CN100584748C - Mid low grade phosphate rock kiln-process phosphoric acid production method and facilities and equipments thereof - Google Patents

Mid low grade phosphate rock kiln-process phosphoric acid production method and facilities and equipments thereof Download PDF

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Publication number
CN100584748C
CN100584748C CN200710049838A CN200710049838A CN100584748C CN 100584748 C CN100584748 C CN 100584748C CN 200710049838 A CN200710049838 A CN 200710049838A CN 200710049838 A CN200710049838 A CN 200710049838A CN 100584748 C CN100584748 C CN 100584748C
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kiln
phosphoric acid
raw material
heater
roasting
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CN101143717A (en
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刘代俊
杨军
邱礼有
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Sichuan University
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Sichuan University
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Abstract

The invention discloses a kind of is the processing method and the facilities and equipments thereof of raw material kiln method production high-quality phosphoric acid with the mid low grade phosphate rock, its production craft step mainly comprises: behind the phosphorus ore of powder shaped and solid fuel or phosphorus ore, solid fuel and the silica mixing moulding, on being deposited at the bottom of the rotary kiln that encircles end kiln, in stove, carry out the reduction-oxidation roasting, maturing temperature is 1300~1550 ℃, time is 1.5~3 hours, the phosphoric anhydride gas of roasting reaction is drawn from roasting kiln and is sent into the dust separation device udst separation, and purified gas is sent into absorption equipment and produced phosphoric acid.Adopt processing method of the present invention and equipment kiln method production high-quality phosphoric acid, the interior ring formation of kiln that has solved the existence of prior art rotary kiln production phosphoric acid is serious, problem that can't industrial implementation, also solve the prior art tunnel furnace and produced the production process complexity that phosphoric acid exists, be difficult to the problem that realizes that single series maximizes.

Description

Mid low grade phosphate rock kiln-process phosphoric acid production method and facilities and equipments thereof
Technical field
The present invention relates to phosphoric acid production technology and equipment, particularly relating to a kind of is the processing method and the equipment of raw material kiln method production high-quality phosphoric acid with the mid low grade phosphate rock.
Background technology
Consumption according to present higher-grade phosphorus ore calculates that worldwide phosphate rock resource will face the danger of dilution between decades, for this reason, the U.S., states such as India and Russia have started emergent research work, attempt to obtain phosphoric acid from the kinds of processes method.In China, list 16,800,000,000 tons of the Rock Phosphate (72Min BPL) reserves of national statistics in, but most of phosphorus ore is difficult to sort P 2O 5Content has only 11.2 hundred million tons greater than 30% rich ore, in low-grade phosphorus ore account for 90%, P 2O 5Content accounts for 50% at the low-grade phosphate ore below 26%.Low-grade phosphorus ore contains a large amount of impurity in these, adopts conventional two water conservancy projects skill to be difficult to produce high-quality phosphoric acid.According to the spending rate of the present phosphorus ore of China, the rich ore of China will be petered out about 10 years, and the resource of phosphorus ore faces dilution.China Ministry of Land and Resources has classified phosphorus ore as one of mineral that can not satisfy the national economy needs in 10 years.
In China, the production of phosphate fertilizer of high density mainly is to adopt mixture of sulfuric phosphoric acid wet extraction technology at present.This technology is had relatively high expectations to phosphorus ore, not only consumes a large amount of sulfuric acid, while by-product calcium sulfate, and annual output reaches 2,500 ten thousand tons.As not adopting the phosphate fertilizer of mixture of sulfuric phosphoric acid acid wet extraction explained hereafter high density, and adopt the fine thermal phosphoric acid to produce high concentration phosphate fertilizer, both can avoid the reluctant problem of calcium sulfate (gypsum), can solve the problem of China's sulphur inadequate resource again.The technology of the hot method production of prior art high-quality phosphoric acid is earlier the phosphorus ore reduction to be obtained yellow phosphorus, again the yellow phosphorus oxidation is obtained phosphoric anhydride, absorbs then and produces phosphoric acid.Produce yellow phosphorus power consumption per ton and reach 17000kWh, energy consumption is high, and the phosphoric acid production price is very high.Therefore adopting the fine thermal phosphoric acid to produce high concentration phosphate fertilizer is difficult to implement in practice.
Solving a good idea of the existing problem of hot method production high-quality phosphoric acid, is that phosphorus production and phosphoric anhydride oxidation are tied, and the heat of oxidation is passed to the reduction space, thereby can reduce or need not outside heat supply promptly finish the reduction process of phosphorus ore significantly.Of paramount importance progress in the evolution of phosphorus ore thermal phosphoric acid is a kiln-process phosphoric acid.U.S.'s research is in this respect gone ahead of the rest, and just begins kiln-process phosphoric acid (KPA) is studied the sixties in 20th century, has successively obtained some achievements in research.1978-1982, U.S. Occidental Petroleum Corporation has carried out the interim test that kiln-process phosphoric acid is produced in the Wisconsin, the emphasis of experimental study is how in rotary kiln oxidation zone and reduction zone to be isolated effectively, the reduction of phosphorus and oxidation is finished simultaneously smoothly, and made full use of its reaction heat.But do not obtain satisfied achievement.Human rare gas elementes such as Megy are made sealing coat, stop the raw material ball that is made into by powder raw material to contact with oxidizing atmosphere, and the measure of being taked is to hole on the rotary kiln body, constantly feed rare gas element with the cleaning reaction bed from raw material ball layer below.Though this method has certain effect, the expense height, structure is all very complicated with operation.Lapple then adopts the topped coke grain that moves about on the raw material ball layer, contacts with oxidizing atmosphere to stop raw material ball.In the experimental study,, in operational process,, therefore protect effect and not obvious because the kiln body rotates, and the coke that moves about separates with spherolite though the add-on of coke grain is very big.
The people such as Jiang Shanxiang of China's Nanhua Group Design Inst steep under the inspiration of this phenomenon at the ceramic glaze, propose to adopt integument to come isolation oxidation district and reduction zone, promptly be coated with the integument of the similar glaze of one deck in raw material ball surface by phosphorus ore silica and coke powder granulating and forming, this integument at high temperature is melt into liquid phase, the P that reduction reaction generates in the liquid layer 2Overflow with the CO bubbling, and the oxygen in the ambient air can not pass liquid film and enters integument inside and material reaction.This has just isolated oxidation zone and reduction zone effectively, and does not hinder mutual heat transfer again.This imagination has obtained desired result through experiment.Under the arrangement of State Planning Commission, cooperated to have carried out kiln-process phosphoric acid (CDK) by Changsha Mining ﹠ Metallurgy Inst and Jiangxi phosphate fertilizer plant and enlarge interim test for 200 tons/year in 1996.The rotary kiln internal diameter 0.62m of test, long 6m.Adopt double-deck pelletizing, spherome surface wraps coke powder with binding agent and does integument, and inside is phosphorus ore, silica, coke, the about 10mm of spherolite diameter.P in the continuous post-installation review through 74 hours, kiln 2O 5Reduction ratio average out to 86%, total recovery are 85%, and acquisition phosphoric acid is 85%H 3PO 4But this processing method is serious because of phenomenons such as ring formation in the kiln, fails to realize industrialization.In order to solve in the kiln problem such as ring formation, there is unit to adopt tunnel furnace to produce phosphoric acid.This processing method is directly formed to the shape of architectural shape with raw material, fragmentation when rolling in rotary kiln for fear of material simultaneously, and the solid kiln slag is with the form kiln discharge of building block or fragment of brick.Tunnel furnace phosphoric acid method has been avoided ring formation phenomenon in the kiln, but the production process complexity is difficult to realize that single series maximizes.
Content of the present invention
The deficiency that exists at the mid low grade phosphate rock kiln-process phosphoric acid production method of prior art, purpose of the present invention aim to provide a kind of new be the processing method and the equipment of raw material kiln method production high-quality phosphoric acid with the mid low grade phosphate rock, serious with ring formation in the kiln in the solution prior art kiln-process phosphoric acid production process, the production process complexity is difficult to the problem that realizes that single series maximizes.
Above-mentioned technical problem can be realized by the kiln-process phosphoric acid processing method of following technical proposals provided by the invention.
A kind of mid low grade phosphate rock kiln-process phosphoric acid production method, its basic production processing step comprises:
(1) phosphorus ore of powder shaped and solid fuel or phosphorus ore, solid fuel and silica mixing aftershaping;
(2) raw material after the moulding insert the ring end kiln be deposited in the ring end kiln rotary kiln at the bottom of on, in stove, carry out the reduction-oxidation roasting, maturing temperature is 1300~1550 ℃, the time is 1.5~3 hours;
(3) the phosphoric anhydride gas that the roasting reaction is obtained is drawn from roasting kiln and is sent into the dust separation device udst separation;
(4) purified gas is sent into absorption equipment, absorbs the P in the gas 2O 5Produce phosphoric acid.
In technique scheme, the feed composition proportioning is joined fully according to the composition of phosphorus ore, contains enough silica compositions in phosphorus ore, can satisfy Ca 3(PO 4) 3+ 5C+3SiO 2=P 2↑+5CO ↑+3CaSiO 3The needs of reaction process then do not need to add silica in addition when batching, if contained silica composition can not satisfy Ca in the phosphorus ore 3(PO 4) 3+ 5C+3SiO 2=P 2↑+5CO ↑+3CaSiO 3The needs of reaction process then just need to add in addition silica when batching.
In technique scheme, can in the outfit of raw material, add Wingdale by the proportioning of producing cement, the reacted kiln slag of roasting promptly can be cement after pulverizing the grinding batching.Be that processing method of the present invention can be combined as a whole the production of Cement Production and phosphoric acid, make full use of resource, and the generation of waste gas, waste residue has fundamentally been eliminated in the production of cement and phosphoric acid.
In technique scheme, before inserting ring behind the material forming kiln carries out roasting at the end, the sealing coat that can raw material and air can be separated in the surface coverage of raw material body can more help the carrying out of redox reaction.The sealing coat of raw material surface has several different methods to cover, and preferably is covered in the raw material surface by the raw material body being dipped in the intravital method of sealing coat liquid.Said sealing coat liquid consists of: carbon 10~20%, and water glass (water glass) 5~10%, wilkinite 5~10%, all the other are water.
In technique scheme, material forming can adopt molding bonded, also can adopt compression moulding, and the type shape can be spherical, also can be building block shape, or other shapes.When molding bonded is adopted in moulding, contain binding agent in the feed composition.Binding agent can be a clay.When compression moulding was adopted in moulding, the type body can design building block.
Be used to implement the facilities and equipments of above-mentioned kiln-process phosphoric acid production method for encircling end kiln, the stove seat of being included in the annular body of heater in its cavity and being used to install body of heater by the raw material body at the bottom of the ring furnace of piling up the raw material body, on will being deposited at the bottom of the ring furnace constitutes, the cavity of body of heater is the open annular cavity of going to the bottom, following bottom opening cooperates with at the bottom of the ring furnace with respect to body of heater turning motion in horizontal plane, and design has relief outlet and raw material body that the reaction of the roasting in body of heater cavity phosphoric anhydride gas is discharged to import and export on the body of heater.
In technique scheme, the top of body of heater annular cavity can be designed as the reflection arch structure, can more help the burning of in the kiln layer and kiln top is obtained reflect heat in the bed of material.Be positioned at phosphoric anhydride gas discharge outlet preferred design on the body of heater at the top of body of heater, directly link up with the top of body of heater annular cavity.Being used for the import and export of charging of raw material body and discharging, can be the bin gate that direct Design and Machining becomes on the ring furnace body wall, also can be other structure formation, preferably with the import and export of one section on the body of heater disconnection section that can open as raw material.
The present invention has also taked other some other technical measures.
The present inventor furthers investigate theoretically to the kiln-process phosphoric acid production process.In the production process of kiln-process phosphoric acid, the process that yellow phosphorus is produced in the phosphorus ore reduction is thermo-negative reaction, need a large amount of heats that adds, and the oxidising process of phosphorus is to generate phosphoric anhydride P 4O 10Thermopositive reaction, this heat generally be to take away with water coolant, so total energy consumption is very big in the kiln-process phosphoric acid of prior art is produced.The reaction process of kiln-process phosphoric acid is:
Ca 3(PO 4) 3+5C+3SiO 2=P 2↑+5CO ↑+3CaSiO 3 ΔH=1548kJ/mol P 2
P2+5/2O2=P2O5 ΔH=-1567kJ/mol P2
2CO+O 2=2CO 2 ΔH=-1373kJ/mol P 2
The thermal discharge that can see below two oxidizing reactions is higher than the caloric receptivity of first equation in reduction process.If oxidation is combined with reduction, the heat that two oxidizing reactions in back are produced is used for the caloric receptivity of reduction process, realizes kiln-process phosphoric acid reaction process self heat balance, does not need extraneous energy supply, can guarantee again that simultaneously the reaction process of the two carries out, this will be a great breakthrough.The processing method and the equipment of kiln method production high-quality phosphoric acid provided by the invention have been realized this hope, and can the higher mid low grade phosphate rock of silicon content be raw material production fine phosphoric acid.
The present invention combines rotary kiln with the advantage of tunnel furnace, avoid the shortcoming of the two, proposes a kind of new technical process, promptly encircles end kiln flow process.Therefore its advantage is: (1) kiln body no longer overturns, and can fundamentally avoid ring formation, for local bonding, except can be from batching solves, can discharge port with outside unload the machinery eliminating.(2) space availability ratio height, thermosteresis is little, can realize few heating or self-heating procedure preferably.(3) simple in structure, the high temperature insulating layer is easy to solve, and is convenient to realize automatization and large-scale production.(4) be convenient to temperature control, atmosphere control and operation automatization control.(5) the raw material body can carry out the secondary parcel, and technical process obtains simplifying.(6) by material is filled a prescription, the kiln slag of kiln discharge can be used as cement or cement clinker through grinding, also can be used as the porous wall material.(7) because raw material body charging bole and discharge port close proximity are convenient to realize importing and exporting heat exchange.(8) with the phosphate fertilizer of the high-quality phosphoric acid production high density of method of the present invention preparation, compare with phosphoric acid by wet process, this technology does not consume sulfuric acid, by-product phosphogypsum not yet.
Adopt processing method of the present invention and device fabrication high-quality phosphoric acid, have very high economic benefit.Workshop Production cost estimation of the present invention sees table.Scale is by producing 10000 tons of 100%H per year 3PO 4Meter.As seen compare with the cost that adopts phosphorus production phosphoric acid, cost is lower.
Title Consume (ton) Unit price (unit/ton) The amount of money
Phosphorus ore (17%P 2O 5) 4.75 40 190
Coke (85%C) 0.9 600 540
Silica 2.2 50 110
Power consumption 700kwh 0.4 280
Fuel (coal) 0.6 250 150
Depreciation (by 6 years) 80
Manually (35 people, 10 yuan of hourly wages) 210
Amount to 1560
About 10,000 yuan/ton of domestic yellow phosphorus price, the present invention can realize that kiln slag produces the comprehensive utilization of cement and building materials, forms a benign recycling economy system, not only has very big economic benefit is arranged, owing to protected environment, has the good social benefit simultaneously.
Description of drawings
Accompanying drawing 1 is the technical process schematic block diagram of one embodiment of the invention.
Accompanying drawing 2 is main TV structure synoptic diagram of kiln at the bottom of the facilities and equipments ring of the present invention.
Accompanying drawing 3 is plan structure synoptic diagram of kiln at the bottom of the facilities and equipments ring of the present invention.
The sign object of each shown by reference numeral is respectively in above-mentioned accompanying drawing: at the bottom of 1 rotatable stove; 2 annular bodies of heater; 3 raw material type bodies; 4 body of heater annular cavities; 5 phosphoric anhydride gas discharge outlets; 6 raw material bodies charging discharge port.
Embodiment
The present invention is further illustrated below in conjunction with the specific embodiment of the present invention; but of particular note; the specific embodiment of the present invention is not limited to the described form of the following examples; the those skilled in the art is not paying creatively work; the embodiment that can content design according to the present invention goes out other, but such embodiment should still belong to protection scope of the present invention.
The umber of being mentioned among the embodiment is parts by weight below.
Embodiment 1
Earlier with phosphorus ore (33%P 2O 5) 300 parts, 220 parts in silica, 90 parts of cokes are pulverized and are finely ground to 100~200 orders, use clay as the binding agent granulation then, and the bonded pelleting moulding about the about 20mm of pellet diameter, is sent into and is encircled on end kiln is deposited at the bottom of the kiln.The annular body of heater 2 that the raw material body 3 of ring end kiln by the rotatable annular furnace bottom 1 of piling up the raw material body, on will being deposited at the bottom of the ring furnace included in its cavity constitutes, the cavity of body of heater is the open annular cavity 4 of going to the bottom, following bottom opening cooperates with at the bottom of the ring furnace with respect to body of heater turning motion in horizontal plane, the top of body of heater annular cavity is the reflection arch structure, the top design of body of heater has phosphoric anhydride gas discharge outlet 5, and the disconnection section that can open with annular body of heater one is the import and export 6 of raw material type body.Along with slowly rotating at the bottom of the kiln, kiln temperature heats up gradually, is warming up to about about 1350 ℃ in temperature, is keeping under this temperature about about 2.0 hours.Oxidising process is finished in bed of material superjacent air space, and transfers heat to simultaneously in the following solid layer.The reacted phosphoric anhydride gas of roasting oxidation is discharged from the gas discharge outlet 5 on the ring kiln top, the end, send into the dust separation device udst separation, purified gas is sent into absorption equipment again, and the P2O5 that absorbs in the gas produces phosphoric acid, can absorb to obtain about 120 parts (the about 80%w H3PO4 of concentration) phosphoric acid.
Embodiment 2
Adopt phosphorus ore (17%P 2O 5) 475 parts, 1200 parts in Wingdale, 76 parts of cokes, 70 parts in bituminous coal, main raw material is pulverized and is finely ground to 100~200 orders, then through compression molding, about type piece equivalent diameter 30mm, without other binding agent.Block raw material body is inserted silk screen by sealing coat liquid soaking pit, make its surface soak attached one deck liquid barrier layer.The sealing coat immersion liquid is made up of following component: carbon 15%, and water glass (water glass) 5%, wilkinite 5%, all the other are water.Airing is promptly sent in the ring end kiln slightly.Ring end kiln is piled up the annular body of heater 2 that the rotatable annular furnace bottom 1 of raw material body, raw material body 3 on will being deposited at the bottom of the ring furnace include in its cavity by stove and is constituted, the cavity of body of heater is the open annular cavity 4 of going to the bottom, following bottom opening cooperates with at the bottom of the ring furnace with respect to body of heater turning motion in horizontal plane, the top of body of heater annular cavity is the reflection arch structure, the top design of body of heater has phosphoric anhydride gas discharge outlet 5, and the disconnection section that can open with annular body of heater one is the dress discharge port 6 of raw material body.Along with rotating at the bottom of the kiln, the raw material body enters main workspace, and oxidation is being carried out above the material and between the material piece.Kiln temperature is warming up to about about 1500 ℃, is keeping under this temperature about about 2.5 hours.Oxidising process is finished in raw material external body and bed of material superjacent air space, and transfers heat to simultaneously in the following solid layer.The reacted phosphoric anhydride gas of roasting oxidation is discharged from the gas discharge outlet 5 on the ring kiln top, the end, send into the dust separation device udst separation, purified gas is sent into absorption equipment again, and the P2O5 that absorbs in the gas produces phosphoric acid, can absorb to obtain about 130 parts of phosphoric acid (the about 75%wH3PO4 of concentration).Kiln slag grinds through pulverizing, and can become cement after the batching.

Claims (9)

1, a kind of mid low grade phosphate rock kiln-process phosphoric acid production method, basic process steps comprises:
(1) phosphorus ore of powder shaped and solid fuel or phosphorus ore, solid fuel and silica mixing aftershaping;
(2) the raw material body after the moulding is inserted roasting kiln and is carried out roasting reaction;
(3) the phosphoric anhydride gas that the roasting reaction is obtained is drawn from roasting kiln and is sent into the dust separation device udst separation;
(4) purified gas is sent into absorption equipment, absorbs the P in the gas 2O 5Produce phosphoric acid;
It is characterized in that described roasting kiln is ring end kiln, on raw material after the moulding is deposited at the bottom of the rotary kiln that encircles end kiln, carry out the reduction-oxidation roasting, maturing temperature is 1300~1550 ℃, time is 1.5~3 hours, at the bottom of the said ring kiln by the ring furnace of piling up the raw material body at the bottom of, can will be deposited in raw material body at the bottom of the ring furnace stove seat including the annular body of heater in its cavity in and be used to install body of heater constitute, the cavity of body of heater is the open annular cavity of going to the bottom, following bottom opening cooperates with at the bottom of the ring furnace with respect to body of heater turning motion in horizontal plane, and design has phosphoric anhydride gas discharge outlet and raw material body to import and export on the body of heater.
2, kiln-process phosphoric acid production method according to claim 1 is characterized in that inserting behind the material forming ring end kiln and carries out before the roasting, covers the sealing coat that raw material and air can be separated in the raw material surface.
3, kiln-process phosphoric acid production method according to claim 2, the sealing coat that it is characterized in that the raw material surface are to be covered in the raw material surface in the sealing coat liquid by the raw material body is dipped in.
4, kiln-process phosphoric acid production method according to claim 3 is characterized in that said sealing coat liquid consists of: carbon 10~20%, and water glass 5~10%, wilkinite 5~10%, all the other are water.
5, kiln-process phosphoric acid production method according to claim 1 is characterized in that containing binding agent in the shaping raw material component, and material forming adopts the bonded pelleting moulding, and the type body is spherical.
6, kiln-process phosphoric acid production method according to claim 1 is characterized in that material forming adopts compression moulding, and the type body is block.
7, be used for implementing the facilities and equipments of the described kiln-process phosphoric acid production method of each claim of claim 1 to 6, it is characterized in that specific equipment is a ring end kiln, the stove seat of being included in the annular body of heater in its cavity and being used to install body of heater by the raw material body at the bottom of the ring furnace of piling up the raw material body, on will being deposited at the bottom of the ring furnace constitutes, the cavity of body of heater is the open annular cavity of going to the bottom, following bottom opening cooperates with at the bottom of the ring furnace with respect to body of heater turning motion in horizontal plane, and design has phosphoric anhydride gas discharge outlet and raw material body to import and export on the body of heater.
8, facilities and equipments according to claim 7, the top that it is characterized in that the body of heater annular cavity is the reflection arch structure.
9, facilities and equipments according to claim 7, the phosphoric anhydride gas discharge outlet design that it is characterized in that encircling end kiln is at the top of body of heater, and the import and export of raw material body are the disconnection section that one section of annular body of heater can be opened.
CN200710049838A 2007-08-24 2007-08-24 Mid low grade phosphate rock kiln-process phosphoric acid production method and facilities and equipments thereof Expired - Fee Related CN100584748C (en)

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CN101597039B (en) * 2009-07-08 2011-06-08 湖北兴发化工集团股份有限公司 Method for producing phosphoric acid by utilizing tunnel kiln
CN102126712B (en) * 2011-04-22 2013-04-24 四川大学 Method for producing phosphoric acid by utilizing middle grade phosphate ore
CN104211028B (en) * 2013-06-04 2017-03-22 四川玖长科技有限公司 Composite pellet material used for kiln method phosphoric acid technology and molding method thereof
CN103496682B (en) * 2013-09-16 2016-03-16 金正大诺泰尔化学有限公司 A kind of Rock Phosphate (72Min BPL), Wingdale and silica produce the method for phosphoric acid jointly producing cement, synthetic ammonia
CN106241760A (en) * 2016-09-13 2016-12-21 江苏省冶金设计院有限公司 A kind of wet bulb bilayer pyrolysis-type phosphoric acid preparation system and method
CN106395772A (en) * 2016-09-13 2017-02-15 江苏省冶金设计院有限公司 Preparation method of phosphoric acid by phosphorite pellet layering
CN106241759A (en) * 2016-09-13 2016-12-21 江苏省冶金设计院有限公司 A kind of wet lump ore is with addition of char particle type phosphoric acid preparation system and method
CN106185851A (en) * 2016-09-13 2016-12-07 江苏省冶金设计院有限公司 A kind of dry bulb pyrolysis-type phosphoric acid preparation system and method
CN106517121A (en) * 2016-12-21 2017-03-22 江苏省冶金设计院有限公司 System for processing phosphorite and application thereof
CN106495116A (en) * 2016-12-21 2017-03-15 江苏省冶金设计院有限公司 Rotary hearth furnace
CN108775817A (en) * 2018-07-27 2018-11-09 江苏凤谷节能科技有限公司 A method of based on Ω types rotary kiln and annular furnace combined sintering powder body material
CN111994886B (en) * 2020-06-19 2021-11-30 成都易态科技有限公司 Production system and production method of high-purity phosphoric acid

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