CN102992285B - Method and equipment for producing yellow phosphorus by utilizing closed annular heating furnace - Google Patents
Method and equipment for producing yellow phosphorus by utilizing closed annular heating furnace Download PDFInfo
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Abstract
The invention discloses a method and equipment for producing yellow phosphorus by utilizing a closed annular heating furnace. The equipment comprises a raw material crusher, a vibrating screen extension set, a drying machine, a metering device, a mixed storage bin and the closed annular heating furnace which are sequentially connected, wherein the closed annular heating furnace is respectively connected with a furnace gas treatment tail gas recovery mechanism and a slag collecting tank; and the furnace gas treatment tail gas recovery mechanism is connected with the closed annular heating furnace through a tail gas recovery pipeline. The method comprises the following steps of: raw material pretreatment, material proportioning, carrying out a reaction in furnace, discharging and performing a tail gas comprehensive utilization process. The equipment is low in power consumption, low in operating cost, low in investment strength and easy to maintain and has good industrial application prospect; and moreover, mature process conditions of yellow phosphorus production are by utilizing the equipment are realized, the yellow phosphorus tail gas heat value can be fully utilized, consumable graphite electrodes and carbon electrodes are not consumed, and the production energy consumption and cost are greatly reduced.
Description
Technical field
The present invention relates to a kind of method and apparatus of producing yellow phosphorus, especially relate to a kind of method and apparatus that utilizes airtight rotary heating furnace to produce yellow phosphorus.
Background technology
Yellow phosphorus is a kind of very important, irreplaceable industrial chemicals, make raw material with it and can produce the multiple products such as phosphoric acid, agricultural chemicals, washing composition, phosphate fertilizer, be widely used in the industrial circles such as fertilizer, food, medicine, electronics, weaving, metallurgy, pottery, in national defense industry, also have critical role.In at present domestic and international phosphorus production, electric furnace process is definitely leading technique, add in closed electric furnace by Rock Phosphate (72Min BPL), silica and carbonaceous reducing agent compound, in electric furnace, the tri-phase current of input produces high temperature with resistance heat form, furnace charge melting carry out chemical reduction reaction under 1300-1500 ℃ of high temperature, produces element phosphor (P
4), the gaseous state thing such as carbon monoxide (CO) carry dust secretly and overflow, claim phosphorous furnace gas, phosphorous furnace gas enters cooling system, refining and obtain phosphorus through condensation separation, reaction formula is:
China is current the first in the world phosphorus production big country, and output phosphor accounts for 85% of global ultimate production, more than 140 of Yue You phosphorus production enterprises.Yellow phosphorus is a kind of high energy consumption product, according to statistics, the average comprehensive energy consumption of national Zhi Lin enterprise yellow phosphorus per ton in 2011 is 3.316 tons of standard coals, in the comprehensive energy consumption of various Industrial products, come out at the top, this is restricted phosphorus industrial expansion processed, also illustrates energy-conservationly in phosphorus industry processed, to seem particularly important and urgent simultaneously.Electric furnace process is prepared the consumption (being all converted to mark coal) that comprehensive energy consumption in yellow phosphorus process comprises electric furnace electricity, coke, power current, water and vapour etc., and the electric energy of electric furnace system consumption accounts for yellow phosphorus comprehensive energy consumption more than 70%, one ton of element phosphor of general every production is minimum needs power consumption 13500 to spend, power consumption accounts for the 55-60% of its manufacturing cost, and electric furnace system is energy-conservation is the emphasis of Yellow Phosphorus Industry energy conservation.
In recent years, for reducing the comprehensive energy consumption level of Yellow Phosphorus Industry, national correlation department has been put into effect series of measures and the policies such as " yellow phosphorus unit product energy consumption limit ", " Yellow Phosphorus Industry entry criteria ", " yellow phosphorus cleaner production assessment indicator system ", to promote cleaner production and the energy-saving and emission-reduction of Yellow Phosphorus Industry.Through great efforts, realizing as electric furnace maximization, DCS Whole Process Control, slag recycling, sewage closed cycle etc. compared with multiple enterprises, domestic Yellow Phosphorus Industry development obtains marked improvement.In addition, for the large drawback of the power consumption of yellow phosphorus electric furnace system, each R&D institution, enterprise also also propose and have adopted many improved measures in practice, as: 1) improve transformer overload; 2) three-phase electrode changes 6 into by 3; 3) transmit electricity short net by copper bar change into pipe in water cooling copper pipe; 4) changing partial component material is stainless steel tube; 5) changing molten bath geometrical shape, size and electrode arranges etc.For Yellow Phosphorus Industry energy consumption, control has obtained certain effect in above measure, solves but the high problem of power consumption does not obtain essence.Particularly, along with the decline year by year of raw material phosphorus ore quality, yellow phosphorus power consumption presents again ascendant trend, the level before even exceeding, and raw material consumption is also high.Therefore, must continue to find other method and measure, adopt new technology to advance the energy-saving and cost-reducing work of yellow phosphorus.
In electric furnace legal system phosphorus production process except obtaining phosphorus product, also with a large amount of by products, as slag, ferrophosphorus, tail gas and mud phosphorus etc.Wherein, produce 1 ton of yellow phosphorus and can produce tail gas 2500-3000Nm simultaneously
3.For the utilization of yellow phosphoric tail gas, can be divided in theory two kinds of approach: because the calorific value of yellow phosphoric tail gas is at 10000KJ/Nm
3left and right, is used so can be used as fuel, in addition, after the tail gas clean-up that is 85-95%, can synthesize multiple carbon-Chemicals as industrial chemicals using CO content, as synthesising acid sodium, formic acid, methyl-formiate etc.But because the phosphorus furnace exhaust gas purification techniques difficulty that is applicable to carbon-chemical industry is large, it is higher to purify cost, suitability is not strong.Most phosphorous chemical industry enterprise tail gas fully utilizes also in low-level operational phase, as only using phosphorus furnace exhaust gas as raw material stoving with the fuel fired of mud phosphorus, all the other tail gas are emptying burning in vain still, has both caused certain environmental pollution, has greatly wasted again the energy.
Production based on current yellow phosphorus and research situation, also there is no a kind of production technique that can conscientiously solve the yellow phosphorus comprehensive energy consumption drawbacks such as particularly energy consumption of electric furnace is high, waste gas utilization rate is low, therefore, find one carries out in airtight rotary heating furnace, and utilize the technique that phosphorus furnace exhaust gas calorific value phosphorus supply ore reduction is yellow phosphorus, must provide possibility for realizing domestic and international Yellow Phosphorus Industry Sustainable development and resource circulation utilization, also will produce good economic benefit and environmental benefit.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of Apparatus and method for that utilizes airtight rotary heating furnace to produce yellow phosphorus.This equipment power consumption is low, running cost is low, investment intensity is little, be easy to safeguard to have good industrial applications prospect; Utilize this equipment to realize the processing condition maturation of phosphorus production, can make full use of yellow phosphoric tail gas calorific value, without consuming easily Graphite Electrodes and the carbon electrode of consumption, greatly reduce phosphorus production energy consumption and cost.
To achieve the above object of the invention, technical scheme provided by the invention is:
A kind of equipment that utilizes airtight rotary heating furnace to produce yellow phosphorus is provided, comprise to raw material (Rock Phosphate (72Min BPL), silica, nut coke) carry out broken material crusher, vibrating screen classifier that the raw material after fragmentation is sieved and by the dryer of release mesh drying materials, described dryer be connected measuring apparatus by charging belt, described measuring apparatus is connected with blending bun, and described blending bun is connected with airtight rotary heating furnace; Described airtight rotary heating furnace processes tail gas recycle mechanism with furnace gas respectively and collection slag bath is connected; Described furnace gas is processed tail gas recycle mechanism and is connected with airtight rotary heating furnace by tail gas recycle pipeline again.
Preferably, described furnace gas is processed tail gas recycle mechanism and is comprised the cooling tower being connected with airtight rotary heating furnace, cooling tower is connected with phosphorus refinery pit with exhaust gas cleaner respectively, and described exhaust gas cleaner connects compressor by pipeline, and compressor is connected with gas holder.
Preferably, described airtight rotary heating furnace comprises the furnace chamber being made up of outer shroud furnace wall, interior ring oven wall, furnace roof and furnace bottom, described furnace bottom can rotate, in described furnace chamber, be furnished with many radiation heating tubes, between described outer shroud furnace wall and interior ring oven wall, be provided with partition wall, the annular chamber between outer shroud furnace wall and interior ring oven wall is isolated into preheating zone I, heating zone II and high temperature reduction district III; The initiating terminal of described preheating zone I is provided with closed-type feed device, and the tail end of described high temperature reduction district III is respectively equipped with airtight deslagging device and phosphorous furnace gas relief outlet; Described closed-type feed device and blending bun outlet connect; Described airtight deslagging device and shrend slag bath connect; Described phosphorous furnace gas relief outlet is connected with cooling tower by pipeline.
Preferably, described radiation heating tube is heat accumulating type radiation heating tube.
Preferably, described gas holder is connected with the radiation tube heater on described airtight rotary heating furnace by gas line.
Correspondingly, the present invention also provides a kind of method of utilizing airtight rotary heating furnace to produce yellow phosphorus, comprises the steps:
1) raw materials pretreatment: by sieving after the fragmentations such as qualified Rock Phosphate (72Min BPL), silica, charcoal element material, the minus mesh of release mesh is delivered in dryer and dries, moisture content in each material is all reached into stove requirement;
2) batching: the each oven dry fine fodder that reaches stove requirement requires to be delivered to blending bun by charging belt after measuring apparatus accurate measurement according to meeting Rock Phosphate (72Min BPL) reduction reaction in stove;
3) reaction in furnace: the raw material preparing is in proportion in closed-type feed device is distributed into airtight rotary heating furnace, each composition in furnace charge rotates with furnace bottom after entering in stove, through preheating zone, heating zone, high temperature reduction district, make furnace charge melting and carry out redox reaction successively;
4) discharging: yellow phosphorus furnace slag is flowed out by airtight slag notch comes together in collection slag bath after shrend is cooling, and the pulp water of quenching recycles; Phosphorous furnace gas enters cooling tower, and phosphorus vapor condensation wherein gets off, and is gathered in and is subject to the thick phosphorus of formation in phosphorus groove; The thick regular siphon of phosphorus, to refinery pit, after using hot water rinsing refining, is separated into mud phosphorus and finished phosphorus, and yellow phosphorus gets final product metering packing;
5) tail gas comprehensive utilization: purify through exhaust gas cleaner from cooling tower yellow phosphoric tail gas out, mainly remove tail gas dustiness, remove portion corrosive gases composition simultaneously, the tail gas CO content after purification reaches 97-99%, be good geseous fuel, after being pressurizeed, be stored in gas holder; By the radiation heating tube geseous fuel import in gas pipeline is delivered to airtight rotary heating furnace of the CO in gas holder, after high concentration CO is lighted, in radiator tube, produce amount of heat, and via radiator tube by heat radiation in airtight rotary heating furnace, make furnace chamber Nei Ge district temperature reach phosphorus production requirement.
Preferably, in described method, described charcoal element material is one or more in bituminous coal, hard coal, brown coal, coke or coke powder.
Preferably, in described method, the temperature of described preheating zone I is 800-1000 ℃, and material is 1-5min in the residence time of preheating zone I; The temperature of described heating zone II is 1000-1250 ℃, and material is 2-10min in the residence time of heating zone II; The temperature of described high temperature reduction district III is 1250-1450 ℃, and material is 3-15min in the residence time of high temperature reduction district III.
Preferably, in described method, when tail gas calorific value deficiency or system start while needing, the fuel that described radiation heating tube uses can adopt other geseous fuel such as CO, methane, coal gas or Sweet natural gas, and the calorific value of fuel should be greater than 4000kJ/Nm
3.
Method and apparatus provided by the invention has following beneficial effect:
1, utilize in yellow phosphoric tail gas high-content CO required for phosphorus production for thermal source, reaction in furnace, without consuming electric energy, Graphite Electrodes and carbon electrode, can make phosphorus production energy consumption and cost all be down to extremely low-level;
2, the utilization ratio of yellow phosphoric tail gas can reach more than 95%, reduces because of the phosphorus furnace exhaust gas emptying topsoil causing of burning, and has greatly saved high-grade fuel;
3, adopt heat accumulating type to add heat radiation tube and farthest retained the heat that combustion gas produces, funnel temperature is low, does not need to arrange pre-heat recovery system, has saved cost of investment;
4, fuel, at radiation combustion inner pipe, does not enter in stove, can control well furnace reduction atmosphere, and radiator tube quantity and position are conducive to improve the homogeneity of temperature distribution in burner hearth, are conducive to reduction reaction and carry out, and reduction efficiency is high, and the recovery time is short;
5, shorten material in the preheating zone time, indirectly increased the time of material in high temperature reduction district, thereby greatly improved calcining furnace output.
Accompanying drawing explanation
Fig. 1 is a kind of equipment flowsheet that utilizes rotary hearth furnace to produce yellow phosphorus in the embodiment of the present invention;
Fig. 2 is airtight rotary heating furnace vertical view in the embodiment of the present invention;
Fig. 3 is the process flow sheet of the embodiment of the present invention.
In figure: 1, material crusher; 2, vibrating screen classifier; 3, dryer; 4, measuring apparatus; 5, blending bun; 6, airtight rotary heating furnace; 6a, closed-type feed device; 6b, airtight deslagging device; 6c, phosphorous furnace gas relief outlet; 6d, radiation heating tube; 7, collection slag bath; 8, cooling tower; 9, phosphorus refinery pit; 10, exhaust gas cleaner; 11, compressor; 12, gas holder; 13, outer shroud furnace wall; 14, interior ring oven wall; 15, furnace roof; 16, furnace bottom.
I, preheating zone; II, heating zone; III, high temperature reduction district.
Embodiment
Below in conjunction with drawings and Examples to the equipment of production yellow phosphorus provided by the invention and utilize the method for this device fabrication yellow phosphorus to be described in detail.
Figure 1 shows that a kind of equipment that utilizes rotary hearth furnace to produce yellow phosphorus, comprise to raw material (Rock Phosphate (72Min BPL), silica, nut coke) carry out broken material crusher 1, the vibrating screen classifier 2 that the raw material after fragmentation is sieved and the dryer 3 that release mesh raw material is dried, dryer 3 be connected measuring apparatus 4 by belt, measuring apparatus 4 is connected with blending bun 5, and blending bun 5 is connected with airtight rotary heating furnace 6; Airtight rotary heating furnace 6 processes tail gas recycle mechanism with furnace gas respectively and collection slag bath 7 is connected; Furnace gas is processed tail gas recycle mechanism and is connected with airtight rotary heating furnace 6 by tail gas recycle pipeline again.Wherein, furnace gas is processed tail gas recycle mechanism and is comprised the cooling tower 8 being connected with airtight rotary heating furnace 6, cooling tower 8 is connected with phosphorus refinery pit 9 with exhaust gas cleaner 10 respectively, and exhaust gas cleaner 10 connects compressor 11 by pipeline, and compressor 11 is connected with gas holder 12.
As shown in Figure 2, airtight rotary heating furnace 6 comprises the burner hearth being made up of outer shroud furnace wall 13, interior ring oven wall 14, furnace roof 15 and rotating furnace bottom 16, and burner hearth is separated by partition wall, is divided into preheating zone I, heating zone II, high temperature reduction district III; The initiating terminal of preheating zone I is provided with closed-type feed device 6a, and the tail end of high temperature reduction district III is respectively equipped with airtight deslagging device 6b and phosphorous furnace gas relief outlet 6c, is furnished with many radiation heating tube 6d in burner hearth; Airtight rotary heating furnace 6 is connected with cooling tower 8 with blending bun 5, collection slag bath 7 respectively with phosphorous furnace gas relief outlet 6c by closed-type feed device 6a, airtight deslagging device 6b.
In specific embodiment, radiation heating tube 6d is heat accumulating type radiation heating tube.
In specific embodiment, gas holder 12 is connected with the radiator tube heating tube 6d on described airtight rotary heating furnace 6 by gas line.
As shown in Figure 3, the phosphorus production processing method flow process that aforesaid device is corresponding is as follows:
1) raw materials pretreatment: qualified Rock Phosphate (72Min BPL), silica, charcoal element material (one or more in bituminous coal, hard coal, brown coal, coke or coke powder) etc. are after material crusher 1 fragmentation, sieve via vibrating screen classifier 2, the oversize of release mesh is delivered in dryer 3 and dries, and moisture content in each material is all reached into stove requirement;
2) batching: the each oven dry fine fodder that reaches stove requirement is delivered to blending bun 5 by charging belt after measuring apparatus 4 accurate measurements, the ratio between each raw material should meet the requirement of Rock Phosphate (72Min BPL) reduction reaction in stove;
3) reaction in furnace: the raw material preparing is in proportion in closed-type feed device 6a is distributed into airtight rotary heating furnace 6, each composition in furnace charge rotates with furnace bottom 16 after entering in stove, through preheating zone I, heating zone II and high temperature reduction district III, make furnace charge high-temperature fusion and carry out redox reaction successively;
4) discharging: yellow phosphorus furnace slag flows out via airtight deslagging device 6b comes together in collection slag bath 7 after shrend is cooling, and the pulp water of quenching recycles; Phosphorous furnace gas enters cooling tower 8 with pipeline, and phosphorus vapor condensation wherein gets off, and is gathered in bottom and is subject to the thick phosphorus of formation in phosphorus groove; The thick regular siphon of phosphorus, to phosphorus refinery pit 9, after using hot water rinsing refining, is separated into mud phosphorus and finished phosphorus, and yellow phosphorus gets final product metering packing;
5) tail gas comprehensive utilization: purify through exhaust gas cleaner 10 from cooling tower 8 yellow phosphoric tail gas out, mainly remove tail gas dustiness, remove portion corrosive gases composition simultaneously, tail gas CO content after purification reaches 97-99%, be good geseous fuel, after compressor 11 pressurizations, be stored in gas holder 12; CO in gas holder 12 is delivered to the geseous fuel import of the interior radiation heating tube 6d of airtight rotary heating furnace 6 through gas pipeline, after high concentration CO is lighted, in radiation heating tube 6d, produce amount of heat, and via himself radiation effect by heat radiation to airtight rotary heating furnace 6, make furnace chamber Nei Ge district temperature reach phosphorus production requirement.The fuel that radiation heating tube 6d uses can adopt other geseous fuel such as CO, methane, coal gas, Sweet natural gas, and the calorific value of fuel should be greater than 4000kJ/Nm
3.
In specific embodiment, the temperature of preheating zone I is 800-1000 ℃, and material is 1-5min in the residence time of preheating zone I; The temperature of heating zone II is 1000-1250 ℃, and material is 2-10min in the residence time of heating zone II; The temperature of high temperature reduction district III is 1250-1450 ℃, and material is 3-15min in the residence time of high temperature reduction district III.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention by the definite protection domain of submitted to claims.
Claims (3)
1. utilize airtight rotary heating furnace to produce a method for yellow phosphorus, it is characterized in that, comprise the steps:
1) raw materials pretreatment: by sieving after qualified Rock Phosphate (72Min BPL), silica, the fragmentation of charcoal element material, the minus mesh of release mesh is delivered in dryer (3) and is dried, moisture content in each material is all reached into stove requirement;
2) batching: step 1) is respectively dried to fine fodder and require to be delivered to blending bun (5) by charging belt after measuring apparatus (4) accurate measurement according to meeting Rock Phosphate (72Min BPL) reduction reaction in stove;
3) reaction in furnace: the raw material preparing is in proportion in closed-type feed device (6a) is distributed into airtight rotary heating furnace (6), each composition in furnace charge rotates with furnace bottom (16) after entering in stove, through preheating zone I, heating zone II and high temperature reduction district III, make furnace charge melting and carry out redox reaction successively;
4) discharging: yellow phosphorus furnace slag is flowed out by airtight deslagging device (6b) comes together in collection slag bath (7) after shrend is cooling, and the pulp water of quenching recycles; Phosphorous furnace gas enters cooling tower (8), is separated into mud phosphorus and finished phosphorus, and yellow phosphorus gets final product metering packing;
5) tail gas comprehensive utilization: purify through exhaust gas cleaner (10) from cooling tower (8) yellow phosphoric tail gas out, be stored in after being pressurizeed in gas holder (12); By radiation heating tube (6d) the geseous fuel import in gas pipeline is delivered to airtight rotary heating furnace (6) of the CO in gas holder (12), and via radiator tube by heat radiation in airtight rotary heating furnace (6);
The temperature of described preheating zone I is 800-1000 ℃, and material is 1-5min in the residence time of preheating zone I; The temperature of described heating zone II is 1000-1250 ℃, and material is 2-10min in the residence time of heating zone II; The temperature of described high temperature reduction district III is 1250-1450 ℃, and material is 3-15min in the residence time of high temperature reduction district III.
2. the method for utilizing airtight rotary heating furnace to produce yellow phosphorus according to claim 1, is characterized in that, described charcoal element material is one or more in bituminous coal, hard coal, brown coal, coke or coke powder.
3. the method for utilizing airtight rotary heating furnace to produce yellow phosphorus according to claim 1, is characterized in that, the fuel that described radiation heating tube (6d) uses adopts CO, methane, coal gas or Sweet natural gas, and the calorific value of fuel should be greater than 4000kJ/Nm
3.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103191635A (en) * | 2013-04-26 | 2013-07-10 | 昆明锦巍自控技术有限公司 | Method and device for purifying slag from yellow phosphorus electric furnace |
| CN104263964B (en) * | 2014-09-25 | 2016-09-28 | 杨建民 | A kind of production system of environmental protection gold mine dressing agent |
| CN106586986A (en) * | 2016-12-23 | 2017-04-26 | 江苏省冶金设计院有限公司 | System for processing phosphorite and application thereof |
| CN107686099A (en) * | 2017-09-18 | 2018-02-13 | 北京迈未科技有限公司 | A kind of device and method that yellow phosphorus is produced using mid low grade phosphate rock stone |
| CN110655050A (en) * | 2019-10-11 | 2020-01-07 | 李树云 | Method for preparing phosphoric acid |
| CN112429707B (en) * | 2020-11-27 | 2022-07-15 | 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 |
| CN113772643A (en) * | 2021-09-16 | 2021-12-10 | 云南澄江华业磷化工有限责任公司 | Intelligent material distributing and batching system of yellow phosphorus furnace |
| CN115212669B (en) * | 2022-06-29 | 2023-07-04 | 成都易态科技有限公司 | Yellow phosphorus flue gas purification system |
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