CN101462703A - Method for preparing phosphoric acid and metallurgy additive from middle and low grade phosphate ore - Google Patents
Method for preparing phosphoric acid and metallurgy additive from middle and low grade phosphate ore Download PDFInfo
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- CN101462703A CN101462703A CNA2009100940162A CN200910094016A CN101462703A CN 101462703 A CN101462703 A CN 101462703A CN A2009100940162 A CNA2009100940162 A CN A2009100940162A CN 200910094016 A CN200910094016 A CN 200910094016A CN 101462703 A CN101462703 A CN 101462703A
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- phosphoric acid
- low grade
- auxiliary agent
- carbon
- grade phosphate
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Abstract
The invention provides a method for preparing a phosphoric acid and a metallurgical auxiliary agent from mid-low grade phosphorite. The mid-low grade phosphate rocks, kaoline, silica and coal or coke are used as raw materials, the raw materials are subjected to drying, crushing, sieving and grinding, according to SiO2/CaO of 0.5-3.4 and the carbon content of 1.1-3 of carbon needed for reduction of P2O5, CO2, CaO, Al2O3, SiO2, MgO and Fe2O3 in total materials to be mixed, and then the materials are mixed, aged and sprayed with proper amount of water to prepare a material blank needed; the material blank is naturally cured and dried, and transferred to a kiln for pre-heating and calcining to prepare the phosphoric acid by kiln gas containing phosphorus pentoxide; the calcined slag blank is added into an electric smelting furnace for carbon thermal reduction; and after cooling and solidifying, the slag blank is crushed into particles which are the metallurgical high-quality composite alloy auxiliary agent. In the process, the phosphorus utilization rate of the ore is over 90 percent, the obtained phosphoric acid can be directly used for producing a phosphate, the calcined slag can be further subjected to carbon thermal reduction to produce the metallurgical auxiliary agent, and the produced metallurgical auxiliary agent has low material cost and energy consumption.
Description
Technical field
The present invention relates to metallurgical technology field, particularly adopt the direct reduction of mid low grade phosphate rock to produce the method for high-concentration phosphoric acid and by-product metallurgy additive.
Background technology
The main method of suitability for industrialized production phosphoric acid is following several: (1) is raw material with yellow phosphorus, absorbs through oxidizing fire, hydration and produces phosphoric acid; High but its raw material production of the good product quality that this method makes, concentration need consume a large amount of electric energy and in high-grade phosphorus ore, energy consumption height, cost height, routine is called thermal phosphoric acid.(2) produce phosphoric acid with the sulfuric acid decomposing phosphate rock; This method production cost is relatively low, but needs to consume a large amount of sulfuric acid and high-quality Rock Phosphate (72Min BPL), poor product quality, and acid concentration is low, generally only is used to produce fertilizer, is difficult to satisfy the sour requirement of industrial phosphoric acid salt production.And above two kinds of production methods all have the discharging of a large amount of solid slag, pose a big pressure to environment.(3) kiln-process phosphoric acid production technique, this method are made reductive agent, silicon-dioxide with carbon and are made auxiliary agent and directly reduce phosphorus ore and produce phosphoric acid, and composition brick, cement clinker etc. are made in the general exploitation of residue.Residue utilizes single, and economic worth is low.
Metallurgy additive is the deoxidation used of metallurgy industry, desulfurization, dephosphorizing agent etc., and its active principle mainly is silicon, aluminium, calcium, barium etc., conventionally uses the melting of industrialness product to produce, and cost height, energy consumption are big.
Summary of the invention
The purpose of this invention is to provide a kind of direct reduction mid low grade phosphate rock and produce the method for high-concentration phosphoric acid and by-product metallurgy additive.This method has changed technical recipe and the raw material that phosphoric acid is produced in the carbothermic reduction of the conventional kiln method of mid low grade phosphate rock, and the ore phosphorus utilization surpasses 90%, and gained phosphoric acid can be directly used in phosphate production, and it burns the further carbothermic reduction production metallurgy of slag auxiliary agent.
The object of the present invention is achieved like this: with Rock Phosphate (72Min BPL), kaolin, silica and coal (or burnt), drying, fragmentation, screening abrasive dust are pressed SiO
2/ C
aO=3.4～0.5, carbon content are P in total material
2O
5And CO
2, CaO, AI
2O
3, SiO
2, MgO, Fe
2O
31.1～3 of the required carbon that reduces is prepared burden, and after mixing ageing, spray adds the material base that 3～8% hydraulic pressure is made needs again; Material base is sent into and is carried out preheating and calcining in the kiln through natural curing and 380 ℃ of-500 ℃ of oven dry, and the phosphorus in 1300 ℃ of left and right sides Rock Phosphate (72Min BPL) is reduced into the elemental phosphorous oxidation step of going forward side by side by the solid carbon of coal (or burnt) and becomes Vanadium Pentoxide in FLAKES to remove to produce phosphoric acid with kiln gas.Its major ingredient of slag base after the calcining is: SiO
2, CaO, AI
2O
3With remaining carbon, it is added in the electric smelting furnace, be heated to 1500～2000 ℃, the silicon in the slag base, aluminium, calcium oxide are become simple substance eutectic liquid alloy to emit from smelting furnace by remaining carbon reduction, through being ground into the particle below the 25mm behind the cooling curing, be metallurgical high-quality composite alloy auxiliary agent.The high-temperature tail gas that smelting furnace produces mainly is a carbonic acid gas, qualified discharge after dust-collecting and heat exchanging cooling washing; Main trioxygen-containingization two aluminium of the dust that dedusting obtains, can be used as aluminium metallurgy or the system chemical aluminum oxide raw material, also can return with the raw material base; The thermal source of heat exchange gained can be used for preheating material base and drying material; Tail gas also can carry out energy recovery through waste heat boiler and produce mesohigh steam heating or generating, and also directly the distribution temperature adjustment is used for preheating material base and drying material.
The utilization that the present invention calcines the slag base is to be the reduction reaction that principal reaction equipment is finished calcining slag base with the electric melting stove.The reduction usefulness residue carbon wherein of calcining slag base is as reductive agent, and its total reaction is summarized as follows:
2Al
2O
3+3C＝4AI+3CO
2↑
2Fe
2O
3+3C＝4Fe+3CO
2↑
SiO
2+C＝Si+CO
2↑
2CaO+C＝2Ca+CO
2↑
The invention solves that present domestic kiln-process phosphoric acid production burns that slag does that brick product is single, the quality stability difference apply bottleneck problem, change the carbothermic reduction of the conventional kiln method of mid low grade phosphate rock and produced technical recipe and the raw material of phosphoric acid, the ore phosphorus utilization surpasses 90%, gained phosphoric acid can be directly used in phosphate production, it burns the further carbothermic reduction production metallurgy of slag auxiliary agent, developed new outlet for the slag roasting high-efficiency comprehensive utilization of kiln-process phosphoric acid, the metallurgy additive raw materials cost of production is low, energy consumption is low.
Description of drawings
Process flow sheet of the present invention is as follows
Embodiment
Embodiment 1:
Yunnan Xun Dian associating phosphorus ore (P
2O
5: 21-25%, CaO:38-41%, SiO
2: 23-29%), seek pasture kaolin (SiO
2: 45-52%, AI
2O
3: 38-45%), silica (SiO
2: 〉=92%), four kinds of raw materials of coal (fixed carbon content 〉=75%) dry the back respectively and wear into 80% or more with ball mill and pass through 200 purpose powders; Part by weight by 1:0.8:0.5:1.12 mixes the water that the back spray adds material gross weight 6%, be pressed into the coccoid material base of Φ 40～60mm with extrusion machine, natural curing three days, again 380 ℃ of-500 ℃ of oven dry, send into carry out preheating in the kiln and about 1300 ℃ the calcining 2-3 hour, phosphorus in the material base is reduced into elemental phosphorous removing by the solid carbon of coal (or burnt), and the elemental phosphorous Vanadium Pentoxide in FLAKES that further is oxidized to discharges with kiln gas and produces phosphoric acid (being prepared by existing method).Slag base major ingredient after the calcining is Al
2O
3: 13～16%, CaO:14～16%, SiO
2: 39～44%, fixed carbon 24%, directly add it in electric smelting furnace, be heated to 1750～1850 ℃, the carbon reduction that is fixed of aluminium in the slag base, silicon, calcium oxide becomes simple substance eutectic liquid alloy to emit from smelting furnace, through being ground into the particle below the 25mm behind the cooling curing, be the aluminium silicocalcium of metallurgical high-quality composite assistant AI25Si50Ca30.The high-temperature tail gas that smelting furnace produces mainly is a carbonic acid gas, qualified discharge after dust-collecting and heat exchanging cooling washing; The dust that dedusting obtains returns with the raw material base; The thermal source of heat exchange gained is used for preheating material base and drying material.
Embodiment 2:
The big village of Yunnan Huaning phosphorus ore (P
2O
5: 21-24%, CaO:27-34%, SiO
2: 30-41%), kaolin (SiO
2: 47-52%, AI
2O
3: 40-45%), silica sand (SiO
2: 〉=95%), four kinds of raw materials of coal (fixed carbon content 〉=65%) dry the back respectively and wear into 80% or more with ball mill and pass through 200 purpose powders; Part by weight by 1:1:0:1.2 mixes the water that the back spray adds material gross weight 4%, be pressed into the coccoid material base of Φ 20-40mm with extrusion machine, natural curing three days, again 380 ℃ of-500 ℃ of oven dry, send into carry out preheating in the kiln and about 1300 ℃ the calcining 1.5-2.5 hour, phosphorus in the material base is reduced into elemental phosphorous removing by the solid carbon of coal (or burnt), and the elemental phosphorous Vanadium Pentoxide in FLAKES that further is oxidized to discharges with kiln gas and produces phosphoric acid (being prepared by existing method).Slag base major ingredient after the calcining is Al
2O
3: 17～21%, CaO:11～13%, SiO
2: 31～39%, fixed carbon 25%, directly add it in electric smelting furnace, be heated to 1550～1650 ℃, aluminium in the slag base, silicon, calcium oxide quilt fixed carbon wherein are reduced into simple substance eutectic liquid alloy and emit from smelting furnace, through being ground into the particle below the 25mm behind the cooling curing, be the aluminium silicocalcium of metallurgical high-quality composite assistant AI24Si38Ca18.The high-temperature tail gas that smelting furnace produces mainly is a carbonic acid gas, and tail gas is directly used in drying material behind heat-exchange dedusting, again qualified discharge after the dedusting washing; The secondary high-temperature gas that heat exchange obtains is used for the preheating material base.Main trioxygen-containingization two aluminium of the dust that dedusting obtains are used to produce chemical aluminum oxide.
Claims (2)
1, a kind of mid low grade phosphate rock is produced the method for phosphoric acid and metallurgy additive, it is characterized in that: with mid low grade phosphate rock stone, kaolin, silica and coal or Jiao is raw material, behind raw material drying, fragmentation, the screening abrasive dust, presses SiO
2/ C
aO=3.4～0.5, carbon content are P in total material
2O
5And CO
2, CaO, AI
2O
3, SiO
2, MgO, Fe
2O
31.1～3 of the required carbon that reduces is prepared burden, through mix, ageing, spray adds the material base that an amount of water etc. is made needs again; Material base is sent into and is carried out preheating and calcining in the kiln through natural curing and oven dry, and the kiln gas that contains Vanadium Pentoxide in FLAKES removes to produce phosphoric acid; Carry out carbothermic reduction in the slag base adding electric smelting furnace after the calcining, be ground into particle behind the cooling curing, be metallurgical high-quality composite alloy auxiliary agent.
2, mid low grade phosphate rock according to claim 1 is produced the method for phosphoric acid and metallurgy additive, it is characterized in that: temperature is 1500～2000 ℃ in the carbothermic reduction reaction in the electric smelting furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100940162A CN101462703A (en) | 2009-01-08 | 2009-01-08 | Method for preparing phosphoric acid and metallurgy additive from middle and low grade phosphate ore |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100940162A CN101462703A (en) | 2009-01-08 | 2009-01-08 | Method for preparing phosphoric acid and metallurgy additive from middle and low grade phosphate ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101462703A true CN101462703A (en) | 2009-06-24 |
Family
ID=40803531
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100940162A Pending CN101462703A (en) | 2009-01-08 | 2009-01-08 | Method for preparing phosphoric acid and metallurgy additive from middle and low grade phosphate ore |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539091A (en) * | 2013-10-30 | 2014-01-29 | 武汉工程大学 | Method for preparing phosphoric acid by catalytic reduction of low-medium-grade phosphorite |
-
2009
- 2009-01-08 CN CNA2009100940162A patent/CN101462703A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539091A (en) * | 2013-10-30 | 2014-01-29 | 武汉工程大学 | Method for preparing phosphoric acid by catalytic reduction of low-medium-grade phosphorite |
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Open date: 20090624 |