CN110240135B - Method and system for pre-dearsenifying of high-arsenic phosphorite - Google Patents
Method and system for pre-dearsenifying of high-arsenic phosphorite Download PDFInfo
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- CN110240135B CN110240135B CN201910628833.5A CN201910628833A CN110240135B CN 110240135 B CN110240135 B CN 110240135B CN 201910628833 A CN201910628833 A CN 201910628833A CN 110240135 B CN110240135 B CN 110240135B
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Abstract
The invention relates to the technical field of phosphorite purification, and provides a method for pre-dearsenifying high-arsenic phosphorite. Further, in order to obtain a clean arsenic product, the flue gas containing a small amount of mineral powder is subjected to dust removal and cooling crystallization, and the generated white arsenic is recovered. The method of the invention ensures that the arsenic removal rate of the high arsenic phosphorite is more than 80 percent, the phosphorus loss rate is less than 3 percent, the process flow is simple, white arsenic can be recycled, waste is changed into valuable, and the method has wide application prospect. The invention utilizes the heat generated by the combustion of high-concentration CO in the yellow phosphorus tail gas to carry out high-temperature heat treatment on the high-arsenic phosphate rock powder, thereby further reducing the cost. The invention also provides a system for pre-dearsenifying the high-arsenic phosphorite, which has a simple structure, and is easy to realize industrial production by using the system to pre-dearsenify the high-arsenic phosphorite.
Description
Technical Field
The invention relates to the technical field of phosphorite purification, in particular to a method and a system for pre-dearsenifying high-arsenic phosphorite.
Background
Phosphorite is a general term for phosphate minerals which can be utilized and is an important chemical mineral raw material. The method is commonly used for preparing yellow phosphorus, phosphoric acid and other phosphates in industry, and can be used in industrial departments of medicine, food, dye, ceramics, national defense and the like. The phosphorite resources in China are rich, but the high-grade phosphorite reserves are low, and according to the current mining mode of 'gathering and abandoning poor', the phosphorite in China is exhausted after 20 years. In recent years, with the development of phosphate fertilizer industry, the demand of phosphate rock is increasing dramatically. Under the background, people begin to exploit phosphorite resources with low grade and produce commercial phosphorite through enrichment processing. Wherein, the high arsenic phosphorite (applicable to the phosphorite with the arsenic content more than 10 ppm) has higher phosphorus content, but the arsenic removal cost is higher. Arsenic released by unreasonable exploitation and utilization mining activities causes environmental pollution and threatens human health through soil, water sources and food chain approaches, so that arsenic removal treatment of arsenic-containing phosphorite is very important. Over the years, people are constantly researching the technology and the method for removing arsenic from phosphorite, wherein the technology mainly comprises a distillation method, a mixed acid method, a chloride method and the like, and various arsenic removal methods are derived along with the development of the technology.
Patent CN 1247835A discloses a method for removing arsenic from phosphorite, which adopts a dissolving and distilling mode to obtain the phosphorite after arsenic removal through multi-stage treatment. The method needs a large amount of solvent to dissolve the phosphorite firstly, and washing is carried out after crystallization, and multiple crystallization washing and distillation are needed subsequently in order to improve the arsenic removal rate. The method has high requirements on equipment, high economic cost, complex manufacturing by multiple washing and long time consumption.
Patent CN 035809A discloses a method for removing arsenic from phosphorite by sulfuric acid, which requires pretreating powdered rock phosphate with dilute sulfuric acid, and then adding cosolvent and reducer, and reacting at above 1000 deg.C to remove arsenic. The method has the advantages of high economic cost, high arsenic removal efficiency, high phosphorus loss rate and certain potential safety hazard due to the use of a large amount of concentrated sulfuric acid.
Patent CN 108892114A discloses an electro-catalytic oxidation dearsenification method, wherein phosphorus powder, electrolyte and electrolyte are respectively added into cathode and anode chambers of an electrolytic cell, and N is required to be introduced during the reaction process2And after the reaction is finished, ultrapure water is used for cleaning the arsenic and phosphorus removal powder. The reaction process is simple, but a large amount of electrolytic waste liquid is generated, and ultrapure water needs to be prepared for providing N2Protection and high energy consumption.
The methods have the problems of high economic cost, high phosphorus loss rate, long time consumption, production waste liquid generation, potential safety hazard and the like.
Disclosure of Invention
The invention aims to provide the method for pre-dearsenifying the phosphorite, which has high safety and simple process flow and can be used for continuous production.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for pre-dearsenifying high-arsenic phosphorite comprises the following steps:
carrying out high-temperature heat treatment on the high-arsenic phosphate rock powder to obtain low-arsenic phosphate rock powder and smoke containing arsenic dust; the temperature of the high-temperature heat is 420-550 ℃;
and (3) cooling and crystallizing the arsenic-containing flue gas after dedusting to obtain solid arsenic trioxide.
The particle size of the high-arsenic phosphate rock powder is 100-600 mu m.
Preferably, the time of the high-temperature heat treatment is 0.5-1.5 h; the heat of the high-temperature heat treatment is derived from the heat generated by the combustion of the yellow phosphorus tail gas.
Preferably, the temperature for dedusting is 380-460 ℃; the temperature of the cooling crystallization is 180-220 ℃.
The invention provides a system for pre-dearsenifying high-arsenic phosphorite, which comprises a fluidized bed furnace, a ceramic dust remover, a condensing tower and a blower, wherein the ceramic dust remover is arranged in the fluidized bed furnace;
the fluidized bed furnace is provided with a solid inlet, a solid outlet, a gas inlet and a gas outlet; the gas inlet is used for introducing yellow phosphorus tail gas and air; the gas outlet of the fluidized bed furnace is communicated with the gas inlet;
the ceramic dust remover is provided with a gas inlet, a gas outlet and a solid outlet; the gas inlet of the ceramic dust remover is communicated with the gas outlet of the fluidized bed furnace; the solid outlet of the ceramic dust remover is communicated with the solid inlet of the fluidized bed furnace;
the condensing tower is provided with a gas inlet, a gas outlet, a liquid inlet and a solid outlet; the gas inlet of the condensing tower is communicated with the gas outlet of the ceramic dust collector;
the blower includes a first blower and a second blower; the blower is communicated with a gas inlet of the boiling furnace and is used for blowing air into the boiling furnace.
Preferably, the system also comprises a high-arsenic phosphorite bin and an ore crusher which are communicated in sequence; and the outlet of the ore crusher is communicated with the solid inlet of the fluidized bed furnace.
Preferably, the system further comprises a high density bag house comprising a gas inlet, a gas outlet and a solids outlet; and a gas inlet of the high-density bag type dust collector is communicated with a gas outlet of the condensing tower.
The invention also provides a method for pre-dearsenifying high-arsenic phosphorite by using the system in the scheme, which comprises the following steps:
(1) conveying high-arsenic phosphate rock powder into a fluidized bed furnace, introducing yellow phosphorus tail gas at the bottom end of the fluidized bed furnace for combustion, introducing air for combustion supporting by using a first air blower, introducing air by using a second air blower for temperature control, disturbing the mineral powder, heating the high-arsenic phosphate rock powder to 420-550 ℃, and performing high-temperature heat treatment to generate low-arsenic phosphate rock powder and arsenic-dust-containing flue gas;
(2) cooling low-arsenic phosphate rock powder, then leading out from a solid outlet of a boiling furnace, leading out arsenic-containing flue gas from a gas outlet of the boiling furnace, returning part of the arsenic-containing flue gas to the boiling furnace, and feeding the rest part of the arsenic-containing flue gas into a high-temperature ceramic dust remover for dust removal; returning the solid generated in the ceramic dust remover to a fluidized bed furnace for continuous high-temperature heat treatment;
(3) and introducing the clean arsenic gas obtained by dust removal into a condensing tower for cooling and crystallization to obtain solid arsenic trioxide.
Preferably, the condensate in the condensing tower is desalted water, and the spraying mode is atomizing spraying.
The arsenic removal method can change high-arsenic phosphorite with low economic value into high-grade phosphorite with high economic value, the arsenic removal rate is more than 80 percent, the phosphorus loss rate is less than 3 percent, the process flow is simple and easy to implement, white arsenic can be recycled, waste is changed into valuable, and the arsenic removal method has wide application prospect; furthermore, the invention utilizes the heat generated by the combustion of the high-concentration carbon monoxide in the yellow phosphorus tail gas to carry out high-temperature heat treatment on the high-arsenic phosphate rock powder, can further reduce the cost and can effectively utilize the yellow phosphorus tail gas.
The invention also provides a system for pre-dearsenifying the high-arsenic phosphorite. The system provided by the invention has a simple structure, and the system is used for pre-dearsenifying the high-arsenic phosphorite, so that the industrial production is easy to realize.
Drawings
FIG. 1 is a schematic view showing a process of pre-dearsenifying of highly arsenic phosphorite using the system of the present invention;
in fig. 1: 1-high arsenic phosphate ore bunker; 2-an ore crusher; 3-fluidized bed furnace; 4-blower number one; 5-blower number two; 6-a draught fan; 7-a ceramic dust remover; 8-second induced draft fan; 9-a cooling tower; 10-a baffle demister; 11-an atomizing sprayer; 12-a water pump; 13-high density bag-type dust collector;
a-yellow phosphorus tail gas; b-low arsenic phosphate rock powder; c-demineralized water; d-white arsenic; e-air.
Detailed Description
The invention provides a method for pre-dearsenifying high-arsenic phosphorite, which comprises the following steps:
carrying out high-temperature heat treatment on the high-arsenic phosphate rock powder to obtain low-arsenic phosphate rock powder and smoke containing arsenic dust; the temperature of the high-temperature heat is 420-550 ℃;
and (3) cooling and crystallizing the arsenic-containing flue gas after dedusting to obtain solid arsenic trioxide.
The invention has no special requirements on the high-arsenic phosphorite powder, and the high-arsenic phosphorite with the arsenic content of more than 10ppm, which is known to the technical personnel in the field, can be treated by the method of the invention.
In the invention, the granularity of the high-arsenic phosphate rock powder is preferably 100-600 μm, more preferably 100-300 μm, and the granularity of the high-arsenic phosphate rock powder is controlled in the range, so that the removal of arsenic is facilitated.
The invention carries out high-temperature heat treatment on the high-arsenic phosphorite powder to obtain low-arsenic phosphorite powder and smoke containing arsenic dust. In the invention, the temperature of the high-temperature heat treatment is 420-550 ℃, more preferably 490-530 ℃, and the time of the high-temperature heat treatment is preferably 0.5-1.5 h, more preferably 1 h; the heat of the high-temperature heat treatment is derived from the heat generated by the combustion of the yellow phosphorus tail gas; the yellow phosphorus tail gas contains high-concentration carbon monoxide. Arsenic in the high-arsenic ground phosphate rock reacts with oxygen at the temperature of 420-550 ℃ to generate gaseous arsenic trioxide, and the arsenic is separated from the ground phosphate rock through gas-solid phase separation, so that arsenic removal is realized.
In the invention, the residual solid after high-temperature heat treatment at 420-550 ℃ is low-arsenic phosphate rock powder, and the arsenic content of the obtained low-arsenic phosphate rock powder is lower than 5ppm, so that the arsenic content of the further prepared yellow phosphorus powder can be lower than 30ppm, and the yellow phosphorus powder can be used as an industrial raw material of a low-arsenic phosphorus product for industrial production.
After the high-temperature heat treatment is finished, the invention removes dust from the flue gas containing arsenic dust, and then carries out cooling crystallization to obtain solid arsenic trioxide. In the invention, the temperature for dedusting is 380-460 ℃, and more preferably 400-450 ℃; the cooling crystallization temperature is 180-220 ℃, and more preferably 190-200 ℃. In the invention, the arsenic-containing flue gas comprises gaseous arsenic trioxide and a small amount of small-particle powdered rock phosphate, the powdered rock phosphate is separated by dedusting, the part of powdered rock phosphate can be returned to the high-temperature heat treatment step for further dearsenification, the clean arsenic-containing flue gas after dedusting is gaseous arsenic trioxide, and the gaseous arsenic trioxide is crystallized at 180-220 ℃ to form solid arsenic trioxide (white arsenic).
In order to realize the dearsenification process, the invention also provides a system for pre-dearsenification of high-arsenic phosphorite, which comprises a fluidized bed furnace, a ceramic dust remover, a condensing tower and a blower.
In the invention, the fluidized bed furnace is provided with a solid inlet, a solid outlet, a gas inlet and a gas outlet; the gas inlet is used for introducing yellow phosphorus tail gas and air; in the present invention, the gas inlet is preferably provided at the bottom end of the fluidized bed furnace; and a gas outlet of the fluidized bed furnace is communicated with a gas inlet, and is used for realizing flue gas circulation. The invention has no special requirements on the specific structure of the boiling furnace, and the boiling furnace which is well known by the technical personnel in the field can be used; in a specific embodiment of the invention, the fluidized bed furnace is preferably divided into a lower space and an upper space, the upper space and the lower space are separated by a grid, high-arsenic phosphate rock powder is placed on the grid and positioned in the upper space, the lower space is used for burning yellow phosphorus tail gas, the yellow phosphorus tail gas is burned in the lower space of the fluidized bed furnace, the generated heat heats the high-arsenic phosphate rock powder, and because the lower space of the fluidized bed furnace is longer and the grid exists, the flame generated by the high-arsenic phosphate rock powder and the yellow phosphorus tail gas cannot be in direct contact, so that the introduced yellow phosphorus tail gas cannot influence the air atmosphere of the upper layer of the fluidized bed furnace.
In the invention, the ceramic dust remover is provided with a gas inlet, a gas outlet and a solid outlet; the gas inlet of the ceramic dust remover is communicated with the gas outlet of the fluidized bed furnace; and a solid outlet of the ceramic dust remover is communicated with a solid inlet of the fluidized bed furnace. The present invention has no special requirement on the specific structure of the ceramic dust remover, and the ceramic dust remover known to those skilled in the art can be used.
In the invention, the condensing tower is provided with a gas inlet, a gas outlet, a liquid inlet and a solid outlet; and a gas inlet of the condensing tower is communicated with a gas outlet of the ceramic dust collector, and a gas outlet of the condensing tower is arranged at the top of the tower and used for discharging air. In the present invention; a baffling demisting plate and an atomizing sprayer are arranged in the condensing tower, and a liquid inlet of the condensing tower is communicated with a water pump and used for conveying demineralized water into the condensing tower; the present invention does not require a special structure for the condensing tower, and a condensing tower known to those skilled in the art can be used.
The air blower comprises a first air blower and a second air blower, the air blower is communicated with a gas inlet of the fluidized bed furnace, the first air blower is used for blowing air to yellow phosphorus tail gas flame at the lower layer of the fluidized bed furnace to support combustion, and the second air blower is used for introducing air to the upper part of the yellow phosphorus tail gas flame to disturb high-arsenic phosphate rock powder, so that the high-arsenic phosphate rock powder is heated more uniformly, meanwhile, the temperature of a hearth can be adjusted, and the high-temperature thermal condition is controlled.
In the invention, the system preferably further comprises a first induced draft fan and a second induced draft fan, wherein the first induced draft fan is arranged on a pipeline communicated with the gas outlet and the gas inlet of the fluidized bed furnace, and the second induced draft fan is arranged on a pipeline communicated with the solid outlet and the solid inlet of the fluidized bed furnace of the ceramic dust remover. The invention realizes the circulation of gas and solid between devices by arranging the first induced draft fan and the second induced draft fan.
In the invention, the system preferably further comprises a high-arsenic phosphorite bin and an ore crusher which are communicated in sequence; the high arsenic phosphorus phosphate ore is crushed to the required granularity in an ore crusher and then is conveyed to a fluidized bed furnace.
In the present invention, the system preferably further comprises a high density bag house comprising a gas inlet, a gas outlet and a solids outlet; and a gas inlet of the high-density bag type dust collector is communicated with a gas outlet of the condensing tower. The invention has no special requirements on the specific structure of the high-density bag-type dust collector, and the high-density bag-type dust collector well known to the technical personnel in the field can be used.
When the device is used for pre-dearsenifying the high arsenic phosphorite, the method comprises the following steps:
the method comprises the steps of conveying high-arsenic phosphate rock powder into a fluidized bed furnace, introducing yellow phosphorus tail gas at the bottom end of the fluidized bed furnace for combustion, introducing air for combustion supporting by using a first air blower, introducing air by using a second air blower, controlling temperature, disturbing mineral powder and adjusting the temperature in the fluidized bed furnace; the high arsenic phosphate rock powder is heated for high temperature heat treatment to produce low arsenic phosphate rock powder and smoke containing arsenic dust. In the present invention, the temperature and time of the high temperature heat treatment are the same as those of the above scheme, and are not described herein again. In the present invention, the time of the high-temperature heat treatment is calculated from the time after heating to a desired temperature.
In the embodiment of the invention, the yellow phosphorus tail gas flow rate and the air flow rate are preferably adjusted according to the processing amount of the ground phosphate rock, the arsenic content in the phosphate rock, the processing time and the required temperature, so that the temperature of the high-temperature heat treatment can meet the requirements.
After the high-temperature heat treatment is finished, the low-arsenic ground phosphate rock is cooled and then is led out from a solid outlet of a boiling furnace, the arsenic-containing flue gas is led out from a gas outlet of the boiling furnace, then part of the arsenic-containing flue gas is returned to the boiling furnace, and the rest part of the arsenic-containing flue gas enters a ceramic dust remover for dust removal. In the invention, part of the flue gas containing arsenic dust is returned to the fluidized bed furnace to play a role in regulating and controlling the temperature in the fluidized bed furnace, and the volume of the flue gas containing arsenic dust returned to the fluidized bed furnace is preferably 20-60% of the total volume of the flue gas containing arsenic dust. The method is characterized in that air is continuously introduced before the low-arsenic ground phosphate rock is led out (at the moment, yellow phosphorus tail gas combustion is stopped), so that the low-arsenic ground phosphate rock is cooled to a proper temperature and then led out, and after the low-arsenic ground phosphate rock is led out, the next batch of high-arsenic ground phosphate rock is input into the fluidized bed furnace.
In the invention, because a large amount of air is introduced into the fluidized bed furnace for disturbance, a part of small-particle powdered rock phosphate can be led out along with the flue gas, the small-particle powdered rock phosphate in the flue gas containing arsenic dust can be removed through dust removal treatment, and the powdered rock phosphate obtained through dust removal can be returned to the fluidized bed furnace for continuous high-temperature heat treatment so as to further remove the arsenic in the flue gas. In the invention, the temperature of the flue gas containing arsenic dust passing through the ceramic dust remover is consistent with the dust removal temperature in the scheme, and the description is omitted.
And introducing the clean arsenic gas obtained by dust removal into a condensing tower for cooling and crystallization to obtain solid arsenic trioxide. In the invention, the condensate in the condensing tower is preferably desalted water, and the spraying mode is preferably atomized spraying; the temperature of the cooling crystallization is consistent with the scheme, and the description is omitted.
In the invention, the cooled and crystallized smoke is discharged from a gas outlet of the condensing tower and enters the high-density bag type dust collector, the smoke discharged from the condensing tower can contain very few white arsenic particles with smaller particles besides air, the part of the white arsenic is separated and recycled by the high-density bag type dust collector, and the air is discharged into the atmosphere from the gas outlet of the high-density bag type dust collector. In the invention, the dust collection temperature of the high-density bag-type dust collector is about 150 ℃, and is consistent with the temperature of the flue gas discharged from the condensing tower.
The process of the present invention is specifically described below with reference to FIG. 1: high arsenic phosphate ore enters an ore crusher 2 from a high arsenic phosphate ore storage bin 1, the high arsenic phosphate ore enters a fluidized bed furnace 3 from a solid inlet, yellow phosphorus tail gas A enters the bottom end of the fluidized bed furnace 3 from a gas inlet for combustion, a first air blower 5 introduces air to a combustion position for supporting combustion, a second air blower 4 introduces air above flame for disturbing the high arsenic phosphate ore powder and adjusting the temperature of a hearth, after high-temperature heat treatment is completed, low arsenic phosphate ore powder B is discharged from a solid outlet of the fluidized bed furnace 3, smoke containing arsenic dust is discharged from a gas outlet of the fluidized bed furnace 3, the rear part of the smoke containing arsenic dust returns to the fluidized bed furnace 3 through a first induced draft fan 6, the rest of the smoke enters a ceramic dust collector 7, after dust removal in the ceramic dust collector 7 is completed, the generated solid returns to the fluidized bed furnace 3 through a second induced draft fan 8 for repeated arsenic removal, clean arsenic gas gets into and cools off the crystallization in condensing tower 9, and demineralized water C is carried to water pump 12 in to condensing tower 9, and white arsenic D that produces after the crystallization is discharged from the solid export of condensing tower 9, and exhaust flue gas gets into high density sack cleaner 13 in the condensing tower 9, retrieves white arsenic D from the solid export of high density sack cleaner 13, and air E is discharged from the gas outlet of high density sack cleaner 13.
The method provided by the invention has the advantages of simple dearsenification process, no pollution to the environment, capability of recovering white arsenic, easy realization of industrial production and industrial value by utilizing the system for dearsenification.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The high-arsenic phosphorite is crushed into high-arsenic phosphorite powder in a crusher and then conveyed into a fluidized bed furnace, yellow phosphorus tail gas is introduced and combusted at the bottom of the fluidized bed furnace, and a large amount of heat is generated to heat the high-arsenic phosphorite powder. In the combustion process of the yellow phosphorus tail gas, air is introduced by an air blower to support combustion, and the ground phosphorite is disturbed to be fully heated to 480 ℃, arsenic is oxidized into gaseous arsenic trioxide, and arsenic dust is formed. After the heating time of 0.5h, the low-arsenic phosphorite powder generated after the reaction and arsenic dust flue gas containing a small amount of phosphorite powder are led out of the fluidized bed furnace. Passing the arsenic dust fume containing phosphorus ore powder through a ceramic filter dust collector, wherein the filtering temperature is 400 ℃, returning the collected and treated phosphorus ore powder to a fluidized bed furnace for continuous arsenic removal, and simultaneously collecting and guiding clean arsenic dust gas into a condensing tower. Gas enters from the lower part of the condensing tower, condensate is sprayed from the upper part of the condensing tower through the atomizing nozzle, the cooling temperature is 180 ℃ through the bottom end temperature detector, and arsenic trioxide in the guided gas is cooled and crystallized to become white arsenic.
Example 2
The high-arsenic phosphorite is crushed into high-arsenic phosphorite powder in a crusher and then conveyed into a fluidized bed furnace, yellow phosphorus tail gas is introduced and combusted at the bottom of the fluidized bed furnace, and a large amount of heat is generated to heat the high-arsenic phosphorite powder. In the combustion process of the yellow phosphorus tail gas, air is introduced through an air blower to support combustion, and meanwhile, the ground phosphorite is disturbed to be fully heated to 480 ℃, arsenic is oxidized into gaseous arsenic trioxide, and arsenic dust is formed. After 1.5h of heating time, the low-arsenic phosphate rock powder produced after the reaction and arsenic dust flue gas containing a small amount of phosphate rock powder are led out of the fluidized bed furnace. Passing the arsenic dust fume containing phosphorus ore powder through a ceramic filter dust collector, wherein the filtering temperature is 400 ℃, returning the collected and treated phosphorus ore powder to a fluidized bed furnace for continuous arsenic removal, and simultaneously collecting and guiding clean arsenic dust gas into a condensing tower. Gas enters from the lower part of the condensing tower, condensate is sprayed from the upper part of the condensing tower through the atomizing nozzle, the cooling temperature is 200 ℃ through the bottom end temperature detector, and arsenic trioxide in the guided gas is cooled and crystallized to become white arsenic.
Example 3
The high-arsenic phosphorite is crushed into high-arsenic phosphorite powder in a crusher and then conveyed into a fluidized bed furnace, yellow phosphorus tail gas is introduced and combusted at the bottom of the fluidized bed furnace, and a large amount of heat is generated to heat the high-arsenic phosphorite powder. In the combustion process of the yellow phosphorus tail gas, air is introduced through an air blower to support combustion, and meanwhile, the ground phosphorite is disturbed to be fully heated to 530 ℃, arsenic is oxidized into gaseous arsenic trioxide, and arsenic dust is formed. After the heating time of 0.5h, the low-arsenic phosphorite powder generated after the reaction and arsenic dust flue gas containing a small amount of phosphorite powder are led out of the fluidized bed furnace. Passing the arsenic dust fume containing phosphorus ore powder through a ceramic filter dust collector, wherein the filtering temperature is 400 ℃, returning the collected and treated phosphorus ore powder to a fluidized bed furnace for continuous arsenic removal, and simultaneously collecting and guiding clean arsenic dust gas into a condensing tower. Gas enters from the lower part of the condensing tower, condensate is sprayed from the upper part of the condensing tower through the atomizing nozzle, the cooling temperature is 200 ℃ through the bottom end temperature detector, and arsenic trioxide in the guided gas is cooled and crystallized to become white arsenic.
Example 4
The high-arsenic phosphorite is crushed into high-arsenic phosphorite powder in a crusher and then conveyed into a fluidized bed furnace, yellow phosphorus tail gas is introduced and combusted at the bottom of the fluidized bed furnace, and a large amount of heat is generated to heat the high-arsenic phosphorite powder. In the combustion process of the yellow phosphorus tail gas, air is introduced through an air blower to support combustion, and meanwhile, the ground phosphorite is disturbed to be fully heated to 530 ℃, arsenic is oxidized into gaseous arsenic trioxide, and arsenic dust is formed. After 1.5h of heating time, the low-arsenic phosphate rock powder produced after the reaction and arsenic dust flue gas containing a small amount of phosphate rock powder are led out of the fluidized bed furnace. Passing the arsenic dust fume containing phosphorus ore powder through a ceramic filter dust collector, wherein the filtering temperature is 430 ℃, returning the collected and treated phosphorus ore powder to a fluidized bed furnace for continuous arsenic removal, and simultaneously collecting and guiding clean arsenic dust gas into a condensing tower. Gas enters from the lower part of the condensing tower, condensate is sprayed from the upper part of the condensing tower through the atomizing nozzle, the cooling temperature is 200 ℃ through the bottom end temperature detector, and arsenic trioxide in the guided gas is cooled and crystallized to become white arsenic.
Example 5
The high-arsenic phosphorite is crushed into high-arsenic phosphorite powder in a crusher and then conveyed into a fluidized bed furnace, yellow phosphorus tail gas is introduced and combusted at the bottom of the fluidized bed furnace, and a large amount of heat is generated to heat the high-arsenic phosphorite powder. In the combustion process of the yellow phosphorus tail gas, air is introduced through an air blower to support combustion, and meanwhile, the ground phosphorite is disturbed to be fully heated to 530 ℃, arsenic is oxidized into gaseous arsenic trioxide, and arsenic dust is formed. After the heating time of 0.5h, the low-arsenic phosphorite powder generated after the reaction and arsenic dust flue gas containing a small amount of phosphorite powder are led out of the fluidized bed furnace. Passing the arsenic dust fume containing phosphorus ore powder through a ceramic filter dust collector, wherein the filtering temperature is 430 ℃, returning the collected and treated phosphorus ore powder to a fluidized bed furnace for continuous arsenic removal, and simultaneously collecting and guiding clean arsenic dust gas into a condensing tower. Gas enters from the lower part of the condensing tower, condensate is sprayed from the upper part of the condensing tower through the atomizing nozzle, the cooling temperature is 200 ℃ through the bottom end temperature detector, and arsenic trioxide in the guided gas is cooled and crystallized to become white arsenic.
Example 6
The high-arsenic phosphorite is crushed into high-arsenic phosphorite powder in a crusher and then conveyed into a fluidized bed furnace, yellow phosphorus tail gas is introduced and combusted at the bottom of the fluidized bed furnace, and a large amount of heat is generated to heat the high-arsenic phosphorite powder. In the combustion process of the yellow phosphorus tail gas, air is introduced through an air blower to support combustion, and meanwhile, the ground phosphorite is disturbed to be fully heated to 530 ℃, arsenic is oxidized into gaseous arsenic trioxide, and arsenic dust is formed. After 1.5h of heating time, the low-arsenic phosphate rock powder produced after the reaction and arsenic dust flue gas containing a small amount of phosphate rock powder are led out of the fluidized bed furnace. Passing the arsenic dust fume containing phosphorus ore powder through a ceramic filter dust collector, wherein the filtering temperature is 430 ℃, returning the collected and treated phosphorus ore powder to a fluidized bed furnace for continuous arsenic removal, and simultaneously collecting and guiding clean arsenic dust gas into a condensing tower. Gas enters from the lower part of the condensing tower, condensate is sprayed from the upper part of the condensing tower through the atomizing nozzle, the cooling temperature is 200 ℃ through the bottom end temperature detector, and arsenic trioxide in the guided gas is cooled and crystallized to become white arsenic.
The test results of the pre-dearsenification of the high arsenic phosphorites of examples 1-6 are shown in Table 1:
TABLE 1 EXAMPLES 1 TO 6 PRE-DESARINATION TEST RESULTS FOR HIGH-As PHOSPHOROUS ORGANES
According to the table, the arsenic removal rate of the arsenic removal method is more than 80%, the phosphorus loss rate is less than 3%, the yield of white arsenic is more than 80%, the process flow is simple and easy to implement, the economic cost is saved, meanwhile, the white arsenic can be recovered, the waste is changed into valuable, secondary pollution is not generated, and the method has a wide application prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The method for pre-dearsenifying the high-arsenic phosphorite is characterized by comprising the following steps of:
(1) conveying high-arsenic phosphate rock powder into a fluidized bed furnace, introducing yellow phosphorus tail gas at the bottom end of the fluidized bed furnace for combustion, introducing air for combustion supporting by using a first air blower, introducing air by using a second air blower, controlling temperature, and disturbing the mineral powder; heating the high-arsenic phosphate rock powder to 420-550 ℃ for high-temperature heat treatment to obtain low-arsenic phosphate rock powder and arsenic-dust-containing flue gas; the particle size of the high-arsenic phosphate rock powder is 100-600 mu m;
(2) cooling low-arsenic phosphate rock powder, then leading out from a solid outlet of a boiling furnace, leading out arsenic-containing flue gas from a gas outlet of the boiling furnace, returning part of the arsenic-containing flue gas to the boiling furnace, and feeding the rest part of the arsenic-containing flue gas into a high-temperature ceramic dust remover for dust removal; returning the solid generated in the ceramic dust remover to a fluidized bed furnace for continuous high-temperature heat treatment;
(3) introducing the clean arsenic gas obtained by dust removal into a condensing tower for cooling and crystallization to obtain solid arsenic trioxide;
the system for pre-dearsenifying the high-arsenic phosphorite comprises a fluidized bed furnace, a ceramic dust remover, a condensing tower and a blower;
the fluidized bed furnace is provided with a solid inlet, a solid outlet, a gas inlet and a gas outlet; the gas inlet is used for introducing yellow phosphorus tail gas and air; the gas outlet of the fluidized bed furnace is communicated with the gas inlet;
the ceramic dust remover is provided with a gas inlet, a gas outlet and a solid outlet; the gas inlet of the ceramic dust remover is communicated with the gas outlet of the fluidized bed furnace; the solid outlet of the ceramic dust remover is communicated with the solid inlet of the fluidized bed furnace;
the condensing tower is provided with a gas inlet, a gas outlet, a liquid inlet and a solid outlet; the gas inlet of the condensing tower is communicated with the gas outlet of the ceramic dust collector;
the air blower comprises a first air blower and a second air blower, and the air blowers are communicated with a gas inlet of the boiling furnace and are used for blowing air into the boiling furnace.
2. The method according to claim 1, wherein the high temperature heat treatment time is 0.5-1.5 h; the heat of the high-temperature heat treatment is derived from the heat generated by the combustion of the yellow phosphorus tail gas.
3. The method according to claim 1, wherein the temperature of the dust removal is 380-460 ℃; the temperature of the cooling crystallization is 180-220 ℃.
4. The method of claim 1, wherein the system further comprises a high arsenic phosphate ore storage bin and an ore crusher in serial communication; and the outlet of the ore crusher is communicated with the solid inlet of the fluidized bed furnace.
5. The method of claim 1 or 4, wherein the system further comprises a high density bag house comprising a gas inlet, a gas outlet, and a solids outlet; and a gas inlet of the high-density bag type dust collector is communicated with a gas outlet of the condensing tower.
6. The method as claimed in claim 1, wherein the condensate in the condensing tower is desalted water, and the spraying manner is atomized spraying.
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| CN111217345A (en) * | 2020-02-28 | 2020-06-02 | 成都易态科技有限公司 | Yellow phosphorus furnace gas preparation device, yellow phosphorus condensation system and yellow phosphorus furnace gas preparation method |
| CN114455558B (en) * | 2022-03-21 | 2024-06-18 | 东华工程科技股份有限公司 | Deep arsenic removal system for arsenic-containing phosphoric acid |
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| SU1472439A1 (en) * | 1987-02-04 | 1989-04-15 | Волжский Филиал Ленинградского Государственного Научно-Исследовательского И Проектного Института Основной Химической Промышленности | Method of sintering initial phosphate stock |
| CN101078057A (en) * | 2007-06-26 | 2007-11-28 | 山东恒邦冶炼股份有限公司 | Method for smelting arsenic-containing gold concentrate |
| CN101492177B (en) * | 2009-03-09 | 2010-11-10 | 昆明理工大学 | Method for reduction and decomposition of phosphogypsum with yellow phosphorus tail gas |
| CN101774553B (en) * | 2010-03-26 | 2012-01-11 | 成都高威节能科技有限公司 | Method for calcining raw materials in furnace in yellow phosphorus production |
| CN103030124B (en) * | 2011-12-16 | 2014-12-31 | 湖北兴发化工集团股份有限公司 | Method for preparing food-grade phosphoric acid from medium/low-grade phosphorite |
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