CN104445113A - Method and raw material for producing yellow phosphorus or phosphoric acid based on electric furnace - Google Patents
Method and raw material for producing yellow phosphorus or phosphoric acid based on electric furnace Download PDFInfo
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- CN104445113A CN104445113A CN201410738992.8A CN201410738992A CN104445113A CN 104445113 A CN104445113 A CN 104445113A CN 201410738992 A CN201410738992 A CN 201410738992A CN 104445113 A CN104445113 A CN 104445113A
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Abstract
The invention discloses a raw material for producing yellow phosphorus or phosphoric acid, and a production method for producing yellow phosphorus or phosphoric acid based on an electric furnace to reduce energy consumption. According to the raw material, phosphate ore, dinas rock, blind coal and a fluxing catalyst are levigated and mixed evenly after being mixed at a ratio, so that the chemical combination temperature of the raw material is reduced; the chemical combination reaction time of the raw material is shortened; the yield of the yellow phosphorus or phosphoric acid in the subsequent production process can be improved; the production cost is reduced; and the raw material is fed to the production system of the yellow phosphorus or phosphoric acid based on the electric furnace, so that the heat energy required for phosphorus reduction can be reduced, i.e., the reaction temperature in the electric furnace is lowered.
Description
Technical field
The present invention relates to chemical field, particularly, relate to a kind of produce yellow phosphorus or phosphoric acid raw material and based on the yellow phosphorus of electric furnace or phosphoric acid production method.
Background technology
The method of producing yellow Phosphorus by electric oven be by, Rock Phosphate (72Min BPL), silica, coke raw material, make the block of about 30mm size respectively, mix thoroughly in rear input electric furnace in proportion, allow Rock Phosphate (72Min BPL), silica, coke raw material, heat in electric furnace, liquid state is molten under high temperature and Carbon monoxide reduction atmosphere existent condition, calcium phosphate molecule and silicon molecule combination reaction in liquid state, generate Calucium Silicate powder (liquid state), matter swaps out elemental phosphorous (or cry evaporate elemental phosphorous), the elemental phosphorous gas of elemental phosphorous at high temperature shape (P4 gas) and CO (carbon monoxide converter) gas, carbon dioxide, impurity dust.Elemental phosphorous gas (P4 gas) and CO (carbon monoxide converter) gas, carbon dioxide, impurity dust, enter spray thrower by vacuum suction and carry out spraying cooling and cleaning removing impurity dust, elemental phosphorous gas (P4 gas) and CO (carbon monoxide converter) gas, carbon dioxide after removing impurity dust, enter in phosphorus groove processed and obtain yellow phosphorus product, the operating voltage of three-phase furnace is 220 ~ 350V.In electric furnace, produce electric arc between each electrode, make in-furnace temperature maintain 1350 ~ 1450 DEG C.In production process, electric furnace converts electric energy to heat energy with the form of raw material resistance and electrode arc, makes furnace charge melting, and therefore electric furnace is main energy consumption equipment.The energy consumption how reducing electric furnace is the integral part of the energy consumption issues solving producing yellow Phosphorus by electric oven or phosphoric acid.
Summary of the invention
The present invention is directed to the weak point of the production method of existing producing yellow Phosphorus by electric oven and phosphoric acid, a kind of raw material producing yellow phosphorus or phosphoric acid and the production method consumed energy based on the reduction that electric furnace produces yellow phosphorus or phosphoric acid are provided, this raw material is by Rock Phosphate (72Min BPL), Red Sandstone, hard coal, flux catalyst, after being mixed in proportion, levigate, mixing, to reduce the composition temperatures of raw material, shorten the combination reaction time of raw material, the yellow phosphorus in subsequent production process or phosphoric acid output can be improved, reduce production cost, this raw material is adopted to put into based in the yellow phosphorus of electric furnace or the production system of phosphoric acid, the heat energy that raw material combination reaction needs can be reduced, namely the temperature of reaction in electric furnace is reduced.
The present invention's adopted technical scheme that solves the problem is:
A kind of raw material producing yellow phosphorus or phosphoric acid, be processed into pulverulent mixture by after the Rock Phosphate (72Min BPL) of suitable weight, Red Sandstone, hard coal, flux catalyst mixing with powder manufacturing apparatus, then pulverulent mixture added the flat oval solids or ball-shaped solids that are pressed into after the appropriate water containing solidifying agent is mixed thoroughly.
Further, by weight, described Rock Phosphate (72Min BPL) is 56-68 part, Red Sandstone is 14-26 part, hard coal is 10-15 part, flux catalyst is 1-6 part.
Solidifying agent to be massfraction be 85% phosphoric acid, the amount of solidifying agent is the 1-6% of Rock Phosphate (72Min BPL), Red Sandstone, hard coal, flux catalyst total amount.The selection of solidifying agent, in fact be also selectable, new impurity can not be introduced, and a lot of prior art all adopts is sodium hydroxide or humic acid, these caking agents can bring the trace element that much cannot remove to be blended in yellow phosphorus, cause yellow phosphorus low quality.
The composition by weight of described flux catalyst is: ferric oxide 0.5-3 part, aluminium sesquioxide 0.5-3 part, magnesium oxide 0.3-2 part, sodium-chlor 1-3 part.
Described flat oval solids size is 20mm × 10mm × 5mm-80mm × 60mm × 40mm.Flat oval solids bonds power by force in stove, not easily flame accident occurs.
Described ball-shaped solids diameter is 20mm-70mm.
The fineness of described pulverulent mixture is 0.01mm-0.5mm.
Traditional method is Rock Phosphate (72Min BPL), silica, coke raw material, make the block of about 30mm size in proportion respectively, block mixing is mixed thoroughly and enters electric furnace, heat and be fused into liquid state, calcium molecule in the calcium phosphate allowing in high-temperature liquid state and silicon molecule combination reaction, generate Calucium Silicate powder molecule (liquid state), and matter swaps out elemental phosphorous (or cry evaporate), the elemental phosphorous gas of elemental phosphorous at high temperature shape (P4 gas), elemental phosphorous gas (P4 gas) obtains yellow phosphorus product through phosphorus system processed.This block is heated the production method (, apart from too far away, combination reaction is slow for intermolecular chemical combination) being fused into liquid combination reaction, and the power consumption that result in phosphorus production increases.
And three of suitable proportion kinds of raw materials are added the flux catalyst of suitable proportion by the present invention and suitable solidifying agent mix grinding becomes meal, the temperature of raw material reaction needed in electric furnace can be reduced, allow molecule in raw material when zero distance or very small distance, quick combination reaction, shorten the chemical combination reaction times, make traditional temperature of reaction be reduced to 1230-1260 DEG C from 1350 ~ 1450 DEG C, also reduce the calcination amount of phosphoric while enhancing productivity, improve the yield of phosphoric.
Produce the method for yellow phosphorus or phosphoric acid based on electric furnace by aforementioned base materials, flat oval solids or ball solids are put into after adding heat extraction material crystal water and organic impurities in vertical solidification storehouse, be warmed to 1230-1260 DEG C and obtain elemental phosphorous gas, after elemental phosphorous gas being entered the insulation proliferation cyclone dedusting of setting up, continue to throw in into yellow phosphorus or phosphoric acid production system yellow phosphorus or phosphoric acid.
The temperature flat oval solids or ball solids being heated to removing material crystal water and organic impurities is 480 DEG C.
The present invention breaches traditional producing yellow Phosphorus by electric oven and the production method of phosphoric acid, change the calcium molecule in calcium phosphate and silicon molecule chemical combination reactive mode, make calcium molecule in calcium phosphate and silicon molecule when reaching combination reaction temperature, without any need for stirring kinetic energy, under the state of zero distance or very little very small distance, speed is fast completes combination reaction.
To sum up, the invention has the beneficial effects as follows:
1, the present invention is by the Rock Phosphate (72Min BPL) of suitable weight, Red Sandstone, hard coal, be processed into the pulverulent mixture of 0.01mm-0.5mm with powder manufacturing apparatus after flux catalyst mixing, again pulverulent mixture is added the flat oval solids or ball-shaped solids that are pressed into after the appropriate water containing solidifying agent is mixed thoroughly, the chemical combination reaction times can be shortened, the power consumption of yellow phosphorus or phosphoric acid produced by reduction electric furnace at double, power consumption is reduced to less than 9000 degree from 15000-16000 degree, production year output refer to more than 50%, the Yellow Phosphorous Plant annual production of former annual production 0.6w ton is made to bring up to more than 1.0w ton,
2, the present invention is owing to shortening the combination reaction time, decreases the ignition loss amount of phosphoric;
3, present invention employs hard coal and reduce raw materials cost;
4, the present invention is owing to shortening the combination reaction time, also reduces the consumption of Graphite Electrodes, and electric furnace production cost is reduced further;
5, the present invention adds at former electric furnace kiln gas exit place or newly-built electric furnace kiln gas exit place sets up insulation proliferation cyclone, eliminate in kiln gas 97% dust impurity (micronutrient levels such as dust impurity middle-weight rare earths is high, can utilize), decrease mud phosphorus to carry under one's arms loss, decrease the yellow phosphorus-refined workload of 97%;
6, the present invention is due to the change of production method, and combination reaction is relatively more complete, and the yield of yellow phosphorus is higher than original production method, and the reduction ratio of phosphorus is up to more than 93%, and total yield, up to more than 90%, considerably reduces production cost.
Embodiment
Below in conjunction with embodiment, to the detailed description further of the present invention's do, but embodiments of the present invention are not limited thereto.
embodiment 1:
P in Rock Phosphate (72Min BPL)
20
5content 26-31%: the tailings after beneficiated phosphate ore can be selected.Si0 in Red Sandstone
2content 75-99%: the yellow ground rock of local silicon content>=95%, white sand rock (these three kinds of sandstone easily grind, economize on electricity), industrial residue can be selected.Hard coal, C content 75-82%: can select through forging sulphur removal processed, the blue charcoal coal of removal of impurities, coke powder.
A kind of raw material producing yellow phosphorus or phosphoric acid, by 56 parts of Rock Phosphate (72Min BPL), 23 parts of Red Sandstone, 15 parts of hard coals, 6 parts of flux catalysts, be processed into the pulverulent mixture of 0.01mm after mixing with vertical grinder or other powder manufacturing apparatus, then pulverulent mixture is added 15% containing raw material weight 2% solidifying agent water in mix thoroughly after the flat oval solids of 20mm × 10mm × 5mm that is pressed into.Flat for 20mm × 10mm × 5mm oval solids is entered in vertical solidification storehouse, with yellow phosphoric tail gas (CO (carbon monoxide converter) gas) in vertical solidification storehouse bottom combustion chamber, burning, heating is to 480 DEG C, flat oval solids is allowed to solidify and after removing material crystal water and organism, directly enter into and original produce yellow phosphorus and the electric furnace of phosphoric acid or the electric furnace of newly-built production yellow phosphorus and phosphoric acid, be heated to 1230-1260 DEG C, just obtain elemental phosphorous gas (P4 gas).Elemental phosphorous gas (P4 gas) enters original phosphorus production system or newly-built yellow phosphorus or phosphoric acid production system and can produce yellow phosphorus or phosphoric acid product after entering the dedusting of insulation proliferation cyclone.Wherein solidifying agent is 85wt% phosphoric acid.Wherein, the composition by weight of flux catalyst is: ferric oxide 0.5 part, aluminium sesquioxide 0.5 part, 0.3 part, magnesium oxide, 2 parts, sodium-chlor.
The power consumption of embodiment 1 is reduced to less than 9000 degree, and production year output refer to more than 50%, and Yellow Phosphorous Plant annual production brings up to more than 1.0w ton from original 0.6w ton; The reduction ratio more than 90.2% of phosphorus, total yield reaches 88%.
embodiment 2
P in Rock Phosphate (72Min BPL)
20
5content 26-31%: the tailings after beneficiated phosphate ore can be selected.Si0 in Red Sandstone
2content 75-99%: the yellow ground rock of local silicon content>=95%, white sand rock (these three kinds of sandstone easily grind, economize on electricity), industrial residue can be selected.Hard coal, C content 75-82%: can select through forging sulphur removal processed, the blue charcoal coal of removal of impurities, coke powder.
A kind of raw material producing yellow phosphorus or phosphoric acid, by 68 parts of Rock Phosphate (72Min BPL), 19 parts of Red Sandstone, 10 parts of hard coals, 3 parts of flux catalysts, be processed into the pulverulent mixture of 0.5mm after mixing with vertical grinder or other powder manufacturing apparatus, then pulverulent mixture is added 15% containing raw material weight 1% solidifying agent water in mix thoroughly after be pressed into diameter 21mm ball-shaped solids.Diameter 21mm ball-shaped solids is entered in vertical solidification storehouse, with yellow phosphoric tail gas (CO (carbon monoxide converter) gas) in vertical solidification storehouse bottom combustion chamber, burning, heating is to 480 DEG C, ball-shaped solids is allowed to solidify and after removing material crystal water and organism, directly enter into and original produce yellow phosphorus and the electric furnace of phosphoric acid or the electric furnace of newly-built production yellow phosphorus and phosphoric acid, be heated to 1230-1260 DEG C, just obtain elemental phosphorous gas (P4 gas).Elemental phosphorous gas (P4 gas) enters original phosphorus production system or newly-built yellow phosphorus or phosphoric acid production system and can produce yellow phosphorus or phosphoric acid product after entering the dedusting of insulation proliferation cyclone.Wherein, the composition by weight of flux catalyst is: ferric oxide 1.5 parts, aluminium sesquioxide 1.8 parts, 0.8 part, magnesium oxide, 1 part, sodium-chlor.Solidifying agent is 85wt% phosphoric acid.
The power consumption of embodiment 2 is reduced to less than 9000 degree, and production year output refer to more than 50%, and Yellow Phosphorous Plant annual production brings up to more than 1.0w ton from original 0.6w ton; The reduction ratio more than 89.2% of phosphorus, total yield reaches 89%.
embodiment 3
P in Rock Phosphate (72Min BPL)
20
5content 26-31%: the tailings after beneficiated phosphate ore can be selected.Si0 in Red Sandstone
2content 75-99%: the yellow ground rock of local silicon content>=95%, white sand rock (these three kinds of sandstone easily grind, economize on electricity), industrial residue can be selected.Hard coal, C content 75-82%: can select through forging sulphur removal processed, the blue charcoal coal of removal of impurities, coke powder.
A kind of raw material producing yellow phosphorus or phosphoric acid, will 63 parts of Rock Phosphate (72Min BPL), 26 parts of Red Sandstone, 10 parts of hard coals, be processed into the pulverulent mixture of 0.08mm after 1 part of flux catalysts mixing with vertical grinder or other powder manufacturing apparatus, then pulverulent mixture is added mix thoroughly in 15% water containing 6% solidifying agent of raw material weight after 80mm × 60mm × 40mm of being pressed into.Flat oval solids, enter in vertical solidification storehouse, with yellow phosphoric tail gas (CO (carbon monoxide converter) gas) in vertical solidification storehouse bottom combustion chamber, burning, heating is to 480 DEG C, flat oval solids is allowed to solidify and after removing material crystal water and organism, directly enter into and original produce yellow phosphorus and the electric furnace of phosphoric acid or the electric furnace of newly-built production yellow phosphorus and phosphoric acid, be heated to 1230-1260 DEG C, just obtain elemental phosphorous gas (P4 gas).Elemental phosphorous gas (P4 gas) enters original phosphorus production system or newly-built yellow phosphorus or phosphoric acid production system and can produce yellow phosphorus or phosphoric acid product after entering the dedusting of insulation proliferation cyclone.
The composition by weight of flux catalyst is: ferric oxide 1.5 parts, aluminium sesquioxide 1.8 parts, 0.8 part, magnesium oxide, 3 parts, sodium-chlor.
The power consumption of embodiment 3 is reduced to less than 9000 degree, and production year output refer to more than 50%, and Yellow Phosphorous Plant annual production brings up to more than 1.0w ton from original 0.6w ton; The reduction ratio more than 89% of phosphorus, total yield reaches 89%.
embodiment 4:
P in Rock Phosphate (72Min BPL)
20
5content 26-31%: the tailings after beneficiated phosphate ore can be selected.Si0 in Red Sandstone
2content 75-99%: the yellow ground rock of local silicon content>=95%, white sand rock (these three kinds of sandstone easily grind, economize on electricity) work waste residue can be selected.Hard coal, C content 75-82%: can select through forging sulphur removal processed, the blue charcoal coal of removal of impurities, coke powder.
A kind of raw material producing yellow phosphorus or phosphoric acid, by 67 parts of Rock Phosphate (72Min BPL), 14 parts of Red Sandstone, 14 parts of hard coals, 5 parts of flux catalysts, be processed into the pulverulent mixture of 0.1mm with vertical grinder or other powder manufacturing apparatus after mixing, again pulverulent mixture is added 15% containing raw material weight 5% solidifying agent water in mix thoroughly, after be pressed into diameter 70mm ball-shaped solids.Diameter 70mm ball-shaped solids is entered in vertical solidification storehouse, with yellow phosphoric tail gas (CO (carbon monoxide converter) gas) in vertical solidification storehouse bottom combustion chamber, burning, heating is to 480 DEG C, flat oval solids is allowed to solidify and after removing material crystal water and organism, directly enter into and original produce yellow phosphorus and the electric furnace of phosphoric acid or the electric furnace of newly-built production yellow phosphorus and phosphoric acid, be heated to 1230-1260 DEG C, just obtain elemental phosphorous gas (P4 gas).Elemental phosphorous gas (P4 gas) enters original phosphorus production system or newly-built yellow phosphorus or phosphoric acid production system and can produce yellow phosphorus or phosphoric acid product after entering the dedusting of insulation proliferation cyclone.
The composition by weight of flux catalyst is: ferric oxide 1.5 parts, aluminium sesquioxide 1.8 parts, 0.8 part, magnesium oxide, 2.4 parts, sodium-chlor.
The power consumption of embodiment 4 is reduced to less than 9000 degree, and production year output refer to more than 50%, and Yellow Phosphorous Plant annual production brings up to more than 1.0w ton from original 0.6w ton; The reduction ratio more than 93% of phosphorus, total yield reaches 90%.
Claims (9)
1. produce the raw material of yellow phosphorus or phosphoric acid for one kind, it is characterized in that, be processed into pulverulent mixture by after the Rock Phosphate (72Min BPL) of suitable weight, Red Sandstone, hard coal, flux catalyst mixing with powder manufacturing apparatus, then pulverulent mixture added the flat oval solids or circular ball-type solids that are pressed into after the appropriate water containing solidifying agent is mixed thoroughly.
2. raw material according to claim 1, is characterized in that, by weight, described Rock Phosphate (72Min BPL) is 56-68 part, Red Sandstone is 14-26 part, hard coal is 10-15 part, flux catalyst is 1-6 part.
3. raw material according to claim 2, is characterized in that, solidifying agent to be massfraction be 85% phosphoric acid, the amount of solidifying agent is the 1-6% of Rock Phosphate (72Min BPL), Red Sandstone, hard coal, flux catalyst total amount.
4. the raw material according to any one of claim 1-3, is characterized in that, the composition by weight of described flux catalyst is: ferric oxide 0.5-3 part, aluminium sesquioxide 0.5-3 part, magnesium oxide 0.3-2 part, sodium-chlor 1-3 part.
5. the raw material according to any one of claim 1-3, is characterized in that, described flat oval solids size is 20mm × 10mm × 5mm-80mm × 60mm × 40mm.
6. the raw material according to any one of claim 1-3, is characterized in that, described ball-shaped solids diameter is 21mm-70mm.
7. raw material according to claim 5, is characterized in that, the fineness of described pulverulent mixture is 0.01mm-0.5mm.
8. produce the method for yellow phosphorus or phosphoric acid based on electric furnace with the raw material described in any one of claim 1-7, it is characterized in that, flat oval solids or ball solids are put into after adding heat extraction material crystal water and organic impurities in vertical solidification storehouse, be warmed to 1230-1260 DEG C and obtain elemental phosphorous gas, after elemental phosphorous gas being entered the insulation proliferation cyclone dedusting of setting up, continue to throw in into yellow phosphorus or phosphoric acid production system yellow phosphorus or phosphoric acid.
9. method according to claim 8, is characterized in that, the temperature flat oval solids or ball solids being heated to removing material crystal water and organic impurities is 480 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104477862A (en) * | 2014-12-16 | 2015-04-01 | 四川有峰环保科技有限公司 | Method and raw material for producing yellow phosphorus or phosphoric acid by adopting rotary kiln |
| CN107055498A (en) * | 2017-04-28 | 2017-08-18 | 北京迈未科技有限公司 | The apparatus and method for producing yellow phosphorus and phosphoric acid simultaneously |
| CN112429707A (en) * | 2020-11-27 | 2021-03-02 | 四川阳华环保科技有限公司 | Method and device for producing yellow phosphorus and phosphoric acid by replacing in kiln method preheating material sealing rotary cylinder |
| CN115744846A (en) * | 2022-11-17 | 2023-03-07 | 云南磷化集团有限公司 | Method for preparing yellow phosphorus by catalyzing carbon thermal reduction of phosphorite |
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| CN112429707A (en) * | 2020-11-27 | 2021-03-02 | 四川阳华环保科技有限公司 | Method and device for producing yellow phosphorus and phosphoric acid by replacing in kiln method preheating material sealing rotary cylinder |
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Effective date of registration: 20160316 Address after: 621000 Sanjiang Road, Mianyang, Sichuan Province Road, No. 39 Applicant after: SICHUAN JINLIN SILICON VALLEY TECHNOLOGY CO., LTD. Address before: 644000 Yibin province Sichuan City Cuiping District An Fu Minjiang River Road No. 100 Applicant before: SICHUAN YOUFENG ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. |
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Application publication date: 20150325 |