CN109928367B - Device and method for preparing sulfur from phosphogypsum - Google Patents
Device and method for preparing sulfur from phosphogypsum Download PDFInfo
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- CN109928367B CN109928367B CN201910306980.0A CN201910306980A CN109928367B CN 109928367 B CN109928367 B CN 109928367B CN 201910306980 A CN201910306980 A CN 201910306980A CN 109928367 B CN109928367 B CN 109928367B
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Abstract
The invention belongs to the technical field of resource utilization and environmental protection, and particularly relates to a device and a method for preparing sulfur from phosphogypsum. The sulfur reaction rotary kiln, the quencher, the heat exchanger, the sulfur cooler and the cooling washer are designed, and the device for preparing the sulfur by the phosphogypsum is formed together with the existing equipment (the ball mill, the bucket elevator, the electric dust remover and the tail gas blower), the device can prepare the sulfur by taking the waste phosphogypsum as a raw material and co-produce the phosphorus-containing soil conditioner, so that the resource utilization is realized, and a new way is opened up for the comprehensive utilization of the phosphogypsum; the device and the method have no secondary pollution in the process of preparing the sulfur, and are environment-friendly production technology; the scheme of the invention can fully utilize energy, has low energy consumption and low operation cost, and has better economic benefit.
Description
Technical Field
The invention relates to the technical field of resource utilization and environmental protection, in particular to a device and a method for preparing sulfur from phosphogypsum.
Background
Phosphoric acid is the main raw material for producing high-concentration phosphorus compound fertilizer (such as diammonium phosphate, monoammonium phosphate, heavy calcium, phosphate compound fertilizer, etc.), and 1 ton phosphoric acid (100% P is used for preparing phosphoric acid)2O5Calculated) produces about 4.5 to 5.5 tons (dry basis) of phosphogypsum.
In 2011, 6750 million tons of Chinese by-product phosphogypsum increases the emission of the phosphogypsum at a speed of 5-10% every year at present, the accumulated stockpiling quantity of the Chinese phosphogypsum exceeds 30000 million tons, but the comprehensive utilization rate is less than 20% of the annual output. In 2012, the phosphogypsum inventory in China is close to 4 hundred million tons, which causes great threat to the environment. The utilization of the phosphogypsum is a worldwide problem, and the problems brought to enterprises and the nature by the emission and stockpiling of the phosphogypsum are highly valued. Meanwhile, the contradiction between resource waste caused by stacking and laying of the phosphogypsum and the large-scale exploitation of natural gypsum is increasingly prominent, and the resource recycling of the phosphogypsum is imperative.
The development time of the comprehensive utilization technology of the phosphogypsum has been about 40 years. Over the years, through the continuous efforts of the majority of researchers, the development of phosphogypsum resource utilization technology has progressed, particularly, the development is faster in recent years, and the main application approaches comprise the co-production of sulfuric acid and cement by using the phosphogypsum, cement retarder, gypsum brick, building block, gypsum plaster board, building gypsum powder, filling of mine goaf, producing potassium sulfate, soil conditioner, co-production of ammonium sulfate and lime and the like. At present, although several production lines for co-producing sulfuric acid and cement by using phosphogypsum are built in China, the production lines are difficult to popularize due to the problems of high energy consumption, poor cement quality, high calcination temperature, difficult operation, poor benefit and the like.
Therefore, the search for a new phosphogypsum utilization technology has important significance for the sustainable development of the phosphorus compound fertilizer industry.
Disclosure of Invention
The invention aims to provide a device and a method for preparing sulfur from phosphogypsum, the device can realize the preparation of sulfur from waste phosphogypsum and the co-production of a phosphorus-containing soil conditioner, and opens up a new way for the comprehensive utilization of the phosphogypsum.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a device for preparing sulfur from phosphogypsum, which comprises a phosphogypsum storage tank 1, a reducing agent storage tank 2, a batching storage tank 3, a ball mill 4, a bucket elevator 5, a sulfur reaction rotary kiln 6, a heat exchanger 8, an electric dust remover 9, a sulfur cooler 10, a cooling washer 11, a tail gas blower 13, a combustor 14 and an air blower 15; the phosphogypsum storage tank 1, the reducing agent storage tank 2 and the ingredient storage tank 3 are respectively communicated with a ball mill 4, and the ball mill 4, a bucket elevator 5 and the kiln head of a sulfur reaction rotary kiln 6 are sequentially communicated; the kiln head and the heat exchanger 8 intercommunication of sulphur reaction rotary kiln 6, heat exchanger 8, electrostatic precipitator 9, sulphur cooler 10, cooling scrubber 11 and tail gas air-blower 13 communicate in order, the export of tail gas air-blower 13 with combustor 14 intercommunication, the export of combustor 14 with the kiln tail intercommunication of sulphur reaction rotary kiln 6, the export of air-blower 15 with combustor 14 intercommunication.
Preferably, the sulfur reaction rotary kiln further comprises a quencher 7, and the quencher 7 is communicated with the kiln tail of the sulfur reaction rotary kiln 6.
Preferably, a washing pump 12 is further included, the washing pump 12 being in communication with the cooling scrubber 11.
The invention provides a method for preparing sulfur by using the device in the technical scheme, which comprises the following steps:
respectively conveying the phosphogypsum, the reducing agent and the ingredients in the phosphogypsum storage tank 1, the reducing agent storage tank 2 and the ingredient storage tank 3 into a ball mill 4 for grinding to obtain a mixed grinding material;
conveying the mixed powder grinding material to a sulfur reaction rotary kiln 6 by using a bucket elevator 5, and carrying out decomposition reduction reaction to obtain a mineral material and sulfur tail gas;
sending the sulfur tail gas into a heat exchanger 8, sending part of the sulfur tail gas in the heat exchanger 8 into an electric dust remover 9 for dust removal, sending the obtained sulfur tail gas after dust removal into a sulfur cooler 10 for cooling, and separating to obtain sulfur and cold sulfur tail gas;
sending the cold sulfur tail gas into a cooling scrubber 11 for purification to obtain cold purified sulfur tail gas;
sending the cold-purified sulfur tail gas into a heat exchanger 8 through a tail gas blower 13, and exchanging heat with the residual sulfur tail gas in the heat exchanger 8 until the temperature of the cold-purified sulfur tail gas is increased to 250-300 ℃ to obtain hot-purified sulfur tail gas;
and (3) feeding the thermally purified sulfur tail gas into a combustor 14 to be mixed with air from an air blower 15, and conveying the obtained mixed gas into a sulfur reaction rotary kiln 6 for combustion to supply heat for the decomposition reduction reaction.
Preferably, the reducing agent is coke or anthracite.
Preferably, the mass ratio of the phosphogypsum to the reducing agent is 100: 21-22.
Preferably, the ingredients are manganese ore powder, bentonite or magnesite powder, and the mass ratio of the phosphogypsum to the ingredients is 1: 0.05-0.1.
Preferably, the rotation speed of the kiln cylinder of the sulfur reaction rotary kiln 6 is 1-2 r/min.
Preferably, the mineral material is fed to a chiller 7 for cooling to obtain a soil conditioner.
Preferably, the temperature of the decomposition reduction reaction is 1150-1250 ℃ and the time is 40-60 min.
The invention provides a device and a method for preparing sulfur by phosphogypsum, wherein a sulfur reaction rotary kiln, a quencher, a heat exchanger, a sulfur cooler and a cooling washer are designed, and compared with the device for preparing sulfur by phosphogypsum which is formed by the existing equipment (a ball mill, a bucket elevator, an electric dust remover and a tail gas blower) together, the device can prepare sulfur by taking waste phosphogypsum as a raw material and co-producing a phosphorus-containing soil conditioner, thereby realizing resource utilization and opening up a new way for the comprehensive utilization of the phosphogypsum;
the device and the method have no secondary pollution in the process of preparing the sulfur, and are environment-friendly production technology;
the scheme of the invention can fully utilize energy, has low energy consumption and low operation cost, and has better economic benefit.
Drawings
FIG. 1 is a schematic structural diagram of a device for preparing sulfur from phosphogypsum, wherein a 1-phosphogypsum storage tank is arranged in the device; 2-a reducing agent storage tank and 3-a batching storage tank; 4-ball mill; 5-bucket elevator; 6-sulfur reaction rotary kiln; 7-a quencher; 8-a heat exchanger; 9-an electric dust collector, 10-a sulfur cooler, 11-a cooling washer and 12-a washing pump; 13-tail gas blower, 14-burner; 15-air blower.
Detailed Description
The invention provides a device for preparing sulfur from phosphogypsum, which comprises a phosphogypsum storage tank 1, a reducing agent storage tank 2, a batching storage tank 3, a ball mill 4, a bucket elevator 5, a sulfur reaction rotary kiln 6, a heat exchanger 8, an electric dust remover 9, a sulfur cooler 10, a cooling washer 11, a tail gas blower 13, a combustor 14 and an air blower 15; the phosphogypsum storage tank 1, the reducing agent storage tank 2 and the ingredient storage tank 3 are respectively communicated with a ball mill 4, and the ball mill 4, a bucket elevator 5 and the kiln head of a sulfur reaction rotary kiln 6 are sequentially communicated; the kiln head and the heat exchanger 8 intercommunication of sulphur reaction rotary kiln 6, heat exchanger 8, electrostatic precipitator 9, sulphur cooler 10, cooling scrubber 11 and tail gas air-blower 13 communicate in order, the export of tail gas air-blower 13 with combustor 14 intercommunication, the export of combustor 14 with the kiln tail intercommunication of sulphur reaction rotary kiln 6, the export of air-blower 15 with combustor 14 intercommunication.
As an embodiment of the invention, the device for preparing sulfur from phosphogypsum further comprises a quencher 7, wherein the quencher 7 is communicated with the kiln tail of the sulfur reaction rotary kiln 6.
As an embodiment of the invention, the device for preparing the sulfur by the phosphogypsum further comprises a washing pump 12, and the washing pump 12 is communicated with the cooling washer 11.
As an embodiment of the invention, the sulfur reaction rotary kiln comprises a kiln head, a kiln cylinder body and a kiln tail. As an embodiment of the invention, the kiln head is fixed, the kiln head is lined with refractory bricks, and a burner is arranged at the kiln head; the kiln cylinder is in a rotary type, the kiln cylinder is made of a carbon steel plate and lined with refractory bricks, and the rotary speed of the kiln cylinder is preferably 1-2 r/min; the kiln tail is fixed, refractory bricks are lined in the kiln tail, a feeder is arranged at the kiln tail and used for feeding phosphogypsum, a reducing agent and ingredients, and the feeders feed materials according to respective proportions.
The invention provides a method for preparing sulfur by using the device in the technical scheme, which comprises the following steps:
respectively conveying the phosphogypsum, the reducing agent and the ingredients in the phosphogypsum storage tank 1, the reducing agent storage tank 2 and the ingredient storage tank 3 into a ball mill 4 for grinding to obtain a mixed grinding material;
conveying the mixed powder grinding material to a sulfur reaction rotary kiln 6 by using a bucket elevator 5, and carrying out decomposition reduction reaction to obtain a mineral material and sulfur tail gas;
sending the sulfur tail gas into a heat exchanger 8, sending part of the sulfur tail gas in the heat exchanger 8 into an electric dust remover 9 for dust removal, sending the obtained sulfur tail gas after dust removal into a sulfur cooler 10 for cooling, and separating to obtain sulfur and cold sulfur tail gas;
sending the cold sulfur tail gas into a cooling scrubber 11 for purification to obtain cold purified sulfur tail gas;
sending the cold-purified sulfur tail gas into a heat exchanger 8 through a tail gas blower 13, and exchanging heat with the residual sulfur tail gas in the heat exchanger 8 until the temperature of the cold-purified sulfur tail gas is increased to 250-300 ℃ to obtain hot-purified sulfur tail gas;
and (3) feeding the thermally purified sulfur tail gas into a combustor 14 to be mixed with air from an air blower 15, and conveying the obtained mixed gas into a sulfur reaction rotary kiln 6 for combustion to supply heat for the decomposition reduction reaction.
The phosphogypsum, the reducing agent and the ingredients in the phosphogypsum storage tank 1, the reducing agent storage tank 2 and the ingredient storage tank 3 are respectively conveyed into a ball mill 4 for grinding to obtain a mixed grinding material. In the invention, the mass ratio of the phosphogypsum to the reducing agent is preferably 100: 21-22; the ingredients are preferably manganese ore powder, bentonite or magnesite powder, and the mass ratio of the phosphogypsum to the ingredients is preferably 1: 0.05-0.1, and more preferably 1: 0.06-0.08. In the present invention, the particle size of the pulverized material is preferably 160 meshes or less, and more preferably 50 to 100 meshes.
After the mixed ground material is obtained, the invention uses a bucket elevator 5 to convey the ground material into a sulfur reaction rotary kiln 6 for decomposition reduction reaction to obtain mineral material and sulfur tail gas. According to the invention, the ground material is preferably added through the kiln head of the sulfur reaction rotary kiln, then combustion gas is used for providing heat in the combustor 4, the ground material moves to the kiln tail by using the inclination of the sulfur reaction rotary kiln and the rotation of the sulfur reaction rotary kiln, and when the temperature is increased to 1150-1250 ℃, the decomposition reduction reaction of phosphogypsum is carried out, so that the mineral material and the sulfur tail gas are obtained.
In the process of decomposition reduction reaction, the phosphogypsum and a reducing agent are subjected to the following two-step reaction:
first step CaSO4+2C＝CaS+2CO2
Second step 3CaS + CaSO4＝4CaO+2S2
Total reaction 2CaSO4+4C+O2＝2CaO+S2+4CO2
In the invention, the sulfur reaction rotary kiln preferably operates under the micro-positive pressure (200 Pa-300 Pa), and external air is not sucked in the operation process, namely, the decomposition reduction reaction of the phosphogypsum is carried out in the reduction environment isolated from air.
In the invention, the main components of the mineral materials are CaO, SiO2 and MgO, and the mineral materials have the characteristics of the soil conditioner, and the soil conditioner is preferably obtained by cooling the mineral materials in a quencher 7 to below 50 ℃, screening and packaging.
In the process of the decomposition reduction reaction, the carbon (reducing agent) used in the invention is excessive, the residual carbon can react with the carbon dioxide generated in the process of the decomposition reduction reaction again to generate carbon monoxide, and tail gas containing CO and sulfur is generated at the kiln tail of the sulfur reaction rotary kiln and is called sulfur tail gas.
After the mineral material and the sulfur tail gas are obtained, the sulfur tail gas is sent into a heat exchanger 8, part of the sulfur tail gas in the heat exchanger 8 is sent into an electric dust remover 9 for dust removal, the obtained sulfur tail gas after dust removal is sent into a sulfur cooler 10 for cooling, and sulfur and cold sulfur tail gas are obtained through separation. In the invention, the dust content in the tail gas after dust removal is less than 20mg/m3. In the invention, the sulfur cooler is a vertical tube type, cooling water is arranged outside the tube, tail gas after dust removal is arranged inside the tube, the tail gas after dust removal is cooled to be below 80 ℃ (cold sulfur tail gas), sulfur steam in the tail gas is condensed into powdery sulfur, and the powdery sulfur is discharged from the bottom of the sulfur cooler to obtain a sulfur product. According to the invention, ammonia water with mass concentration of 8-10% is preferably used for washing the cold sulfur tail gas, SO that SO in the tail gas is removed2And recovering the sulfur carried out with the tail gas from the sulfur cooler.
After sulfur and cold sulfur tail gas are obtained, the cold sulfur tail gas is sent into a cooling washer 11 for purification to obtain cold purified sulfur tail gas; and (3) sending the cold-purified sulfur tail gas into the heat exchanger 8 through the tail gas blower 13, and exchanging heat with the residual sulfur tail gas in the heat exchanger 8 until the temperature of the cold-purified sulfur tail gas is increased to 250-300 ℃ to obtain the hot-purified sulfur tail gas. In the invention, the temperature of the cold sulfur tail gas is 35-40 ℃, after heat exchange, the temperature of the rest sulfur tail gas is reduced to 220-250 ℃, and the temperature of the hot purified sulfur tail gas obtained after heat exchange is 250-300 ℃. The invention preferably automatically quantifies the proportion of the sulfur tail gas entering the tail gas blower to the residual sulfur tail gas according to the requirement of the temperature of the kiln head.
After the thermally purified sulfur tail gas is obtained, the thermally purified sulfur tail gas is sent into a combustor 14 to be mixed with air from an air blower 15, and the obtained mixed gas is sent into a sulfur reaction rotary kiln 6 to be combusted so as to supply heat for the decomposition reduction reaction. In the invention, the hot purified sulfur tail gas is preferably pressurized to 5kPa and then sent into a combustor to be mixed with air from an air blower 15 for combustion so as to meet the heat required by the sulfur reaction rotary kiln. In the invention, the consumption of the heat-purified sulfur tail gas required by the burner is automatically controlled by the combustion temperature of the kiln head of the sulfur reaction rotary kiln, the consumption of air in the burner is preferably automatically controlled by the oxygen content in the sulfur tail gas, and the oxygen content in the sulfur tail gas is preferably controlled to be less than 1 percent so as to keep the system to operate in a reduction state.
In the invention, the thermally purified sulfur tail gas and air are combusted in a sulfur reaction rotary kiln through a combustor to form combustion flue gas, when the temperature of the combustion flue gas reaches 1150-1250 ℃, the combustion flue gas reaches the high-temperature decomposition and reduction temperature of phosphorite powder, phosphogypsum is subjected to decomposition reduction reaction to generate combustible gas containing sulfur and CO, the combustion flue gas is called sulfur tail gas, as heat is consumed during reduction, the heat of the residual sulfur tail gas after heat consumption is used for heating and warming the phosphogypsum, the temperature of the sulfur tail gas after heat consumption is gradually 600-650 ℃, then measures such as heat exchange, cooling, sulfur removal and the like are carried out on the sulfur tail gas to recover sulfur, and the purified sulfur tail gas is returned to be combusted as a heat source. In the invention, the preferred residence time of the ground material in the sulfur reaction rotary kiln is 40-60 min, namely the total time of the decomposition reduction reaction, and the decomposition rate of the phosphogypsum can reach more than 80-85%.
And controlling the content of CO in the sulfur tail gas discharged from the kiln tail to be within 8-10% by using the amount of the reducing agent, and returning the sulfur tail gas to the kiln head for combustion gas.
Fig. 1 is a schematic structural diagram of an apparatus for preparing sulfur from phosphogypsum according to the present invention, and the method for preparing sulfur from phosphogypsum according to the present invention is now described with reference to fig. 1: firstly, respectively conveying the phosphogypsum, the reducing agent and ingredients in a phosphogypsum storage tank 1, a reducing agent storage tank 2 and an ingredient storage tank 3 into a ball mill 4 for grinding to obtain a grinding material; then, the ground material is conveyed into a sulfur reaction rotary kiln 6 by a bucket elevator 5, combustion heat supply of combustion gas is carried out by a combustor 14, so that phosphogypsum is decomposed and reduced to obtain a mineral material and sulfur tail gas, and the mineral material is cooled by a quencher 7 to obtain a soil conditioner product; the sulfur tail gas enters a heat exchanger 8, part of the sulfur tail gas enters an electric dust remover 9 for dust removal, the tail gas after dust removal enters a sulfur cooler 10 for cooling, and a sulfur product and a cold sulfur tail gas are obtained through separation; the cold sulfur tail gas enters a cooling washer 11 for washing to obtain cold purified sulfur tail gas; the cold-purified sulfur tail gas enters the heat exchanger 8 through the tail gas blower 13, and exchanges heat with the residual sulfur tail gas in the heat exchanger 8 to obtain hot-purified sulfur tail gas; the heat-purified sulfur tail gas and air from an air blower 15 are mixed and enter a combustor 14 for combustion, the generated heat supplies heat to a sulfur reaction rotary kiln, and the decomposition reduction reaction of phosphogypsum is continuously carried out.
The apparatus and method for preparing sulfur from phosphogypsum provided by the present invention are described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Processing 7500 tons of phosphogypsum every year, adding 1000kg/h of phosphogypsum from a phosphogypsum storage tank 1, adding 220kg/h of nut coke from a reducing agent storage tank 2, adding 100kg/h of manganese mineral powder from a batching storage tank 3, feeding the manganese mineral powder into a ball mill 4 through a weighing scale, and grinding until the material is ground to below 160 meshes to obtain a ground material; feeding the ground material into a kiln head of a sulfur reaction rotary kiln 6 by using a bucket elevator 5, and allowing the ground material to enter the sulfur reaction rotary kiln 6 for decomposition reduction reaction to obtain a mineral material and sulfur tail gas, wherein the mineral material enters a quencher 7 from the kiln tail of the sulfur reaction rotary kiln and is cooled to below 50 ℃ to obtain a soil conditioner containing phosphorus, calcium and manganese;
the method comprises the following steps that sulfur tail gas (the temperature is 600-650 ℃) enters a heat exchanger 8 from a kiln head of a sulfur reaction rotary kiln to exchange heat with cold-purified sulfur tail gas from a tail gas blower 13, the temperature of the cold-purified sulfur tail gas is increased to 250-300 ℃, the temperature of hot sulfur tail gas is reduced to 220-250 ℃, the hot sulfur tail gas enters an electric dust remover 9 to be subjected to fine dust removal, the tail gas after dust removal enters a sulfur cooler 10 to be cooled to a temperature below 80 ℃, sulfur is separated out, the tail gas obtained after separation enters a cooling washer 11 and is washed by ammonia water, the obtained cold-purified sulfur tail gas is pressurized to 5kPa by the tail gas blower 13, and the tail gas is sent out at3And h, the mixture enters a heat exchanger 8 for heat exchange, the temperature is increased to 250-300 ℃, the mixture enters a combustor 14, and the mixture is mixed with air from an air blower 15 in the combustor for combustion and heat supply.
By calculation, the method of example 1 produces 1200 tons of sulfur powder annually and 5600-5700 tons of soil conditioner containing phosphorus, calcium and manganese.
Example 2
25000 tons of phosphogypsum are treated in one year, 3300kg/h of phosphogypsum is added from a phosphogypsum storage tank 1, 720kg/h of nut coke is added from a reducing agent storage tank 2, 300kg/h of bentonite is added from a batching storage tank 3, the mixture enters a ball mill 4 through a weighing scale and is crushed to below 160 meshes to obtain a ground material, the ground material is sent to a kiln head of a sulfur reaction rotary kiln 6 by a bucket elevator 5 and then enters the sulfur reaction rotary kiln 6 to be subjected to decomposition reduction reaction to obtain a mineral material and sulfur tail gas, and the mineral material enters a quencher 7 from the kiln tail to be cooled to below 50 ℃ to obtain the soil conditioner containing phosphorus, calcium and manganese.
The sulfur tail gas (the temperature is 600-650 ℃) enters a heat exchanger from the kiln head of the sulfur reaction rotary kiln to exchange heat with cold purification sulfur tail gas from a tail gas blower, the temperature of the cold purification sulfur tail gas is increased to 250-300 ℃, the temperature of the hot sulfur tail gas is reduced to 220-250 ℃, the hot sulfur tail gas enters an electric dust remover 9 to be subjected to fine dust removal, and the tail gas after dust removal is subjected to fine dust removalCooling in a sulfur cooler 10 to below 80 deg.C to separate sulfur, washing the separated tail gas in a cooling washer 11 with ammonia water, pressurizing the cold purified sulfur tail gas to 5kPa with a tail gas blower 13, and delivering 3000m tail gas3And h, the mixture enters a heat exchanger 8 for heat exchange, the temperature is increased to 250-300 ℃, the mixture enters a combustor 14, and the mixture is mixed with air from an air blower 15 in the combustor for combustion and heat supply.
By calculation, 4000 tons of sulfur powder are produced annually by implementing the method 2, and 19000-21000 tons of soil conditioner containing phosphorus, calcium and manganese are produced annually.
Example 3
Treating 50000 tons of phosphogypsum annually, adding 6600kg/h of phosphogypsum from a phosphogypsum storage tank 1, adding 1440kg/h of coke from a reducing agent storage tank 2, adding 500kg/h of magnesite powder from a batching storage tank 3, feeding the mixture into a ball mill 4 through a weighing scale, crushing the mixture to below 160 meshes to obtain a ground material, feeding the ground material into a sulfur reaction rotary kiln 6 through a bucket elevator 5, feeding the ground material into a sulfur reaction rotary kiln 6 to perform decomposition reduction reaction, obtaining a mineral material and sulfur tail gas, feeding the mineral material into a quencher 7 from a kiln tail, and cooling the mineral material to below 50 ℃ to obtain the soil conditioner containing phosphorus, calcium and magnesium.
The method comprises the following steps that sulfur tail gas (the temperature is 600-650 ℃) enters a heat exchanger from a kiln head of a sulfur reaction rotary kiln to exchange heat with cold-purified sulfur tail gas from a tail gas blower, the temperature of the cold-purified sulfur tail gas is increased to 250-300 ℃, the temperature of hot sulfur tail gas is reduced to 220-250 ℃, the hot sulfur tail gas enters an electric dust remover 9 to be subjected to fine dust removal, the tail gas after dust removal enters a sulfur cooler 10 to be cooled to a temperature below 80 ℃, sulfur is separated out, the tail gas obtained after separation enters a cooling washer 11 and is washed by ammonia water, the obtained cold-purified sulfur tail gas is pressurized to 5kPa by a tail gas blower 13, and the tail gas of 6000m is3The heat exchange is carried out in a heat exchanger 8, the temperature is increased to 250-300 ℃, the heat exchange enters a combustor 14, and the heat exchange is mixed with air from an air blower 15 in the combustor for combustion and heat supply
By calculation, 8000 tons of sulfur powder and 42000-44000 tons of soil conditioner containing phosphorus, calcium and magnesium are produced annually by the method in the embodiment 3.
According to the embodiment, the invention provides the device and the method for preparing the sulfur by the phosphogypsum, the sulfur reaction rotary kiln, the quencher, the heat exchanger, the sulfur cooler and the cooling washer are originally created, and the device for preparing the sulfur by the phosphogypsum and the existing equipment (the ball mill, the bucket elevator, the electric dust remover and the tail gas blower) are jointly formed into the device for preparing the sulfur by the phosphogypsum, the device can prepare the sulfur by taking the waste phosphogypsum as a raw material and co-produce the phosphorus-containing soil conditioner, so that the resource utilization is realized, and a new way is opened up for the comprehensive utilization of the phosphogypsum; the device and the method have no secondary pollution in the process of preparing the sulfur, and are environment-friendly production technology; the scheme of the invention can fully utilize energy, has low energy consumption and low operation cost, and has better economic benefit.
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 (9)
1. The device for preparing the sulfur from the phosphogypsum is characterized by comprising a phosphogypsum storage tank (1), a reducing agent storage tank (2), a batching storage tank (3), a ball mill (4), a bucket elevator (5), a sulfur reaction rotary kiln (6), a heat exchanger (8), an electric dust remover (9), a sulfur cooler (10), a cooling washer (11), a tail gas blower (13), a combustor (14) and an air blower (15); the phosphogypsum storage tank (1), the reducing agent storage tank (2) and the batching storage tank (3) are respectively communicated with the ball mill (4), and the ball mill (4), the bucket elevator (5) and the kiln head of the sulfur reaction rotary kiln (6) are communicated in sequence; the kiln head of the sulfur reaction rotary kiln (6) is communicated with a heat exchanger (8), the heat exchanger (8), an electric dust remover (9), a sulfur cooler (10), a cooling washer (11) and a tail gas blower (13) are sequentially communicated, an outlet of the tail gas blower (13) is communicated with a burner (14), an outlet of the burner (14) is communicated with the kiln tail of the sulfur reaction rotary kiln (6), and an outlet of an air blower (15) is communicated with the burner (14);
the sulfur reaction rotary kiln also comprises a quencher (7), wherein the quencher (7) is communicated with the kiln tail of the sulfur reaction rotary kiln (6);
the ingredients in the ingredient storage tank (3) are manganese ore powder, bentonite or magnesite powder.
2. The device according to claim 1, further comprising a wash pump (12), said wash pump (12) being in communication with said cooling scrubber (11).
3. A process for the production of sulphur using the apparatus of any one of claims 1 to 2, comprising the steps of:
respectively conveying the phosphogypsum, the reducing agent and the ingredients in the phosphogypsum storage tank (1), the reducing agent storage tank (2) and the ingredient storage tank (3) into a ball mill (4) for grinding to obtain a mixed grinding material;
conveying the mixed powder grinding material to a sulfur reaction rotary kiln (6) by using a bucket elevator (5), and heating for decomposition reduction reaction to obtain a mineral material and sulfur tail gas;
feeding the sulfur tail gas into a heat exchanger (8), feeding part of the sulfur tail gas in the heat exchanger (8) into an electric dust remover (9) for dust removal, feeding the obtained sulfur tail gas after dust removal into a sulfur cooler (10) for cooling, and separating to obtain sulfur and cold sulfur tail gas;
sending the cold sulfur tail gas into a cooling scrubber (11) for purification to obtain cold purified sulfur tail gas;
sending the cold-purified sulfur tail gas into a heat exchanger (8) through a tail gas blower (13), and exchanging heat with the residual sulfur tail gas in the heat exchanger (8) until the temperature of the cold-purified sulfur tail gas is increased to 250-300 ℃ to obtain hot-purified sulfur tail gas;
feeding the thermally purified sulfur tail gas into a combustor (14) to be mixed with air from an air blower (15), and conveying the obtained mixed gas into a sulfur reaction rotary kiln (6) for combustion to supply heat for the decomposition reduction reaction;
the ingredients are manganese ore powder, bentonite or magnesite powder.
4. The method of claim 3, wherein the reductant is coke or anthracite.
5. The method according to claim 3 or 4, wherein the mass ratio of the phosphogypsum to the reducing agent is 100: 21-22.
6. The method according to claim 3, wherein the mass ratio of the phosphogypsum to the ingredients is 1: 0.05-0.1.
7. A method according to claim 3, wherein the rotation speed of the kiln cylinder of the sulfur reaction rotary kiln (6) is 1-2 r/min.
8. A method according to claim 3, characterized in that the mineral material is fed to a chiller (7) for cooling to obtain a soil conditioner.
9. The method according to claim 3, wherein the temperature of the decomposition reduction reaction is 1150-1250 ℃ and the time is 40-60 min.
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| SU1516463A1 (en) * | 1984-03-30 | 1989-10-23 | Научно-Производственное Объединение "Техэнергохимпром" | Method of producing sulphur from calcium sulfate |
| US6024932A (en) * | 1993-05-11 | 2000-02-15 | Gas Research Institute | Method for the conversion of gypsum to elemental sulfur |
| CN101054166B (en) * | 2007-04-11 | 2011-05-25 | 张跃 | Method of producing sulfur from low-grade pyrites by two-section fluid bed |
| CN101468792B (en) * | 2007-12-28 | 2013-03-20 | 尹小林 | Novel technique for producing sulfur from industrial waste gypsum |
| JP2011020881A (en) * | 2009-07-15 | 2011-02-03 | Akita Univ | Method for converting calcium sulfate-containing material into calcium oxide and elemental sulfur, and method and system for recycling calcium sulfate-containing material |
| CN102303883B (en) * | 2011-07-11 | 2013-05-01 | 中国石油化工集团公司 | Method for preparing calcium oxide and sulfur by double-atmosphere fluidized roasting of desulfurated gypsum |
| CN106187484A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of desulfurated plaster improveing Wheat Growing Soils and production technology thereof |
| CN109573955B (en) * | 2018-12-17 | 2020-09-01 | 山东大学 | Device and process for preparing sulfur and recovering desulfurizer through sulfate carbon thermal reduction |
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