CN104445115A - Preparation method of raw material phosphate ores for yellow phosphorus production - Google Patents
Preparation method of raw material phosphate ores for yellow phosphorus production Download PDFInfo
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Abstract
The invention discloses a preparation method of raw material phosphate ores for yellow phosphorus production. According to the preparation method, the powdered phosphate ores which are taken as the raw material are sintered by a box-type sintering furnace to form sintered phosphate ores, and then the sintered phosphate ores are crushed to obtain the raw material lump phosphate ores for yellow phosphorus production. According to the preparation method of the raw material phosphate ores for yellow phosphorus production, the powdered phosphate ores are agglomerated by use of the sintering method to meet the granularity need of the raw material lump phosphate ores for yellow phosphorus production, and meanwhile, after the low-grade powdered ores are sintered, the grade of the sintered ores is improved by about 2% as compared with the powdered ores, the CO2 content is reduced by 9% and the silicon-calcium ratio is increased by 0.15; in theory, the power consumption can be reduced by 2600kwh if the sintered ores are used for smelting the yellow phosphorus. Besides, the preparation method of the raw material phosphate ores for yellow phosphorus production has the advantages that a large quantity of low-grade powdered phosphate ores are well utilized, the resources are recycled, meanwhile, the sintered lump phosphate ores are used for phosphorus production, and therefore, the energy consumption is reduced, the production cost is saved, and the discharge of phosphorus slag and phosphorus sludge in the yellow phosphorus production process can be reduced and the quality of the yellow phosphorus product can be improved; the preparation method is economic and environmental friendly.
Description
Technical field
The present invention relates to a kind of preparation method of Rock Phosphate (72Min BPL), be specifically related to a kind of sintering method utilizing ground phosphate rock to prepare phosphorus production phosphorus ore, belong to technical field of phosphorous chemical industry.
Background technology
Yellow phosphorus is the basic material of phosphorous chemical industry, its production technique is comparatively simple, that Rock Phosphate (72Min BPL), silica and coke are put in electric furnace with granularity by a certain percentage, solution estranged, reduction reaction is issued at the high temperature of 1300 DEG C, phosphorus steam is cooled together with stove dirt, obtain product after rinsing, and high temperature furnace slag is then direct discharges from electric furnace.Production principle be Rock Phosphate (72Min BPL) at high temperature, by carbon reduction generting element phosphorus, after collecting, obtain product P
4.
Rock Phosphate (72Min BPL) is the main raw material of phosphorus production, and the quality of ore quality directly has influence on operation and the technic index of electric furnace, namely has influence on the Yield and quality of yellow phosphorus, energy consumption, cost and economic benefit.
Rock Phosphate (72Min BPL) component is except P
2o
5outside component, also have CaO, SiO
2, Fe
2o
3, Al
2o
3, CO
2, the component such as F.SiO
2be one of useful component participating in Phosphate ore reduction reaction, in furnace charge, control the acidity index S iO of slag
2/ CaO(mass ratio) in 0.75 ~ 0.85 scope, furnace charge can be made to have lower melt temperature, impelling the direction of reacting to generating phosphorus to carry out, usually needing when preparing burden to add silica to supplement middle SiO
2the deficiency of content; Carbonate is the adverse factor in phosphorus production, and the existence of a large amount of carbonate can cause in-furnace temperature to decline, meanwhile, and the CO released after carbonate decomposition
2the phosphorus vapor action distilled out with reaction zone generates the suboxide of phosphorus, as P
3o
4, P
2o
3etc. the loss bringing phosphorus, reduce the rate of recovery of phosphorus, the decomposition of carbonate and CO
2reduction, also want consumed energy, CO in Rock Phosphate (72Min BPL)
2content often increases by 1%, if Restore All becomes CO, yellow phosphorus per ton will increase power consumption 200kwh, many consumption coke 29kg.
Produce yellow phosphorus to furnace charge except chemical composition has requirement, also have certain particle size requirement, the size of furnace size directly can affect normally carrying out of electric reaction in furnace.It is ensure that furnace gas evenly can discharge the essential condition of electric furnace that furnace size meets processing requirement, and can also obtain normal furnace gas temperature and dustiness, improves yellow phosphorus quality, reduces mud phosphorus output.Production practice show, the yellow phosphorus electric furnace that watt level is different, also have different requirements to furnace size.Such as, yellow phosphorus electric furnace power is when 2000-5000KVA, and the granularity of Rock Phosphate (72Min BPL) should control at 4-25mm, and silica granularity should be consistent with the granularity of Rock Phosphate (72Min BPL), and the granularity of coke should control at 3-15mm, and all feed stock for blast furnace should not contain the fine powder of below 3mm.
Current most phosphorus production enterprise is in order to reduce the production cost of yellow phosphorus, and phosphorus ore raw material is based on the natural lump ore of mining, and natural lump ore is of high grade, P
2o
5content, more than 28%, can be directly used in phosphorus production, but in natural lump ore, carbon dioxide content is high, causes a large amount of electric energy in phosphorus production process for the decomposition of carbonic acid gas, to add power consumption and the cost of phosphorus production.The fine ore amount simultaneously produced in phosphorate rock mining process accounts for 50% of produced quantity, due to the lower (P of fine ore grade
2o
5content is low), the fine powder that fineness is less than 3mm all can not enter stove production yellow phosphorus, therefore causes a large amount of wastes of Rock Phosphate (72Min BPL) fine ore.Along with day by day exhausted, the dilution of phosphate rock resource, not only cost is more and more higher still to use natural lump ore to produce yellow phosphorus, also unrealistic, therefore carries out process to phosphorus production phosphorus ore raw material imperative.
Phosphorus production has grade requirement and granularity requirements to raw ore, and the ore therefore adopting Rock Phosphate (72Min BPL) agglomeration of fine ore to be used as phosphorus production is best selection.Because can produce the phosphorus powder ore deposit accounting for produced quantity 50% in mining process, in transport drying process, also can produce breeze, this fine ore is not all utilized effectively, and causes a large amount of wastes of resource simultaneously.
There are two kinds of Technologies for agglomeration of fine ore at present, one is pelletizing method, and one is knurl connection.Knurl connection is calcined under 1200 ~ 1400 DEG C of high temperature in rotary kiln by chip phosphorus ore, the mutual adhesive aggregation of ore particles is made to become spheroid, organism simultaneously in ore, carbonic acid gas and 10% ~ 30% fluorine be discharged in calcination process, after cooling, fragmentation, screening, obtain the knurl ramming material of qualified particle diameter, again calcine in the fines retrieval system under sieve.The method makes material be difficult to process when ring formation and knot kliner coating in rotary kiln, and labor condition is poor, heat utilization efficiency is low, fuel consumption is large, tail gas from electric furnace can only about the half of the amount of satisfying the demand, therefore processing costs is higher, and the method uses clay as caking agent, phosphorus ore grade to be declined, slag amount increase when simultaneously causing phosphorus production.The sixties, new construction device did not adopt this technique substantially.
When adopting pelletizing method machining chips shape raw material phosphorus ore or selected ground phosphate rock, phosphorus ore first through super-dry, levigate to 60% ~ 80% by 200 mesh sieves, a certain amount of clay is added as caking agent in balling disc or drum pelletizer, make the green-ball that granularity is 10 ~ 20mm, then through the operations such as super-dry, preheating, roasting, cooling i.e. obtained phosphorus ore pelletizing.What adopt is exactly pelletizing method to such as patent CN 101973536 B disclosed " phosphorus fine ore pelletizing produces the preparation method of yellow phosphorus ".The roasting apparatus that pelletizing method is commonly used has drying grate and rotary kiln two class.There are German Knapsack, Dutch Vlissingen, Chinese Kunming tripoly phosphate sodium STPP factory in typical factory, employing be that roasting apparatus has drying grate and cooling drying grate tandem process; Also have German Piessteritz factory, employing be drying grate drying, preheating, enter the technical process of rotary kiln baking.
Pelletizing method is higher to phosphorus ore ingredient requirement, need carry out drying and abrasive dust to ore, investment and power consumption higher; The phosphorus ore higher to carbonate containing, due to CO
2decreasing ratio is low, and yellow phosphorus power consumption is corresponding higher; Need add water glass etc. when pelletizing as binding agent, production cost is higher; Larger on the impact of yellow phosphorus quality product after interpolation organic adhesive; Balling ratio is low.
Summary of the invention
Object of the present invention is just the deficiency proposed for above-mentioned prior art, a kind of processing technology of phosphorus agglomeration of fine ore is provided, phosphorus powder ore deposit sinters after mix makes the Rock Phosphate (72Min BPL) raw material that phosphorus production enters stove, there is comprehensive utilization of resources, reduce carbon dioxide content in yellow phosphorus furnace charge, improve output phosphor, reduce energy consumption, reduce phosphorus production cost, improve the feature of yellow phosphorus quality product.
To achieve these goals, the technical solution used in the present invention is such:
A preparation method for phosphorus production raw material phosphorus ore, it is with Rock Phosphate (72Min BPL) fine ore for raw material, and form Rock Phosphate (72Min BPL) agglomerate through chamber type sintering stove sintering, Rock Phosphate (72Min BPL) agglomerate obtains phosphorus production raw material phosphor ore lump ore through fragmentation, and its concrete production stage is:
(1) raw material prepares:
With go-cart, the Rock Phosphate (72Min BPL) fine ore after weighing is put into stirrer, add coal dust by the mark sense fine ore of coal blending amount 3% ~ 15%, start stirrer mixing, evenly spray into atomized water during mixing, ensure that in compound, moisture content is 3% ~ 12%, mixing time is 1 ~ 20 minute, stop stirring, discharging.
(2) sinter
A, shop fixtures of returning mine
For preventing fine ore to bleed air channel and protection fire grate, on fire grate, even lay one deck granularity is greater than the Rock Phosphate (72Min BPL) of 5mm, the preferred small sintering ore of Rock Phosphate (72Min BPL), without under the condition of returning mine with natural Rock Phosphate (72Min BPL) lump ore replacement
B, cloth
After returning mine and completing, utilize portable belt conveyer to lay compound in chamber type sintering stove, compound requires that lay is smooth, thickness is 100 ~ 600mm, and above the bed of material lay coal dust, the lay thickness of coal dust is 1 ~ 10mm, and after cloth completes, whether each seal point of inspection sintering oven has the situation of leaking out.
C, igniting
After cloth completes, lighter for ignition moves in parallel above agglomerating chamber, starts burner blower and vacuum fan, regulates vacuum fan air quantity, by-pass valve control opening amount about 10%, open tail gas of yellow phosphorus boiler through valve of supplying gas to light a fire, when ignition temperature reaches 600 ~ 1300 DEG C, standard-sized sheet vacuum fan air-quantity adjusting valve carries out exhausting, ignition time is 1 ~ 10 minute, point fire cover leaves agglomerating chamber, sinters, and sintering tail gas is through smoke stack emission.
D, discharging
When temperature at the bottom of sinter machine reach 100 ~ 600 DEG C then start to decline time, represent and arrive sintering end point, after having sintered, turn down vacuum fan volume damper, sinter box bottom discharge push-pull valve is opened after the cooling of ore deposit to be sintered, then open excellent valve extraction road and bridge and carry out discharging, finished product agglomerate drops out from bottom discharge openings.
(3) broken and screening
Agglomerate finished product carries out fragmentation after cooling, and the agglomerate that broken rear particle diameter is less than 5mm re-starts sintering after batching, and gets a certain amount of agglomerate as grate-layer material of returning mine, and residue agglomerate is then sent in Yellow phosphorus furnace and carried out phosphorus smelting.
The present invention replaces binding agent with atomized water in stock preparation process, with low cost.In process of production, compound will keep suitable moisture all the time, water plays a part wetting material, promotes material balling-up in the preparation process of sintered material, suitable sintered material moisture content can guarantee ventilation property material bed in sintering process, thus raising vertical sintering speed, the raising of acceleration of sintering ore deposit quantity and quality, simultaneously, water also plays a part transferring heat and oxygen amount in sintering process, the present invention utilizes atomized water granulation both can improve the contact area of material and water, also can improve the homogeneity of material balling-up simultaneously.
Mix the coal dust of 3% ~ 15% in fine ore, ensure that the sintering of fine ore is even.In process of production, the seed output and quality of height on agglomerate of mixed carbon comtent has obvious impact.Mixed carbon comtent is too high, can expand zone of combustion, increases the resistance of sintered layer, causes production declining, also can directly affect the quality of agglomerate because of the enhancing of reducing atmosphere simultaneously.Mixed carbon comtent is too low, sintering zone temperature will be caused not enough, make the decrease in yield of agglomerate, thus affect the seed output and quality of agglomerate.
Compound layer thickness is 100 ~ 600mm, and bed thickness can impact the quality of agglomerate, and when the bed of material is crossed thin, because materialbeds comminution is little, productivity is high, but the bad upper strata agglomerate proportion of intensity is large, causes agglomerate yield rate low, increase of returning mine.When the bed of material is blocked up, sintering process heat utilization ratio is better, firing rate reduces, and reductibility improves, and median particle size level increases simultaneously, to return mine minimizing, yield rate improves, but after improving bed thickness, adds the ununiformity of levels agglomerate, and because materialbeds comminution increases, productivity will decline.
Ignition temperature, at 600 ~ 1300 DEG C, keeps 1 ~ 10 minute ignition time, ensures the coal dust layer Thorough combustion on the mixing bed of material, ensures carrying out smoothly of Rock Phosphate (72Min BPL) powder mine sintering.The object of igniting is that the solid carbon in the sintered material of top layer is caught fire, and makes top layer clinkering, then relies on exhausting that sintering process is proceeded downwards.Therefore ignition temperature must reach the optimum temperature of zone of combustion, in order to ensure the Thorough combustion of sinter bed surface solid carbon, also has certain requirement to ignition time.Therefore, the present invention, by the control of preparation of raw material, lay and sintering oven, ensure that carrying out smoothly of Rock Phosphate (72Min BPL) powder mine sintering.
Compared with prior art, the present invention adopts the method for sintering by Rock Phosphate (72Min BPL) agglomeration of fine ore to meet the granularity requirements of phosphorus production raw material phosphor ore, and fine ore is in sintering process simultaneously, and in mineral, institute's carbonate containing is deviate from, and improves P in feed stock for blast furnace
2o
5grade, simultaneously carbonate deviate to considerably reduce CO in feed stock for blast furnace
2content.Low-grade fine ore through sintering after grade comparatively fine ore exceed about 2%, CO
2content declines 9%, and silico-calcium is than raising 0.15, and data shows CO
2content often declines and about 1% can reduce power consumption 200kwh, reduces coke consumption simultaneously and is about 29Kg; P
2o
5content often promotes 1%, can reduce power consumption 400kwh, namely uses agglomerate to smelt yellow phosphorus and can reduce power consumption 2600kwh in theory.Ore silico-calcium ratio after sintering can improve about about 0.15, and when phosphorus production, silica consumption can reduce about 1.2t; Fine ore, after sintering, can deviate from the organism in ore, thus improves yellow phosphorus quality product.
Therefore the present invention makes a large amount of low-grade phosphorus powder ore deposits obtain comparatively good utilisation, achieve the recycling of resource, the Rock Phosphate (72Min BPL) lump ore simultaneously obtained through the inventive method is for phosphorus production, both energy consumption was reduced, save production cost, the quantity discharged of phosphorus slag and mud phosphorus in phosphorus production process can be reduced again, improve the quality product of yellow phosphorus, economic environmental protection.
Accompanying drawing explanation
Fig. 1 is technological process of production schematic diagram of the present invention.
Embodiment
In order to the object of the present invention of understanding clearly, technical scheme and beneficial effect, below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention do not limited in the examples below.
One, phosphorus ore mine ore deposit is prepared:
(1) embodiment 1:
As shown in Figure 1, get the raw materials ready as follows: the phosphorus powder ore deposit of 960Kg grade 23%, mixed carbon comtent 8%, water distribution quantity 6%.
Preparation method is as follows:
Step 1: add in mixing tank by the phosphorus powder ore deposit after weighing, add load weighted hard coal, starts mixing tank and mixes, spray into appropriate atomized water during mixing.
Step 2: the raw material mixed enters in box sinter machine through transfer roller, ensure the smooth of charge level, raw thickness is 350mm, and the bed of material after completing shows lay coal particle.
Step 3: utilize lighter for ignition ignite the bed of material surface coal particle, start vacuum fan, after-8.5kpa, open exhausting valve until vacuum fan negative regulation, sintering start to carry out.Raw material reaches 1150 DEG C at chamber type sintering built-in temperature.
Step 4: exhaust temperature starts to decline, then sintering process terminates, opens chamber type sintering motor spindle blow-off valve discharge.
Step 5: the agglomerate of discharge obtains qualified phosphorus production furnace charge after crushing and screening.
After testing, agglomerate product comparatively fine ore phosphorus pentoxide content improves 1.3%, and carbon dioxide content declines 8.9%, and silico-calcium is than raising 0.12.
(2) embodiment 2:
As shown in Figure 1, get the raw materials ready as follows: the phosphorus powder ore deposit of 960Kg grade 23%, mixed carbon comtent 7%, water distribution quantity 9%.
Preparation method is as follows:
Step 1: add in mixing tank by the phosphorus powder ore deposit after weighing, add load weighted hard coal, starts mixing tank and mixes, spray into appropriate atomized water during mixing.
Step 2: the raw material mixed enters in box sinter machine through transfer roller, ensure the smooth of charge level, raw thickness is 350mm, and the bed of material after completing shows lay coal particle.
Step 3: utilize lighter for ignition ignite the bed of material surface coal particle, start vacuum fan, after-8.5kpa, open exhausting valve until vacuum fan negative regulation, sintering start to carry out.Raw material reaches 1050 DEG C at chamber type sintering built-in temperature.
Step 4: exhaust temperature starts to decline, then sintering process terminates, opens chamber type sintering motor spindle blow-off valve discharge.
Step 5: the agglomerate of discharge obtains qualified phosphorus production furnace charge after crushing and screening.
After testing, agglomerate product comparatively fine ore phosphorus pentoxide content improves 2.3%, and carbon dioxide content declines 9%, and silico-calcium is than raising 0.12.
(3) embodiment 3:
As shown in Figure 1, get the raw materials ready as follows: the phosphorus powder ore deposit of 960Kg grade 23%, mixed carbon comtent 6%, water distribution quantity 6%.
Preparation method is as follows:
Step 1: add in mixing tank by the phosphorus powder ore deposit after weighing, add load weighted hard coal, starts mixing tank and mixes, spray into appropriate atomized water during mixing.
Step 2: the raw material mixed enters in box sinter machine through transfer roller, ensure the smooth of charge level, raw thickness is 350mm, and the bed of material after completing shows lay coal particle.
Step 3: utilize lighter for ignition ignite the bed of material surface coal particle, start vacuum fan, after-8.5kpa, open exhausting valve until vacuum fan negative regulation, sintering start to carry out.Raw material reaches 950 DEG C at chamber type sintering built-in temperature.
Step 4: exhaust temperature starts to decline, then sintering process terminates, opens chamber type sintering motor spindle blow-off valve discharge.
Step 5: the agglomerate of discharge obtains qualified phosphorus production furnace charge after crushing and screening.
After testing, agglomerate product comparatively fine ore phosphorus pentoxide content improves 1.8%, and carbon dioxide content declines 8.9%, and silico-calcium is than raising 0.12.
Two, contrast experiment
Respectively phosphorus ore mine ore deposit obtained for embodiment 1-3 and natural Rock Phosphate (72Min BPL) lump ore are used for phosphorus smelting, find agglomerate be used for phosphorus smelting comparatively natural lump ore can reduce power consumption about 2600kwh, reduce silica about add-on 1.2t, reduce coke about add-on 260kg, and smelt organic impurity content in the yellow phosphorus obtained with agglomerate also lower than natural lump ore.
Claims (6)
1. the phosphorus production preparation method of raw material phosphorus ore, it with Rock Phosphate (72Min BPL) fine ore for raw material is prepared from phosphorus production raw material phosphor ore lump ore, it is characterized in that: obtain Rock Phosphate (72Min BPL) agglomerate with chamber type sintering stove sintering Rock Phosphate (72Min BPL) fine ore, Rock Phosphate (72Min BPL) agglomerate obtains phosphorus production raw material phosphor ore lump ore through fragmentation;
Before with chamber type sintering stove sintering Rock Phosphate (72Min BPL) fine ore, by coal blending amount 3% ~ 15% coal dust added in Rock Phosphate (72Min BPL) fine ore and mix to obtain compound, atomized water is added in mixing process, ensure that in compound, moisture content is 3% ~ 12%, then by compound lay in chamber type sintering stove, compound repaves and puts coal dust and sinter;
The granularity of described Rock Phosphate (72Min BPL) fine ore is less than 5mm.
2. the preparation method of a kind of phosphorus production raw material phosphorus ore according to claim 1, is characterized in that: the lay thickness of described compound lay in chamber type sintering stove is 100 ~ 600mm.
3. the preparation method of a kind of phosphorus production raw material phosphorus ore according to claim 1, is characterized in that: the lay thickness of described coal dust is 1 ~ 10mm.
4. the preparation method of a kind of phosphorus production raw material phosphorus ore according to claim 1, is characterized in that: the ignition temperature of described chamber type sintering stove is 600 ~ 1300 DEG C, and ignition time is 1 ~ 10 minute.
5. the preparation method of a kind of phosphorus production raw material phosphorus ore according to claim 1, is characterized in that: even lay one deck Rock Phosphate (72Min BPL) on the fire grate of chamber type sintering stove, and the granularity of described Rock Phosphate (72Min BPL) is greater than 5mm, and then on Rock Phosphate (72Min BPL) lay compound.
6. the preparation method of a kind of phosphorus production raw material phosphorus ore according to claim 5, is characterized in that: described Rock Phosphate (72Min BPL) is selected from natural Rock Phosphate (72Min BPL) lump ore and Rock Phosphate (72Min BPL) agglomerate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844006A (en) * | 2020-12-28 | 2021-05-28 | 马边长和电力有限责任公司 | Yellow phosphorus tail gas purification method |
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| SU1423496A1 (en) * | 1987-01-08 | 1988-09-15 | Казахский Научно-Исследовательский И Проектный Институт Фосфорной Промышленности | Method of sintering phosphate raw material |
| CN102602900A (en) * | 2012-03-20 | 2012-07-25 | 昆明理工大学 | Method for pelletizing powdered rock phosphate by digesting, carbonizing and pelletizing |
-
2014
- 2014-12-15 CN CN201410770216.6A patent/CN104445115A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SU1423496A1 (en) * | 1987-01-08 | 1988-09-15 | Казахский Научно-Исследовательский И Проектный Институт Фосфорной Промышленности | Method of sintering phosphate raw material |
| CN102602900A (en) * | 2012-03-20 | 2012-07-25 | 昆明理工大学 | Method for pelletizing powdered rock phosphate by digesting, carbonizing and pelletizing |
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| CN112844006A (en) * | 2020-12-28 | 2021-05-28 | 马边长和电力有限责任公司 | Yellow phosphorus tail gas purification method |
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