and quartz stone consumption per ton of ore is 0.31 t; the output condition is that the slag rate is 82%, the smoke rate of the side blown molten smoke dust of ton phosphorus is 176kg, the smoke rate is 1.52%, and the smoke gas quantity of ton ore is 485Nm 3.
(2) Reduction of
Transferring the high-phosphorus slag of the side-blown converter into an electric furnace, maintaining the temperature of the melt at 1400 ℃ by utilizing electric heat, adding reducing agent coke, wherein the addition amount of the coke is 1.25 times of the theoretical amount, and the particle size of the coke is 15-35 mm. In the electric furnace reduction and volatilization phosphorus smelting stage, the electricity consumption per ton of phosphorus is 3875 kW h, the electricity consumption per ton of phosphorus is 1.19t of anthracite, the smoke volume of the electric furnace per ton of phosphorus is 2085Nm 3, the phosphorus production per ton of phosphorus is 0.138t, and the phosphorus volatilization smoke is 4.30kg.
(3) Yellow phosphorus acquisition
The main component volume fraction of the phosphorus-containing flue gas is P 4: 8.6%, CO:86%. The yellow phosphorus tail gas is obtained after phosphorus is recovered by a water leaching tower, the volume fraction of CO in the yellow phosphorus tail gas reaches 93 percent, HF is 0.01 percent, and the estimated heat value of the yellow phosphorus tail gas is about 12280KJ/Nm 3 according to the smoke component, and the yield of the yellow phosphorus is 94 percent.
Example 5
A method for producing yellow phosphorus by smelting phosphorite comprises the following steps:
(1) Liquid high phosphorus slag acquisition
Mixing phosphate ore and silica in the embodiment 1 to obtain a mixed material with the particle size less than or equal to 50mm and the acidity coefficient SiO 2/CaO of 0.80, adjusting the water content of the mixed material to 4.5%, adding the mixed material through a charging port of an oxygen-enriched side-blowing furnace, spraying pulverized coal into a melt by using a spraying mode, wherein the back pressure of a spray gun is 0.2-0.35 Mpa, the oxygen combustion excess coefficient is 1.2, and controlling the temperature of the melt to 1400 ℃ and the oxygen concentration to 75%.
After the pulverized coal is added, the phosphorus grade P 2O5 in the side-blown slag (liquid high-phosphorus slag) is 25.60%. The flue gas is mainly CO 2 due to complete combustion, and the volume fraction of CO 2 is 67%. The defluorination rate of slag reaches 94%, and the volume fraction of SiF 4 in flue gas is 1.35%.
The side blowing stage input conditions are as follows: coal consumption per ton of ore is 0.20t, oxygen consumption per ton of ore is 272 Nm 3, compressed air consumption per ton of ore is 118 Nm 3, quartz stone consumption per ton of ore is 0.31 t; the output condition is 78% of slag rate, 172kg of ton phosphorus side blown molten smoke, 1.46% of smoke rate and 487Nm 3 of ton ore smoke.
(2) Reduction of
And transferring the high-phosphorus slag of the side-blown furnace into the side-blown reduction furnace, as shown in fig. 3, using a side-blown spray gun to burn to maintain the temperature of the melt at 1400 ℃, adding reducing agent coke, wherein the addition amount of the coke is 1.6 times of the theoretical amount, and the particle size of the coke is 15-35 mm. In the side blowing reduction and volatilization phosphorus smelting stage, the ton phosphorus consumption is 1.7t, the smoke volume of a ton phosphorus electric furnace is 3500Nm 3, the ton phosphorus yield is 0.12t, and the ton phosphorus volatilizes smoke and dust is 7.6kg.
(3) Yellow phosphorus acquisition
The main component volume fraction of the phosphorus-containing flue gas is P 4: 6.78%, CO:72%. And (3) collecting phosphorus by a water leaching tower to obtain yellow phosphorus tail gas, wherein the volume fraction of CO in the yellow phosphorus tail gas reaches 80%, the HF is 0.01%, the estimated heat value is about 10500KJ/Nm 3 according to the smoke component, and the yield of yellow phosphorus is 92%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
1. A method for producing yellow phosphorus by smelting phosphorite comprises the following steps: obtaining liquid high-phosphorus slag, adding a reducing agent into the liquid high-phosphorus slag for reduction to obtain phosphorus-containing flue gas, and condensing the phosphorus-containing flue gas to obtain yellow phosphorus; it is characterized in that the method comprises the steps of,
The liquid high-phosphorus slag is obtained in an oxidation smelting furnace, and the addition of the reducing agent and the obtaining of yellow phosphorus are carried out in the reduction furnace; the reduction furnace is an electric furnace;
The liquid high phosphorus slag is obtained by the following steps: mixing phosphate ore and slag-forming flux to obtain a mixed material with an acidity coefficient of 0.65-0.85, and carrying out oxidation smelting on the mixed material in an oxidation smelting furnace to obtain molten liquid high-phosphorus slag;
The temperature of the oxidation smelting and the reduction is 1350-1500 ℃;
the addition amount of the reducing agent in the liquid high-phosphorus slag is 1-2 times of the theoretical amount;
The reducing agent comprises at least one of anthracite, semi-coke, graphite powder and coke.
2. The method of claim 1, wherein the water content of the mixture is 12% or less.
3. The method of claim 2, wherein the water content of the mixed material is 2% -5%.
4. The method of claim 1, wherein the mixed material has a particle size of 50mm or less.
5. The method of claim 1, wherein the particle size of the reducing agent is 15-35 mm.
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| CN104477862A (en) * | 2014-12-16 | 2015-04-01 | 四川有峰环保科技有限公司 | Method and raw material for producing yellow phosphorus or phosphoric acid by adopting rotary kiln |
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| CN104477862A (en) * | 2014-12-16 | 2015-04-01 | 四川有峰环保科技有限公司 | Method and raw material for producing yellow phosphorus or phosphoric acid by adopting rotary kiln |
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