CN116692792A - Method and device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore - Google Patents
Method and device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore Download PDFInfo
- Publication number
- CN116692792A CN116692792A CN202310677965.3A CN202310677965A CN116692792A CN 116692792 A CN116692792 A CN 116692792A CN 202310677965 A CN202310677965 A CN 202310677965A CN 116692792 A CN116692792 A CN 116692792A
- Authority
- CN
- China
- Prior art keywords
- tail gas
- yellow phosphorus
- grade
- combustion
- fluidized bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 59
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 59
- 239000010452 phosphate Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 105
- 239000002367 phosphate rock Substances 0.000 claims abstract description 94
- 238000002485 combustion reaction Methods 0.000 claims abstract description 78
- 239000000428 dust Substances 0.000 claims abstract description 45
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003546 flue gas Substances 0.000 claims abstract description 35
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000008878 coupling Effects 0.000 claims abstract description 9
- 238000010168 coupling process Methods 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 238000005243 fluidization Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000003860 storage Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 4
- 238000005096 rolling process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 29
- 239000011574 phosphorus Substances 0.000 description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
Abstract
The invention discloses a method and a device for improving the grade of yellow phosphorus tail gas dry desulphurization coupling phosphate ore, which grind low-grade phosphate ore, sieve, fully mix low-grade phosphate ore powder, yellow phosphorus tail gas and air, blow into a combustion fluidized bed for circular combustion, form a fluidized rolling suspension layer in the combustion fluidized bed, and H in the yellow phosphorus tail gas in the process 2 O、H 2 S、SO 2 The components such as HF and the like are combined with alkaline substances such as CaO, mgO and the like in the phosphate ore, so that the yellow phosphorus tail gas desulfurization and impurity removal are realized, and meanwhile, the PH in the phosphate ore is realized 3 、P 4 Is oxidized to P 2 O 5 Gas-solid separation is carried out on the flue gas after combustion by a cyclone separator, and phosphorite in dust collection enters fluidization combustion along with blast air again, so that the grade of the phosphorite after roasting in the furnace body is higher; the invention realizes yellow phosphorus tail gas combustion, tail gas desulfurization, impurity removal and phosphate rock grade improvement in the same furnace bodyThe method has single equipment, simple operation and low cost, and realizes gas-solid resource treatment.
Description
Technical Field
The invention belongs to the field of solid waste recycling environmental protection, and particularly relates to a method and a device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ores.
Background
Yellow phosphorus is almost produced by an electric furnace method, and a large amount of yellow phosphorus tail gas is generated in the production process. 2500-3000 Nm of tail gas produced by yellow phosphorus per 1 ton 3 The tail gas is rich in CO (85% -92%), and the heat value is up to 11704KJ/m 3 . Yellow phosphorus tail gas has complex components and contains Phosphorus (PH) in addition to CO 3 500～900mg/Nm 3 、P 4 300～700mg/Nm 3 ) Sulfur (H) 2 S800～3000mg/Nm 3 ) Fluoride (500 mg/Nm) 3 Left and right) and a small amount of water, which is a secondary resource. However, because yellow phosphorus tail gas contains harmful and corrosive components such as phosphorus, sulfur, fluorine and the like, in the tail gas emission or utilization process, equipment used is seriously corroded to lose effectiveness in a short time, normal production is affected, huge loss is caused, and life safety of equipment users can be threatened in serious cases.
The phosphate ore is the main raw material for producing yellow phosphorus, and the quality of the phosphate ore directly influences the operation and process indexes of the electric furnace. Component removal of P from phosphate ore 2 O 5 In addition, contains CaO and SiO 3 、Al 2 O 3 、Fe 2 O 3 、MgO、CaF 2 Etc. In generalThe higher the grade of the phosphate rock is, the better the grade of the phosphate rock is. Generally, the grade of the phosphate ore is low, the content of the corresponding impurities is increased, the generated slag, ferrophosphorus and phosphorus mud are increased, and the taken phosphorus is increased, so that the yield of the phosphorus is reduced. According to rough estimation, the phosphorus ore grade is reduced by about 0.5 percent every time, and the phosphorus yield is reduced, so that a great amount of phosphorus resource waste is caused.
Disclosure of Invention
The invention provides a method and a device for improving the grade of yellow phosphorus tail gas dry desulphurization coupling phosphate rock, which are characterized in that the yellow phosphorus tail gas is fully mixed with low-grade phosphate rock and air, the low-grade phosphate rock is roasted in a combustion fluidized bed, sulfide and fluoride in the yellow phosphorus tail gas are absorbed by the low-grade phosphate rock, and the phosphate in the yellow phosphorus tail gas is oxidized and enriched in the phosphate rock, so that the grade of the phosphate rock is improved while the problems of traditional yellow phosphorus tail gas utilization and gas purification are solved.
The technical scheme of the invention is as follows:
a method for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore comprises the following specific steps:
(1) Grinding low-grade phosphate rock and sieving;
(2) Fully mixing the sieved low-grade phosphate ore, yellow phosphorus tail gas and air, feeding the mixture into a combustion fluidized bed, and performing circulating fluidization to realize combustion, gas desulfurization and P 2 O 5 Enrichment, namely synchronously realizing heat value utilization, gas purification and phosphate ore grade improvement;
(3) After fluidization combustion, the roasted phosphate rock enters a cyclone separator for gas-solid separation to obtain high-temperature flue gas and roasted phosphate rock, the roasted phosphate rock is returned to a combustion fluidized bed through a blower, small-particle phosphate rock is roasted again, and large-particle phosphate rock is deposited to a fluidized bed ash bucket to be discharged, so that higher-grade phosphate rock is obtained;
(4) The high-temperature flue gas enters a heat exchange device, and is subjected to heat exchange to obtain low-temperature flue gas, the low-temperature flue gas enters an electric dust removal device to be subjected to dust removal treatment, and the mixed gas of nitrogen and carbon dioxide is obtained and stored, so that the mixed gas can be used for CO with different concentrations 2 Gas productionAnd (5) preparing the product.
The low-grade phosphate ore in the step (1) is ground and sieved by a 200-mesh sieve, and the low-grade phosphate ore sieved after the process is operated enters the step (2) after heat exchange is carried out by adopting the high-temperature flue gas in the step (4).
The yellow phosphorus tail gas in the step (2) is yellow phosphorus tail gas generated in the production of yellow phosphorus by an electric furnace method, and the components of the yellow phosphorus tail gas mainly comprise CO (85% -92%) and PH (potential of hydrogen) 3 (500～900mg/Nm 3 )，P 4 (300～700mg/Nm 3 ) Sulfur (H) 2 S 800～3000mg/Nm 3 ) Fluoride (500 mg/Nm) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the yellow phosphorus tail gas is 600-850 ℃, the temperature of fluidization combustion is 850-1000 ℃, and the mixing proportion of the yellow phosphorus tail gas and air is adjusted according to the concentration of CO in the yellow phosphorus tail gas, so that O in the air 2 The molar ratio of the phosphorus and CO in the yellow phosphorus tail gas is not lower than 1.5, the excessive oxygen is ensured, the phosphorus compound in the yellow phosphorus tail gas is oxidized while burning, and the low-grade phosphorus ore is circularly burned, so that the calcium-sulfur ratio reaches 2-2.5, and the desulfurization rate can reach more than 90%.
And (3) preheating air in the air feeder by using high-temperature flue gas waste heat, blowing the roasted phosphate ore into the combustion fluidized bed for circulation, and simultaneously providing oxygen for combustion of the combustion fluidized bed.
In the step (4), the heat exchanger adds water vapor by using the waste heat of high-temperature flue gas, then preheats the low-grade phosphate ore, and is connected with a combustion fluidized bed steam drum, and the air preheater preheats the blown air.
The invention also provides a device for improving the grade of the yellow phosphorus tail gas dry desulfurization coupling phosphate rock, which comprises a phosphate rock bin 1, a combustion fluidized bed 2, a fluidized bed ash bucket 2-1, a cyclone separator 3, a high grade phosphate rock storage tank 4, a heat exchange device 5, a heat exchanger I5-1, a heat exchanger II 5-2, an air preheater 5-3, a heat exchange ash bucket 5-4, a blower 6, an electric dust collector 7, a dust removal ash bucket I7-1, a dust removal ash bucket II 7-2 and a gas storage cabinet 8;
the phosphorus ore bin 1 is connected with the side surface of the lower part of the combustion fluidized bed 2, the side surface of the combustion fluidized bed 2 below the inlet of the phosphorus ore bin 1 is also provided with a yellow phosphorus tail gas inlet, the upper part of the side surface of the combustion fluidized bed 2 is connected with the top of the cyclone separator 3, the bottom of the cyclone separator 3 is connected with the lower part of the combustion fluidized bed 2, the bottom of the combustion fluidized bed 2 is provided with a fluidized bed ash bucket 2-1, the fluidized bed ash bucket 2-1 is communicated with a high-grade phosphorus ore storage pool 4, and the high-grade phosphorus ore storage pool 4 is filled with the fluidized bed ash bucket 2-1 to discharge roasted phosphorus ore;
the top of the cyclone separator 3 is connected with a heat exchange device 5, a heat exchanger I5-1, a heat exchanger II 5-2 and an air preheater 5-3 are sequentially arranged in the heat exchange device 5, a heat exchange ash bucket 5-4 is arranged at the bottom of the heat exchange device 5, high-temperature flue gas sequentially passes through the heat exchanger I5-1, the heat exchanger II 5-2 and the air preheater 5-3, dust enters the ash bucket 5-4 at the bottom, two ends of the air preheater 5-3 are respectively connected with the lower part of the cyclone separator 3 and a blower 6, the lower part of the heat exchange device 5 is connected with an electric dust collector 7, the bottom of the electric dust collector 7 is provided with a dust collection ash bucket I7-1 and a dust collection ash bucket II 7-2, and the dust enters the dust collection ash bucket I7-1 and the dust collection ash bucket II 7-2, and the electric dust collector 7 is connected with a gas storage cabinet 8.
The heat exchangers I5-1 and II 5-2 are spiral pipelines, water is filled in the spiral pipelines, the spiral pipelines are connected with the heating pipeline 1-1, and the heating pipeline 1-1 is arranged outside the phosphorite storage bin 1.
The air preheater 5-3 is a double-layer pipe, the outer layer of the double-layer pipe is filled with water, the double-layer pipe traverses the heat exchange device 5, the inner pipe is communicated with the inside of the heat exchange device 5, and the two ends of the inner pipe are respectively connected with the lower part of the cyclone separator 3 and the air feeder 6.
The technical principle of the invention is as follows:
in the roasting process of low-grade phosphate ore, CO in yellow phosphorus tail gas is subjected to combustion reaction, the low-grade phosphate ore is roasted, heat is provided, and Phosphorus (PH) in the yellow phosphorus tail gas 3 、P 4 ) Oxidized by oxygen in the air to P 2 O 5 And enriching, wherein sulfur and fluorine in the yellow phosphorus tail gas are absorbed by phosphate rock after being oxidized, and the specific equation is as follows.
2CO+O 2 →2CO 2
2PH 3 +4O 2 →3H 2 O+P 2 O 5
P 4 +5O 2 →2P 2 O 5
2H 2 S+3O 2 →2SO 2 +2H 2 O
2SO 2 +O 2 →2SO 3
CaO+H 2 S→CaS+H 2 O
CaO+SO 2 →CaSO 3
CaO+SO 3 →CaSO 4
CaO+2HF＝CaF 2 +H 2 O
MgO+2H 2 S＝Mg(HS) 2 +H 2 O
MgO+SO 2 ＝MgSO 3
MgO+SO 3 ＝MgSO 4
MgO+2HF＝MgF 2 +H 2 O
The invention utilizes the characteristics that the yellow phosphorus tail gas contains CO, impurity phosphorus and alkaline components in the phosphate ore, on one hand, the yellow phosphorus tail gas is utilized to provide heat (CO combustion), and the impurity phosphorus in the yellow phosphorus tail gas is oxidized and enriched with P 2 O 5 In the phosphate ore, the grade of the phosphate ore is improved, and on the other hand, the alkaline component in the phosphate ore is utilized to purify sulfur, fluorine and other impurities in the yellow phosphorus tail gas, so that the impurities in the yellow phosphorus tail gas are removed, and harmless gas can be recovered.
The invention not only realizes the utilization and purification of the yellow phosphorus tail gas, but also fixes the phosphorus in the yellow phosphorus tail gas into the phosphate rock, improves the grade of the phosphate rock and avoids secondary pollution caused by the utilization of the yellow phosphorus tail gas; the method has the advantages of simple equipment, simple operation, low cost and synchronous realization of gas-solid treatment and recycling.
Drawings
FIG. 1 is a schematic diagram of the structure of the device of the present invention;
in the figure: 1-a phosphate rock bin; 1-1-heating the pipeline; 2-burning the fluidized bed; 2-1-a fluidized bed ash bucket; a 3-cyclone separator; 4-a high-grade phosphorite storage tank; 5-a heat exchange device; 5-1-heat exchanger I; 5-2-heat exchanger II; 5-3-air preheater; 5-4-heat exchange ash bucket; 6-a blower; 7-an electric dust removing device; 7-1 of a dust removing ash bucket I; 7-2 dust and ash removing hopper II; 8-a gas storage cabinet.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
A device for improving grade of yellow phosphorus tail gas dry desulfurization coupling phosphate rock is shown in figure 1, and comprises a phosphate rock bin 1, a heating pipeline 1-1, a combustion fluidized bed 2, a fluidized bed ash bucket 2-1, a cyclone separator 3, a high-grade phosphate rock storage tank 4, a heat exchange device 5, a heat exchanger I5-1, a heat exchanger II 5-2, an air preheater 5-3, a heat exchange ash bucket 5-4, a blower 6, an electric dust collector 7, a dust collection ash bucket I7-1, a dust collection ash bucket II 7-2 and a gas storage cabinet 8;
the phosphorus ore bin 1 is connected with the side surface of the lower part of the combustion fluidized bed 2, the side surface of the combustion fluidized bed 2 below the inlet of the phosphorus ore bin 1 is also provided with a yellow phosphorus tail gas inlet, the upper part of the side surface of the combustion fluidized bed 2 is connected with the top of the cyclone separator 3, the bottom of the cyclone separator 3 is connected with the lower part of the combustion fluidized bed 2, the bottom of the combustion fluidized bed 2 is provided with a fluidized bed ash bucket 2-1, the fluidized bed ash bucket 2-1 is communicated with a high-grade phosphorus ore storage pool 4, and large-particle phosphorus ore enters the high-grade phosphorus ore storage pool 4 through the fluidized bed ash bucket 2-1 and is discharged to bake phosphorus ore;
the top of the cyclone separator 3 is connected with a heat exchange device 5, a heat exchanger I5-1, a heat exchanger II 5-2 and an air preheater 5-3 are sequentially arranged in the heat exchange device 5, a heat exchange ash bucket 5-4 is arranged at the bottom of the heat exchange device 5, high-temperature flue gas sequentially passes through the heat exchanger I5-1, the heat exchanger II 5-2 and the air preheater 5-3, dust enters the ash bucket 5-4 at the bottom, the heat exchanger I5-1 and the heat exchanger II 5-2 are spiral pipelines, water is filled in the spiral pipelines, the spiral pipelines are connected with a heating pipeline 1-1, and the heating pipeline 1-1 is arranged outside a phosphorite bin 1; the air preheater 5-3 is a double-layer pipe, the outer layer of the double-layer pipe is provided with water, the double-layer pipe transversely passes through the heat exchange device 5, an inner pipe of the double-layer pipe is communicated with the inside of the heat exchange device 5, two ends of the inner pipe are respectively connected with the lower part of the cyclone separator 3 and the blower 6, the lower part of the heat exchange device 5 is connected with the electric dust collector 7, the bottom of the electric dust collector 7 is provided with a dust collection hopper I7-1 and a dust collection hopper II 7-2, dust enters the dust collection hopper I7-1 and the dust collection hopper II 7-2, and the electric dust collector 7 is connected with the gas storage cabinet 8.
A plurality of temperature measuring probes are arranged in the combustion fluidized bed 2 and the heat exchange device 5 and are used for monitoring the temperature. The air in the air feeder 6 is preheated by the waste heat of high-temperature flue gas, and the roasted phosphate ore is blown into the combustion fluidized bed 2 for circulation and oxygen is provided for the combustion of the combustion fluidized bed 2; the heat exchangers I5-1 and II 5-2 are used for adding water vapor by using the waste heat of high-temperature flue gas, preheating low-grade phosphate ores, connecting a steam drum of the combustion fluidized bed 2, and the air preheater 5-3 is used for preheating the blown air.
Example 2
A method for upgrading yellow phosphorus tail gas by dry desulfurization coupling phosphate ore adopts the device system in the embodiment 1, adopts medium and low grade phosphate ore stored in a yellow phosphorus factory from Yunnan Qujing, and P of the phosphate ore 2 O 5 Medium grade phosphorite with 28.6 percent of MgO content and 1.57 percent of MgO content; the adopted yellow phosphorus tail gas comprises CO85 percent and PH 3 500mg/Nm 3 ，P 4 300mg/Nm 3 、H 2 S800mg/Nm 3 Fluoride 500mg/Nm 3 The method comprises the following specific steps:
(1) Grinding low-grade phosphate rock by using a ball mill, and then sieving with a 200-mesh sieve;
(2) The sieved low-grade phosphorite Dan Chu is stored in a phosphorite bin 1, and phosphorite in the phosphorite bin 1 is led into a combustion fluidized bed 2;
(3) Introducing 600 ℃ yellow phosphorus tail gas into a combustion fluidized bed 2 from a yellow phosphorus tail gas inlet, fully mixing with low-grade phosphate rock, preheating the low-grade phosphate rock by utilizing the temperature of the yellow phosphorus tail gas before combustion, forming a fluidized rolling suspension layer, performing fluidized combustion at 850 ℃, roasting the phosphate rock powder, supplying oxygen required by combustion by air blown by a blower 6, and supplying CO in the yellow phosphorus tail gas and O in the air 2 The ratio of the calcium to the sulfur is 1:1.5, and the low-grade phosphate ore is circularly combusted to enable the ratio of the calcium to the sulfur to reach 2-2.5;
(4) After fluidization combustion, the roasted phosphate rock enters a cyclone separator 3 for gas-solid separation to obtain high-temperature flue gas at about 850 ℃ and roasted phosphate rock, the roasted phosphate rock returns to a fluidized bed 2 through a blower 6, small-particle phosphate rock is roasted again, and large-particle phosphate rock is deposited to a fluidized bed ash bucket 2-1 and discharged to obtain higher-grade phosphate rock;
(5) The high-temperature flue gas enters a heat exchange device 5, passes through a heat exchanger I5-1, a heat exchanger II 5-2 and an air preheater 5-3 to obtain low-temperature flue gas with the temperature of 150-200 ℃, water heated in the heat exchanger I5-1 and the heat exchanger II 5-2 is communicated with a heating pipeline 1-1, and the heating pipeline 1-1 preheats low-grade phosphate ore at the outlet of a phosphate rock bin 1, so that the fluidized combustion in the step (2) is facilitated, and energy is saved; the air preheater 5-3 blows the roasted phosphate ore into the combustion fluidized bed 2 for circulation and simultaneously provides oxygen for combustion of the combustion fluidized bed 6;
(6) The obtained low-temperature flue gas enters an electric dust removing device 7 for dust removal treatment to obtain standard flue gas, namely, mixed gas of nitrogen and carbon dioxide;
(7) The flue gas reaching the standard enters a gas storage cabinet 8 and can be used for CO with different concentrations 2 And (5) preparing a gas product.
In the stable operation of the embodiment, the utilization efficiency of CO can reach 100 percent, and P in the higher-grade phosphorite discharged from the fluidized bed ash bucket 2-1 2 O 5 The content is 34.9%, phosphorus is enriched, compared with the original low-grade phosphorite MgO removal rate of 92.9%, the removal efficiency of sulfide in yellow phosphorus tail gas is 95%, and carbonate substances are basically eliminated.
Example 3
A method for upgrading yellow phosphorus tail gas by dry desulfurization coupling phosphate ore adopts the device system in the embodiment 1, adopts medium and low grade phosphate ore stored in a yellow phosphorus factory from Yunnan Qujing, and P of the phosphate ore 2 O 5 Low-grade phosphorite with the content of 19.8 percent and the MgO content of 1.60 percent; the adopted yellow phosphorus tail gas comprises CO 92% (volume fraction, same below) and PH 3 900mg/Nm 3 ，P 4 700mg/Nm 3 、H 2 S3000mg/Nm 3 Fluoride 500mg/Nm 3 The method comprises the following specific steps:
(1) Grinding low-grade phosphate rock by using a ball mill, and then sieving with a 200-mesh sieve;
(2) The sieved low-grade phosphorite Dan Chu is stored in a phosphorite bin 1, and phosphorite in the phosphorite bin 1 is led into a combustion fluidized bed 2;
(3) Introducing 700 ℃ yellow phosphorus tail gas into a combustion fluidized bed 2 from a yellow phosphorus tail gas inlet, fully mixing with low-grade phosphate rock, preheating the low-grade phosphate rock by utilizing the temperature of the yellow phosphorus tail gas before combustion, forming a fluidized rolling suspension layer, performing fluidized combustion at 900 ℃, roasting the phosphate rock powder, supplying oxygen required by combustion by air blown by a blower 6, and supplying CO in the yellow phosphorus tail gas and O in the air 2 The ratio of the calcium to the sulfur is 1:1.6, and the low-grade phosphate ore is circularly combusted to enable the ratio of the calcium to the sulfur to reach 2-2.5;
(4) After fluidization combustion, the roasted phosphate rock enters a cyclone separator 3 for gas-solid separation to obtain high-temperature flue gas at about 900 ℃ and roasted phosphate rock, the roasted phosphate rock returns to a combustion fluidized bed 2 through a blower 6, small-particle phosphate rock is roasted again, and large-particle phosphate rock is settled to a fluidized bed ash bucket 2-1 and discharged to obtain higher-grade phosphate rock;
(5) The high-temperature flue gas enters a heat exchange device 5, passes through a heat exchanger I5-1, a heat exchanger II 5-2 and an air preheater 5-3 to obtain low-temperature flue gas with the temperature of 150-200 ℃, water heated in the heat exchanger I5-1 and the heat exchanger II 5-2 is communicated with a heating pipeline 1-1, and the heating pipeline 1-1 preheats low-grade phosphate ore at the outlet of a phosphate rock bin 1, so that the fluidized combustion in the step (2) is facilitated, and energy is saved; the air preheater 5-3 blows the roasted phosphate ore into the combustion fluidized bed 2 for circulation and simultaneously provides oxygen for the combustion of the combustion fluidized bed 2;
(6) The obtained low-temperature flue gas enters an electric dust removing device 7 for dust removal treatment to obtain standard flue gas, namely, mixed gas of nitrogen and carbon dioxide;
(7) The flue gas reaching the standard enters a gas storage cabinet 8 and can be used for CO with different concentrations 2 And (5) preparing a gas product.
In the stable operation of the embodiment, the utilization efficiency of CO can reach 100 percent, and the CO is arranged in the fluidized bed ash bucket 2-1P in discharged higher grade phosphorite 2 O 5 The content is 33.6%, phosphorus is enriched, compared with the original low-grade phosphorite MgO removal rate of 80%, the removal efficiency of sulfide in yellow phosphorus tail gas is 90%, and carbonate substances are basically eliminated.
Example 4
A method for upgrading yellow phosphorus tail gas by dry desulfurization coupling phosphate ore adopts the device system in the embodiment 1, adopts medium and low grade phosphate ore stored in a yellow phosphorus factory from Yunnan Qujing, and P of the phosphate ore 2 O 5 Low-grade phosphorite with the content of 19.8 percent and the MgO content of 1.60 percent; the adopted yellow phosphorus tail gas comprises the components of CO 92 percent and PH 3 900mg/Nm 3 ，P 4 700mg/Nm 3 、H 2 S3000mg/Nm 3 Fluoride 500mg/Nm 3 The method comprises the following specific steps:
(1) Grinding low-grade phosphate rock by using a ball mill, and then sieving with a 200-mesh sieve;
(2) The sieved low-grade phosphorite Dan Chu is stored in a phosphorite bin 1, and phosphorite in the phosphorite bin 1 is led into a combustion fluidized bed 2;
(3) Introducing 850 ℃ yellow phosphorus tail gas into a combustion fluidized bed 2 from a yellow phosphorus tail gas inlet, fully mixing with low-grade phosphate rock, preheating the low-grade phosphate rock by utilizing the temperature of the yellow phosphorus tail gas before combustion to form a fluidized rolling suspension layer, performing fluidized combustion at 1000 ℃, roasting the phosphate rock powder, supplying oxygen required by combustion by air blown by a blower 6, and supplying CO in the yellow phosphorus tail gas and O in the air 2 The ratio of the calcium to the sulfur is 1:2, and the low-grade phosphate ore is circularly combusted to enable the ratio of the calcium to the sulfur to reach 2-2.5;
(4) After fluidization combustion, the roasted phosphate rock enters a cyclone separator 3 for gas-solid separation to obtain high-temperature flue gas at about 1000 ℃ and roasted phosphate rock, the roasted phosphate rock returns to a combustion fluidized bed 2 through a blower 6, small-particle phosphate rock is roasted again, and large-particle phosphate rock is settled to a fluidized bed ash bucket 2-1 and discharged to obtain higher-grade phosphate rock;
(5) The high-temperature flue gas enters a heat exchange device 5, passes through a heat exchanger I5-1, a heat exchanger II 5-2 and an air preheater 5-3 to obtain low-temperature flue gas with the temperature of 150-200 ℃, water heated in the heat exchanger I5-1 and the heat exchanger II 5-2 is communicated with a heating pipeline 1-1, and the heating pipeline 1-1 preheats low-grade phosphate ore at the outlet of a phosphate rock bin 1, so that the fluidized combustion in the step (2) is facilitated, and energy is saved; the air preheater 5-3 blows the roasted phosphate ore into the combustion fluidized bed 2 for circulation and simultaneously provides oxygen for the combustion of the combustion fluidized bed 2;
(6) The obtained low-temperature flue gas enters an electric dust removing device 7 for dust removal treatment to obtain standard flue gas, namely, mixed gas of nitrogen and carbon dioxide;
(7) The flue gas reaching the standard enters a gas storage cabinet 8 and can be used for CO with different concentrations 2 And (5) preparing a gas product.
In the stable operation of the embodiment, the utilization efficiency of CO can reach 100 percent, and P in the higher-grade phosphorite discharged from the fluidized bed ash bucket 2-1 2 O 5 The content is 33.6%, phosphorus is enriched, compared with the original low-grade phosphorite MgO removal rate of 80%, the removal efficiency of sulfide in yellow phosphorus tail gas is 90%, and carbonate substances are basically eliminated.
Claims (7)
1. A method for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore is characterized by comprising the following specific steps:
(1) Grinding low-grade phosphate rock and sieving;
(2) Fully mixing low-grade phosphate ore, yellow phosphorus tail gas and air, and feeding the mixture into a combustion fluidized bed for fluidized combustion;
(3) After fluidization combustion, gas-solid separation is carried out to obtain high-temperature flue gas and roasted phosphate ore, the roasted phosphate ore is returned to a combustion fluidized bed, small-particle phosphate ore is roasted again, large-particle phosphate ore is deposited to a fluidized bed ash bucket, and higher-grade phosphate ore is obtained after discharge;
(4) The high-temperature flue gas is subjected to heat exchange to obtain low-temperature flue gas, the low-temperature flue gas is subjected to dust removal treatment to obtain mixed gas of nitrogen and carbon dioxide, and the mixed gas is stored and used for different concentrations of CO 2 And (5) preparing a gas product.
2. The method for upgrading yellow phosphorus tail gas dry desulfurization coupled phosphate ores according to claim 1, wherein the low-grade phosphate ores in the step (1) are ground and screened by a 200-mesh sieve.
3. The method for upgrading yellow phosphorus tail gas dry desulfurization coupled phosphate ore according to claim 1, wherein the yellow phosphorus tail gas in the step (2) is tail gas generated in the production of yellow phosphorus by an electric furnace method, and the components of the tail gas mainly comprise 85% -92% of CO and pH 3 500～900mg/Nm 3 ，P 4 300～700mg/Nm 3 、H 2 S 800～3000mg/Nm 3 Fluoride 500mg/Nm 3 。
4. The method for upgrading yellow phosphorus tail gas dry desulfurization coupled phosphate ore according to claim 1, wherein the temperature of the yellow phosphorus tail gas in the step (2) is 600-850 ℃, the temperature of fluidized combustion is 850-1000 ℃, and O in air is contained 2 The molar ratio of the catalyst to CO in the yellow phosphorus tail gas is not lower than 1.5.
5. The method for upgrading the yellow phosphorus tail gas dry desulfurization coupled phosphate ore according to claim 1, wherein the low-grade phosphate ore screened in the step (1) enters the step (2) after heat exchange by adopting the high-temperature flue gas in the step (4).
6. The device for improving the grade of the yellow phosphorus tail gas dry desulfurization coupling phosphate rock is characterized by comprising a phosphate rock bin, a combustion fluidized bed, a fluidized bed ash bucket, a cyclone separator, a high-grade phosphate rock storage tank, a heat exchange device, a heat exchanger I, a heat exchanger II, an air preheater, a heat exchange ash bucket, a blower, an electric dust collector, a dust removal ash bucket I, a dust removal ash bucket II and a gas storage cabinet; the phosphorite bin is connected with the side surface of the lower part of the combustion fluidized bed, a yellow phosphorus tail gas inlet is further arranged below the phosphorite bin inlet of the side surface of the combustion fluidized bed, the upper part of the side surface of the combustion fluidized bed is connected with the top of the cyclone separator, the bottom of the cyclone separator is connected with the lower part of the combustion fluidized bed, a fluidized bed ash bucket is arranged at the bottom of the combustion fluidized bed, and the fluidized bed ash bucket is communicated with the high-grade phosphorite storage tank; the top of the cyclone separator is connected with a heat exchange device, a heat exchanger I, a heat exchanger II and an air preheater are sequentially arranged in the heat exchange device, a heat exchange ash bucket is arranged at the bottom of the heat exchange device, two ends of the air preheater are respectively connected with the lower part of the cyclone separator and a blower, the lower part of the heat exchange device is connected with an electric dust collector, a dust collection ash bucket I and a dust collection ash bucket II are arranged at the bottom of the electric dust collector, and the electric dust collector is connected with a gas storage cabinet.
7. The device for upgrading phosphate rock by coupling dry desulfurization of yellow phosphorus tail gas according to claim 6, wherein the heat exchanger I and the heat exchanger II are spiral pipelines, water is filled in the spiral pipelines, the spiral pipelines are connected with heating pipelines, and the heating pipelines are arranged outside a phosphate rock bin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310677965.3A CN116692792A (en) | 2023-06-08 | 2023-06-08 | Method and device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310677965.3A CN116692792A (en) | 2023-06-08 | 2023-06-08 | Method and device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116692792A true CN116692792A (en) | 2023-09-05 |
Family
ID=87838734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310677965.3A Pending CN116692792A (en) | 2023-06-08 | 2023-06-08 | Method and device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116692792A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016058141A1 (en) * | 2014-10-15 | 2016-04-21 | 北京中科净原环保科技有限公司 | Method and device for dedusting and desulphurizing flue gas |
| CN110745798A (en) * | 2019-10-17 | 2020-02-04 | 昆明理工大学 | Method and device for removing carbon dioxide in phosphate ore by calcining CO-containing industrial tail gas |
| CN112325312A (en) * | 2020-10-21 | 2021-02-05 | 昆明理工大学 | Method and device for reducing emission of acidic harmful gas in CO industrial tail gas by pyrolysis of carbonate ore |
| CN115491487A (en) * | 2022-08-11 | 2022-12-20 | 昆明理工大学 | Method and device for red mud dry desulphurization coupling submerged arc furnace gas heat recovery |
| US20230002692A1 (en) * | 2021-06-30 | 2023-01-05 | Kunming University Of Science And Technology | System for combined production of yellow phosphorus and syngas |
-
2023
- 2023-06-08 CN CN202310677965.3A patent/CN116692792A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016058141A1 (en) * | 2014-10-15 | 2016-04-21 | 北京中科净原环保科技有限公司 | Method and device for dedusting and desulphurizing flue gas |
| CN110745798A (en) * | 2019-10-17 | 2020-02-04 | 昆明理工大学 | Method and device for removing carbon dioxide in phosphate ore by calcining CO-containing industrial tail gas |
| CN112325312A (en) * | 2020-10-21 | 2021-02-05 | 昆明理工大学 | Method and device for reducing emission of acidic harmful gas in CO industrial tail gas by pyrolysis of carbonate ore |
| US20230002692A1 (en) * | 2021-06-30 | 2023-01-05 | Kunming University Of Science And Technology | System for combined production of yellow phosphorus and syngas |
| CN115491487A (en) * | 2022-08-11 | 2022-12-20 | 昆明理工大学 | Method and device for red mud dry desulphurization coupling submerged arc furnace gas heat recovery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3492083A (en) | Process for the removal of sulphur from industrial gases and to apparatus for use in such a process | |
| CN103011090B (en) | Method for producing sulfur by using pyrolysis-reducing united technique | |
| US4539188A (en) | Process of afterburning and purifying process exhaust gases | |
| CN104211035B (en) | From the kiln discharge flue gas of kiln-process phosphoric acid technique, aquation inhales phosphorus and the method reclaiming fluorine | |
| CN102442650B (en) | Method for producing sulfuric acid and co-producing calcium carbide by phosphogypsum | |
| CN102367169B (en) | Method for preparation of sulfuric acid and combined production of fine flour iron through calcination of coal-derived pyrite in presence of oxygen-rich air | |
| CN104870659B (en) | Molten iron manufacturing apparatus and molten iron manufacturing method | |
| JPH0421524B2 (en) | ||
| CN111498811B (en) | Process and device for gypsum calcination and CO coupling carbon thermal reduction | |
| WO2020024350A1 (en) | System and method for recovering sulfur during copper smelting process | |
| CN104894366B (en) | A kind of system and method for low-grade manganese dioxide ore fluidized reduction | |
| CN109573955B (en) | Device and process for preparing sulfur and recovering desulfurizer through sulfate carbon thermal reduction | |
| WO2016086826A1 (en) | Improved device for preparing phosphoric acid from kiln egression flue gas of phosphoric acid process of kiln method, and phosphoric acid preparing process | |
| CN104878193B (en) | A kind of system and method for Low grade manganese ore fluidized reduction roasting | |
| CN106669962A (en) | Beneficiation method and system for calcium or calcareous and siliceous phosphorite and application method of beneficiation system | |
| CN1301584A (en) | Complex utilization method for boiler fume | |
| US20050002845A1 (en) | Method of forming phosphoric acid from phosphate ore | |
| CN212585474U (en) | System for decomposing metal salt through heat storage ball heat storage self-circulation | |
| CN115491487B (en) | Method and device for recycling heat of red mud dry desulfurization coupled submerged arc furnace gas | |
| US2075212A (en) | Manufacture of phosphoric acid | |
| CN116692792A (en) | Method and device for improving grade of yellow phosphorus tail gas dry desulfurization coupled phosphate ore | |
| CN104911334A (en) | High-grade manganese dioxide ore fluidized reduction system and method | |
| CN107108211A (en) | The increased phosphorus pentoxide preparation method of aggregation block compressive strength and system | |
| CN109592647B (en) | Process for preparing sulfur and recovering desulfurizing/nitre agent by sulfur/nitrate iron-carbon reduction | |
| CN111363591A (en) | Device and method for co-producing yellow phosphorus and synthesis gas by utilizing phosphorus coal to perform pressurized gasification and reduction on phosphate ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |