CN101037193A - Technology and device for producing yellow Phosphorus by electric oven process - Google Patents

Abstract

The present invention relates to a process and equipment for producing phosphor, in particular to a process and device for producing phosphor by electric process and for the comprehensive utilization of emissions. The tail gas generated from the electric process for phosphor preparation is purified by a tail gas clean-up device, the heat generated from the combustion in regenerative heat exchanger is transmitted to the heat transfer medium and then the heat transfer medium is sent into the improved circulating fluidized bed boiler, the flue gas nozzle is sent into the circulating fluidized bed boiler furnace, the generated vapor drives the turbo unit to generate electricity, the flue gas from the circulating fluidized bed boiler is subjected to dust separation procedure and is mixed with the flue gas from the nonmetal combustion heat exchanger, then the mixed flue gas is sent into the raw material segment to dry raw material for producing phosphor, the slag quenching with wind is made into slag particle and then is sent into the improved circulating fluidized bed boiler by wind to execute heat exchange. The present invention has the advantages of that the flue gas can be recovered furthest, the slag can be used for power generation by waste heat, the energy saving and consumption decreasing effect is obviously.

Description

The technology of producing yellow Phosphorus by electric oven and device

Technical field

The present invention relates at phosphorus production technology and equipment, particularly the technology and the device of the comprehensive utilization of producing yellow Phosphorus by electric oven discharge.

Background technology

Yellow phosphorus is main industrial raw material, and present in the commercial run of yellow phosphorus, the tail gas of discharge and slag difficulty have always given more excellent method, and the utilization to tail gas mainly contains two kinds of methods in the technology of comparatively advanced producing yellow Phosphorus by electric oven exactly:

(1) utilize yellow phosphoric tail gas to produce Chemicals such as oxalic acid, formic acid; Owing to utilize yellow phosphoric tail gas to produce Chemicals such as oxalic acid, formic acid, tail gas clean-up technology more complicated, to purify cost higher and effect is unsatisfactory.

(2) utilize tail gas to do raw ore exsiccant thermal source.Can utilize 30% of tail gas amount but this always accounts for, all the other yellow phosphoric tail gas remain the burning of emptying in vain, have both caused certain environmental pollution, have greatly wasted the energy again.

Utilization to the yellow phosphorus slag mainly contains: produce yellow phosphorus per ton and can produce 1280 ℃ of about 8-10t of left and right sides high temperature furnace slag, main component is CaO:45-53%, SiO ₂: 38-43%, P ₂O ₅: 0.8-2%, F:1-3%; Now domestic production technique all is with generating Water Quenching Slag after the shrend, and the Water Quenching Slag of generation is used for the cement building material raw material or paves; Contain the waste that corrosive vapor causes environmental pollution and water in a large number after the shrend; Particularly the heat of high temperature of slag is wasted, and does not utilize.

Summary of the invention

The objective of the invention is to: provide a kind of the utilization to produce use device and the using method that the tail gas that produces in the yellow phosphorus process comes the producing yellow Phosphorus by electric oven tail gas of circulating fluid bed burning boiler by the indirect heat exchange mode with the calorific value of tail gas, utilize and produce the yellow phosphorus slag of discharging in the yellow phosphorus process.

Technical scheme of the present invention is: the technology of a kind of tail gas of producing yellow Phosphorus by electric oven, the energy utilization of yellow phosphorus slag, it is characterized in that: the tail gas that producing yellow Phosphorus by electric oven produces purifies through exhaust gas cleaner from spray absorber by yellow phosphoric tail gas, mainly remove the tail gas dustiness, remove simultaneously after the partial corrosion gaseous constituent in the regenerative heat exchanger internal combustion the heat transferred heat transferring medium, the thermal medium after the heat exchange is delivered to through the circular fluid bed device flue gas nozzle that improves design and is sent into the burning in circulating fluid bed boiler chamber; Circular fluid bed produces steam and promotes the turbine driven set generating, utilizes circular fluid bed flue gas of 150 ℃ of temperature after dedusting to mix with nonmetal combustion heat-exchange device gas fume after burning simultaneously and is sent to raw material workshop section drying phosphorus stove raw material.The slag that comes from yellow phosphorus electric furnace is sent into the wind system of quenching through slag ladle, and the quench slag particle after wind of making 2-10mm of slag wind is sent into the circular fluid bed device that improves design and carried out heat exchange.

The heat that enters the hypoxemia thermal medium of circular fluid bed device is burnt through the regenerative heat exchanger indirect heat exchange by yellow phosphoric tail gas; Temperature is controlled at 800-1100 ℃.

Tail gas clean-up is meant it is characterized by and adopts Venturi meter to add at least a in water (or 5～10% bucks) washing, water wash column washing, the soda-wash tower (5～10% buck).

The effect of regenerative heat exchanger and method is characterized by tail gas and in the regenerative heat exchanger internal combustion heat are stored in the regenerative heat exchanger; To be stored in heat energy in the regenerative heat exchanger by heat transferring medium displaces by a plurality of high temperature nozzle that are installed on the circulating fluidized bed combustor and sends into circulating fluidized bed combustor.

The described wind system of quenching refers to that the high temperature furnace slag of molten state is poured into regenerative heat exchanger burner hearth (43) in from regenerative heat exchanger slag inlet (42) through slag ladle and is incubated; Insulating process is after entering regenerator B (44) from the normal temperature air that gas blower (54) comes out by the reversing valve switching, be heated through regenerator B (Ceramic Balls or honeycomb) time, the utmost point in the short period of time normal temperature air be heated near burner hearth (43) temperature (generally 50～100 ℃ lower than furnace temperature), after heated high temperature air enters burner hearth (43), entrainmenting flue gas in the stove on every side forms one oxygen level and is significantly less than 21% thin oxygen deprivation high temperature gas flow, toward injecting yellow phosphoric tail gas (40) near the thin high temperature air, fuel is realized burning under oxygen deprivation (2～20%) state simultaneously; Meanwhile, hot flue gas after the burner hearth internal combustion enters atmosphere through another regenerator A (44), when the elevated temperature heat flue gas is by regenerator A (44) in the burner hearth, sensible heat is stored in the heat-storage type burner A (44), discharges through reversing valve (51) with the low-temperature flue gas that is lower than 150 ℃ then.The reversing valve that working temperature is not high (51) switches with certain frequency, makes two regenerator be in accumulation of heat and heat release alternation state; Energy storage by utilizing regenerative heat exchanger and heating function guarantee the molten state of phosphorus slag (45), adjust the position of wind quenching mouth (46), allow the phosphorus slag flow into the wind chamber (50) of quenching equably, the wind that comes by booster fan (47) sprays into the wind chamber (50) of quenching by wind chamber (50) tangent line of quenching, in quenching chamber (50), wind forms whirlwind, the warm sludge wind that will flow down is quenched into the small-particle of 3-10mm, with booster fan (58) quench slag and air of the wind that falls is together being sent into the coal-fired inlet of circulating fluidized bed combustor and is removed to carry out combustion heat-exchange; The crucial homo(io)thermism of phosphorus slag and the pressure-controlling that wind is quenched booster fan of guaranteeing of this operation.

The circular fluid bed device mainly by combustion chamber, cyclonic separator, material returning device, form for wind fume extractor, the ash exhauster of delivering coal, it is characterized in that middle and lower part, side, combustion chamber is provided with two phosphorus furnace exhaust gas heat transferring medium nozzles at least, the phosphorus slag inlet after a wind identical with the coal inlet is quenched is set at least.

Slag inlet after described wind is quenched is arranged on former coal arbitrarily ingress.

Described regenerative heat exchanger principle of work as shown in the figure, the normal temperature air that comes out from gas blower (54) by reversing valve switch enter regenerator B (44) after, be heated through regenerator B (Ceramic Balls or honeycomb) time, the utmost point in the short period of time normal temperature air be heated to enter burner hearth (43) near the heated high temperature air of burner hearth (43) temperature (generally 50～100 ℃ lower than furnace temperature) after, entrainmenting flue gas in the stove on every side forms one oxygen level and is significantly less than 21% thin oxygen deprivation high temperature gas flow, toward injecting fuel (fuel oil or combustion gas) near the thin high temperature air, fuel is realized burning under oxygen deprivation (2～20%) state simultaneously; Meanwhile, hot flue gas after the burner hearth internal combustion enters atmosphere through another regenerator A (44), when the elevated temperature heat flue gas is by regenerator A (44) in the burner hearth, sensible heat is stored in the heat-storage type burner A (44), discharges through reversing valve (51) with the low-temperature flue gas that is lower than 150 ℃ then.The reversing valve that working temperature is not high (51) switches with certain frequency, makes two regenerator be in accumulation of heat and heat release alternation state, thereby reaches energy-conservation heat exchange and reduce NO _XPurposes such as quantity discharged.

Principle of work of the present invention is that the combustion chamber heat exchange that utilizes the phosphorus furnace exhaust gas that produces in the producing yellow Phosphorus by electric oven process to send into circulating fluidized bed boiler after regenerative heat exchange apparatus internal combustion is by the heat transferring medium heat exchange produces the generating of superheated vapour pushing turbine.

Adopting the effect of regenerative heat exchanger is to burn by heat exchange, give heat transferring medium with the thermal energy transfer of tail gas, the flue gas that exhaust combustion produces does not directly contact with the boiler surface metallic conduit, has therefore stopped the corrosion of obnoxious flavoures such as the P4 that tail gas contains, PH3, H2S, HF to boiler surface fully.The key problem in technology that utilizes this combustion system of regenerative heat exchanger simultaneously is in the high-efficiency thermal storage chamber by alternation combustion air to be preheated to 800～1200 ℃ of pyritous simultaneously from room temperature, go into the flow velocity of stove stream thigh by effectively organizing fuel and combustion air, the angle of cut, means such as hybrid mode, making fuel be controlled at 2～15% furnace inner space in oxygen level burns, thereby can reduce the NOx quantity discharged significantly, but high-efficiency thermal storage chamber effectively catching fume afterheat, funnel temperature is controlled at more than the dew point, in the scope below 150 ℃, reclaim fume afterheat to greatest extent, the interior temperature of stove is more become evenly, use this advanced person's combustion system can reach fuel economy 20%～50% simultaneously, improve output 10%～30%, reduce environmental protection such as 20%～50% smoke discharge amount, energy-conservation and improve the effect of heat exchange quality.

If it is big to enter simultaneously the tail gas dustiness of regenerative heat exchange apparatus, will influence the heat exchange efficiency of regenerative heat exchange apparatus, therefore, guarantee heat exchange efficiency in the capable udst separation of advancing of regenerative heat exchange apparatus.

In the udst separation process of tail gas,, environment there is the better protecting effect because water (or buck) washing can be removed partial corrosion gas simultaneously.

Utilization comes from the slag of yellow phosphorus electric furnace, sends into the wind system of quenching through slag ladle, and the quench slag particle after wind of making 2-10mm of slag wind is sent into the circular fluid bed device that improves design and carried out heat exchange.Purpose is to utilize the heat energy of phosphorus slag to produce steam, but that the phosphorus slag of molten state is unfavorable for is heat passage, and it is to increase heat interchanging area that phosphorus slag wind is quenched into the small-particle purpose, improves heat exchange efficiency.

Boiler of the present invention adopts circulating fluid-bed (CFB) boiler with " environmental protection boiler " title, circulating fluidized bed combustion is a newer technology, its firing system is simpler, have take up an area of little, coal adaptability strong, can fire low grade coal, the desulfurization operation cost is low, can control characteristics such as NOx discharging, meets the requirement of national industry development policies.

Advantage of the present invention is to reclaim flue gas, phosphorus slag cogeneration to greatest extent, reach fuel economy 20%～50%, improve output 10%～30%, reduce environmental protection such as 20%～50% smoke discharge amount, energy-conservation and improve the effect of heat exchange quality, meet the requirement of national industry development policies.

Description of drawings

Fig. 1 is a technological process block-diagram of the present invention.

Fig. 2 is that the yellow phosphoric tail gas energy of the present invention and yellow phosphorus high heating value slag comprehensive utilization of energy device flow path device are equipped with synoptic diagram.

Fig. 3 is circulating fluidized bed combustor one-piece construction figure of the present invention.

Fig. 4 is that quench slag, fire coal of tail gas heat transferring medium of the present invention, wind enters circulating fluidized bed combustor facade A-A and analyse and observe distribution schematic diagram.

Fig. 5 is that quench slag, fire coal of tail gas heat transferring medium of the present invention, wind enters circulating fluidized bed combustor facade position view.

Fig. 6 is the wind of the present invention system architecture synoptic diagram of quenching.

Fig. 7 is a regenerative heat exchanger structural representation of the present invention.

Among the figure: the 1-yellow phosphorus electric furnace, 2-washes spray column, the water seal of 3-tail gas, 4-tail gas booster fan, 5-Venturi Scrubber, 6-water circulating pump, the 7-steam separator, 8-Safety water seal, 9-regenerative heat exchanger, the 10-gas blower, 11-circulating sulfuration bed combustor, 12-phosphorus slag slag ladle, 13-dry method slag wind quenching device, 14-phosphorus slag feeder, 15-heat transferring medium high temperature nozzle, 16-circulating fluid-bed flue, 17-cyclonic separator, 18-electrostatic precipitator, the 19-smoke induced draught fan, 20-chimney, 21-tail gas return valve, 22-circulation technology water pipe, 40-fuel oil or fuel gas inlet, 41-trip valve, 42-phosphorus slag inlet, the 43-burner hearth, the 44-regenerator, 45-phosphorus slag, 46-wind quenching mouth, the 47-wind booster fan of quenching, 48-send the slag blower fan, the 49-wind airduct of quenching, the 50-wind chamber of quenching, the 51-reversing valve, the 52-induced draft fan, 53-waste gas flue, 54-gas blower, wind inlet of 71-, the 72-air distribution device, 73-Wingdale inlet, 74-coal supply inlet, quench slag inlet of 75-wind, 76-secondary air inlet, 77-tail gas heat transferring medium inlet, 78-furnace outlet, the 79-downtake, the 80-high-abrasive material.

Embodiment

This patent is further described it by following embodiment, but is not limited to embodiment.

Example 1 is an example for 7000 tons with existing annual output throughput: with 7000 tons/year yellow phosphorus electric furnaces is example, utilizes the calorific value of phosphorus furnace exhaust gas, slag to produce steam-electric power by circular fluid bed, for the personal requirement of satisfied generating, joins and burns local low grade coal simultaneously.

Parameter is as follows: yellow phosphorus electric furnace throughput: 7000t/ produces tail gas amount: 2700NM ³/ t produces slag amount: 9.2t/t, current consumption: 13500KW.h/t, exhaust gas component: co content 89-95%; Dustiness: 65～95mg/NM3, boiler: JG-75/9.9 rated capacity 75t/h, nominal steam pressure (gauge pressure): 5.4MPa, steam turbine: N20-4.93 rated output: 20MW, generator: FQ-20-2 rated output: 20MW tail gas energy utilization system.

1, the present invention is provided with bleeding point by the top of the total water sealed tank of yellow phosphoric tail gas (3), extracts out by water-circulation type gas compressor (4) tail gas; Because the phosphorus furnace exhaust gas contains corrosive gases, water ring vacuum pump is selected corrosion resistant water ring vacuum pump for use, adopts two parallel connections simultaneously, the operation scheme of the using and the reserved.

2, for guaranteeing the safe ordinary production of phosphorus stove, total water seal pressure must keep pressure-fired, imports and exports at water ring vacuum pump and installs return line and automatic regulating valve additional; Adjust the aperture of reverse flow valve by monitoring total water seal pressure.

3, entering the two-stage Venturi Scrubber through the tail gas of water-circulation type gas compressor and carry out the dedusting washing, is to guarantee washing effect, requires the one-level Venturi Scrubber intake pressure must be in the 15-25KPa scope; The Venturi Scrubber throat flow velocity is controlled at 85-100m/s.

4, the washing water of Venturi Scrubber are from process recycled water, separate to import Safety water seal (8) through secondary Venturi meter (5) spray back by steam separator (7), spray into by the nozzle of water circulating pump (6) pressurization back by one-level Venturi meter (5) and tail gas is carried out dedusting wash; Washing water after washing flows into Safety water seal (8) and through clarifying tank dust-laden is carried out the spray water that post precipitation is used for yellow phosphorus stove phosphorus collecting tower; Parameter request: the washing water pressure that enters the two-stage Venturi meter is not less than 1.5MPa; Water to steam ratio: 0.8.

5, tail gas enters nonmetallic ceramics regenerative heat exchange device after the washing of two-stage Venturi meter; Yellow phosphoric tail gas and air are in the thermophore internal combustion, and the heat storage in the heating porcelain thermophore stores heat, carries out heat exchange with special-purpose heat transferring medium then; Two heat storage type combustion heat-exchanger rigs of nonmetal combustion heat-exchange device employing hocket and burn and heat exchange, a burning heating thermophore, another and heat transferring medium heat exchange, tail gas and air be oxygen debt burning in regenerative apparatus, the heating heat storage gets up thermal energy storage, carry out heat exchange with special-purpose heat transferring medium then, the thermal medium after the heat exchange is sent into the burner hearth burning of circulating fluidized bed device by booster fan.

6, spray into the combustion chamber by the nozzle that is contained in four jiaos of circulating fluidized beds after the special-purpose heat transferring medium heat exchange and produce steam, the high temperature thermal medium temperature that enters circulating fluidized bed is controlled at 880-1000 ℃, with boiler load 75t/h, pressure 4.53MPa is an example, and nozzle height is 8 meters absolute altitude places of boiler absolute altitude.

7, the high temperature furnace slag of molten state is poured insulation in the regenerative heat exchanger through slag ladle into from (1), energy storage by utilizing regenerative heat exchanger and heating function guarantee the molten state of phosphorus slag, adjust the position of wind quenching mouth (6), allow the phosphorus slag flow into the wind chamber (50) of quenching equably, the wind that comes by booster fan (7) sprays into the wind chamber (50) of quenching by wind chamber (50) tangent line of quenching, in quenching chamber (50), wind forms whirlwind, the warm sludge wind that will flow down is quenched into the small-particle of 3-10mm, with booster fan (8) quench slag and air of the wind that falls is together being sent into the coal-fired inlet of circulating fluidized bed combustor and is removed to carry out combustion heat-exchange; The crucial homo(io)thermism of phosphorus slag and the pressure-controlling that wind is quenched booster fan of guaranteeing of this operation.

8, tail gas heat transferring medium, phosphorus stove wind are quenched slag, low grade coal in the generating of circulating sulfuration bed apparatus internal combustion heat exchange generation sub-high pressure steam promotion steam turbine.

By utilizing phosphorus furnace exhaust gas, slag comprehensive utilization of energy, can produce the electric energy of total power consumption 20%, energy-saving effect is very remarkable.

2 examples of example mainly be on the dedusting washing process with example 1 difference, rest part is all identical; This routine dedusting washing adopts one-level Venturi meter (5) spray back to separate by steam separator (7), and washings imports Safety water seal (8), and tail gas enters soda-wash tower by pipeline and carries out secondary washing; Enter the regenerative heat exchange device through the yellow phosphoric tail gas behind the alkali liquid washing.

Claims (8)

1, the technology of producing yellow Phosphorus by electric oven, it is characterized in that: the tail gas that producing yellow Phosphorus by electric oven produces purifies through exhaust gas cleaner from spray absorber by yellow phosphoric tail gas, mainly remove the tail gas dustiness, remove simultaneously after the partial corrosion gaseous constituent in the regenerative heat exchanger internal combustion the heat transferred heat transferring medium, thermal medium after the heat exchange is delivered to through the circular fluid bed device flue gas nozzle that improves design and is sent into the burning in circulating fluid bed boiler chamber, circular fluid bed produces steam and promotes the turbine driven set generating, utilize the flue gas of circular fluid bed after dedusting to mix simultaneously and be sent to raw material workshop section dry phosphorus stove raw material with nonmetal combustion heat-exchange device gas fume after burning, the slag that comes from yellow phosphorus electric furnace, send into the wind system of quenching through slag ladle, the quench slag particle after wind of making 2-10mm of slag wind is sent into the circular fluid bed device that improves design and carried out heat exchange.

2, the technology of producing yellow Phosphorus by electric oven according to claim 1, the heat of hypoxemia thermal medium that it is characterized in that entering the circular fluid bed device by the yellow phosphoric tail gas burning through the regenerative heat exchanger indirect heat exchange; Temperature is controlled at 800-1100 ℃.

3, the technology of producing yellow Phosphorus by electric oven according to claim 1 is characterized in that tail gas clean-up is meant that it is characterized by the employing Venturi meter adds water washing.

4, the technology of producing yellow Phosphorus by electric oven according to claim 3 is characterized in that tail gas clean-up is to adopt at least a in water wash column washing, soda-wash tower 5～10% bucks.

5, the technology of producing yellow Phosphorus by electric oven according to claim 1 is characterized in that it is characterized by the effect and the method for regenerative heat exchanger tail gas and in the regenerative heat exchanger internal combustion heat is stored in the regenerative heat exchanger; To be stored in heat energy in the regenerative heat exchanger by heat transferring medium displaces by a plurality of high temperature nozzle that are installed on the circulating fluidized bed combustor and sends into circulating fluidized bed combustor.

6, the technology of producing yellow Phosphorus by electric oven according to claim 1, it is characterized in that the described wind system of quenching refers to that the high temperature furnace slag of molten state is poured into regenerative heat exchanger burner hearth (43) in from regenerative heat exchanger slag inlet (42) through slag ladle and is incubated, insulating process is after entering regenerator B (44) from the normal temperature air that gas blower (54) comes out by the reversing valve switching, be heated through regenerator B (Ceramic Balls or honeycomb) time, the utmost point in the short period of time normal temperature air be heated near burner hearth (43) temperature lower 50～100 ℃ than furnace temperature, after heated high temperature air enters burner hearth (43), entrainmenting flue gas in the stove on every side forms one oxygen level and is significantly less than 21% thin oxygen deprivation high temperature gas flow, simultaneously toward injecting yellow phosphoric tail gas (40) near the thin high temperature air, fuel is realized burning under oxygen deprivation (2～20%) state, meanwhile, hot flue gas after the burner hearth internal combustion enters atmosphere through another regenerator A (44), when the elevated temperature heat flue gas is by regenerator A (44) in the burner hearth, sensible heat is stored in the heat-storage type burner A (44), discharge through reversing valve (51) with the low-temperature flue gas that is lower than 150 ℃ then, the reversing valve that working temperature is not high (51) switches with certain frequency, make two regenerator be in accumulation of heat and heat release alternation state, energy storage by utilizing regenerative heat exchanger and heating function guarantee the molten state of phosphorus slag (45), adjust the position of wind quenching mouth (46), allow the phosphorus slag flow into the wind chamber (50) of quenching equably, the wind that comes by booster fan (47) sprays into the wind chamber (50) of quenching by wind chamber (50) tangent line of quenching, in quenching chamber (50), wind forms whirlwind, the warm sludge wind that will flow down is quenched into the small-particle of 3-10mm, with booster fan (58) quench slag and air of the wind that falls together sent into the coal-fired inlet of circulating fluidized bed combustor and removed to carry out combustion heat-exchange, the crucial homo(io)thermism of phosphorus slag and the pressure-controlling that wind is quenched booster fan of guaranteeing of this operation.

7, the device of producing yellow Phosphorus by electric oven, it is characterized in that the circular fluid bed device is mainly by the combustion chamber, cyclonic separator, material returning device, give wind, fume extractor, deliver coal, ash exhauster forms, it is characterized in that middle and lower part, side, combustion chamber is provided with two phosphorus furnace exhaust gas heat transferring medium nozzles at least, the phosphorus slag inlet after a wind identical with the coal inlet is quenched is set at least.

8, the device of producing yellow Phosphorus by electric oven according to claim 7 is characterized in that the slag inlet after described wind is quenched is arranged on former coal arbitrarily ingress.