CN101481222B - Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum - Google Patents
Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum Download PDFInfo
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- CN101481222B CN101481222B CN2009103006174A CN200910300617A CN101481222B CN 101481222 B CN101481222 B CN 101481222B CN 2009103006174 A CN2009103006174 A CN 2009103006174A CN 200910300617 A CN200910300617 A CN 200910300617A CN 101481222 B CN101481222 B CN 101481222B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1031—Lime-free or very low lime-content materials
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Abstract
The invention discloses a method of partially converting phosphorous plaster to prepare side product ammonium sulfate of aluminum sulfate, which has the main steps of converting phosphorous plaster, filtering and separating converted substances, neutralizing converted liquid, concentrating, crystallizing and drying aluminum sulfate solution, drying filtrated cake and bauxite, blending and homogenizing raw material, calcining and cooling grog, modifying, grinding and homogenizing grog, processing calcination tail gas and the like. The mixed material satisfying materials required by the production of aluminum sulfate cement is achieved by partially converting the phosphorous plaster which does not need to be preprocessed. No limestone is required to be additionally added, the application range of the phosphorous plaster with high ferric and aluminum impurity contents is widened, the procedures and the converting equipment are simplified, ammonia consumption and operation difficulty are reduced, the cost is saved, the discharge of secondary polluting substances is eliminate, the heat and the carbon dioxide carried out by the calcination tail gas are recovered and utilized, and the energy consumption can be effectively reduced to further save the cost. In addition, the method does not have high requirements on the impurity content of the phosphorous plaster and has strong suitability on the raw material.
Description
Technical field
The present invention relates to the preparing technical field of aluminosulfate cement, especially a kind of is the method that main raw material, part transform system aluminosulfate cement, while producing ammonium sulfate byproduct with the phosphogypsum slag.
Background technology
China has become the multiple fertile big producing country of world's phosphorus; High-concentration phosphate compound fertilizers accounts for more than 50% of ultimate production; The phosphogypsum volume of cargo in storage of by-product reaches several hundred million tons in its production process, about 5,000 ten thousand tons of annual new increment, and the recycling of phosphogypsum has become the important topic of phosphorous chemical industry industry Sustainable development.
Usually, phosphogypsum is powdery, and outward appearance generally is greyish white, sallow, light green, dark-grey isochrome, volume density 0.7～0.9g/cm
3, particle diameter is generally 5～20um, and its staple is terra alba (CaSO
42H
2O), its content generally can reach 75～95%, and accessory constituent is phosphorus ore grain, silicate and the sulphur fluoride compound organic matter etc. of a spot of not complete reaction.The main chemical constitution (mass percent) of phosphogypsum generally includes: CaO:28～33%, SO
3: 38～44%, water-soluble P
2O
5: 0.05～0.5%, insoluble P
2O
5: 0.5～2%, Fe
2O
3: 0.2～2.5%, Al
2O
3: 0.5～4%, SiO
2: 0.5～6%, MgO:0.1～0.5%, F:0.1～0.5%, crystal water: 14.5 18%.
With bauxitic clay and Wingdale is that the chemical constitution of the aluminosulfate cement of main material production mainly contains CaO, Al
2O
3, SiO
2, SO
3Deng, and in the aluminosulfate cement production process, also must add a certain amount of gypsum, this gives high ferro, aluminium foreign matter of phosphor gypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting provides technical qualification preferably.
Bauxitic clay is to be commonly used to produce the uneven material that a kind of nature of aluminum oxide and aluminium exists.The major ingredient of bauxitic clay comprises three water http://knology.chinaccm.com/phrase-2006030911434300310.html aluminium ores, boehmite and water
) generally include: CaO:0～2.5%, SO
3: 0～1%, Fe
2O
3: 0～6%, Al
2O
3: 50～75%, SiO
2: 5～15%, MgO:0～1%, Ti:0～4%.
At present, the technical process with high ferro, aluminium foreign matter of phosphor gypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting does not appear in the newspapers as yet.Comparatively approaching prior art has: " with the research of phosphogypsum for sintering sulpho-aluminate cement " (" cement " magazine; Sponsor: building material industrial technology Institute of Social Science Information; 1999 4 phases; P1-P4) introduce the flow process of burning till the system aluminosulfate cement with phosphogypsum in the literary composition, this flow process is to be that main raw material is configured to raw material with Wingdale, bauxitic clay and phosphogypsum, further burns till to be the sulfate-phosphate cement clinker.Its weak point is: 1. the phosphogypsum proportion is 20-25% in the raw material, insufficiently calcareously still need add Wingdale, and the phosphogypsum quantity of ton product consumption only accounts for 20 25% of whole raw materials.2. this flow process adopts shaft kiln calcination, and energy consumption is higher, and the incinerating reducing atmosphere is wayward, unstable product quality, and production cost is also higher.
With the phosphogypsum is that raw material is more through the report that carbonated aqueous ammonia transforms system ammonium sulfate; Mainly comprise: " utilizing phosphogypsum to produce ammonium sulfate " (" Henan chemical industry " magazine; Sponsor: Henan Province's chemical institute, 1997 9 phases, P37-P38) phosphogypsum of a literary composition introduction transforms through carbonated aqueous ammonia and makes the fertilizer grade ammonium sulfate product; Its weak point is: 1. the raw material phosphogypsum must pass through selected to improve the quality that gets into the production system phosphogypsum; Could guarantee higher phosphogypsum transformation efficiency and quality product, increase processing cost thus, the utilization of the phosphogypsum slag that foreign matter content is high is restricted.2. this flow process has secondary residue to produce, a part be foreign matter content very high select surplus phosphogypsum, another part then is the lime carbonate waste residue that needs secondary to utilize again." the multiple fertile commerical test research of phosphogypsum comprehensive utilization system high density NPK " (" design of sulphur phosphorus and powder technology " magazine; Sponsor: Nanhua Group Design Inst; 2004 5 phases, P7-P9) phosphogypsum of a literary composition introduction transforms through carbonated aqueous ammonia and makes ammoniumsulphate soln, further carries out metathetical with Repone K and must be used for the multiple fertile flow process that required intermediates are grabbed potassium-ammonium sulfate solution and ammonium chloride solution of producing of NPK; Its weak point: after 1. phosphogypsum need pass through rinsing processing; Get into carbonization ammonium water conversion system again, increased the phosphogypsum processing cost thus, phosphogypsum washing water and solid impurity in the flow process have produced secondary wastewater and waste residue.2. this flow process produces has the lime carbonate waste residue that needs secondary to utilize again.
Summary of the invention
The purpose of this invention is to provide a kind of phosphogypsum that adopts fully as body material, after transforming, all produce required gypsum matter, calcareous composition raw material, simultaneously the novel method of producing ammonium sulfate byproduct as the preparation aluminosulfate cement.Guaranteeing to simplify technology under the product quality premise, reduce comprehensive energy consumption and cost, do not produce secondary pollution.
In order to realize the foregoing invention purpose, the technical scheme that the present invention adopts is following:
The method of phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting, key step comprise neutralization, condensing crystal drying, filter cake and aluminium vanadine drying, raw meal proportioning and homogenizing, clinker burning and cooling, the modified grinding of grog and the homogenizing of ammoniumsulphate soln, the calcining vent gas treatment of phosphogypsum conversion, conversion product filtering separation, conversion fluid.
Calcining vent gas treatment in the above-mentioned steps; The waste gas (promptly calcining tail gas) that is carbonated that the clinker burning process is produced and small amount of sulfur, oxynitride etc. is recycled; The calcining tail gas that goes out rotary calciner is introduced in the drying plant filter cake is carried out the heat exchange drying; Reclaim after the heat cooling gathers dust, get into water wash column purifications of further lowering the temperature, get into again in the ammonia absorption carbonating tower; Carry out combination reaction with strong aqua and obtain carbide ammonia solution, go out carbide ammonia solution that ammonia absorbs carbonating tower and close the symbol carbide ammonia solution that requires that feeds intake and participate in the phosphogypsum conversion reaction again through being deployed into; Go out ammonia-contaminated gas emptying after phosphoric acid by wet process or the washing of other acidic liq of ammonia absorption carbonating tower, can be utilized again by the phosphoric acid by wet process of part ammonification or other acidic liq, as can be used as the raw materials for production of phosphoric acid salt or phosphate fertilizer or other corresponding salt etc.
Concrete steps are following:
(1) phosphogypsum transforms
The carbonated aqueous ammonia that is absorbed carbonating tower by step (10) calcining vent gas treatment operation ammonia is introduced in the allotment dashpot, is adjusted to its composition with volatile salt or bicarbonate of ammonia, ammonium sulfate, water and meets and feed intake that (its mass percent consists of the carbonated aqueous ammonia that requires: NH
4 +Content is 8～12%, CO
2Content is: 9～15%, SO
3Content is: 0.5～5%); With the carbonated aqueous ammonia after regulating and phosphogypsum butt (the phosphogypsum butt is meant the phosphogypsum that does not contain free-water) by 1.7～2.2: 1 mass ratio carries out the phosphogypsum conversion reaction in conversion tank; The control conversion reaction time is 60～120min, 30～60 ℃ of temperature of reaction; Reaction finishes, and must transform slip; The phosphogypsum transformation efficiency is 75～95%.
The transformation efficiency of phosphogypsum can calculate through following formula:
X＝(100A-100C)/(100A-0.45AC-BC)
Wherein: X: phosphogypsum transformation efficiency, %
A: SO in the raw material phosphogypsum
3Content, %
B: crystal water content in the raw material phosphogypsum, %
C: SO in the conversion product
3Content, %
(2) conversion product filtering separation
The conversion slip (being conversion product) of above-mentioned steps (1) gained is carried out solid-liquid separation (can preferably adopt diaphragm filter press to carry out press filtration, also can adopt vacuum, other filter type such as centrifugal), respectively filter cake and conversion fluid; With water filter cake is carried out unidirectional or two-way washing, SO3 content≤0.5% (mass percent) to the effluent is washed in control.
(3) neutralization of conversion fluid
The pH value that above-mentioned steps (2) is separated the conversion fluid of back gained with a small amount of sulfuric acid is adjusted to 4.3～4.6, and the ammoniumsulphate soln of acquisition wherein contains (NH
4)
2SO
420～40% (mass percents).
(4) the concentrating of ammoniumsulphate soln, crystallization, drying
The ammoniumsulphate soln that above-mentioned steps (3) neutralization is obtained concentrates, crystallization, drying (can preferably adopt methods such as economic benefits and social benefits concentrate, vacuum crystallization, fluidized drying), the fertilizer grade ammonium sulfate product.This sub product reaches the technical requirements of the salable product of stipulating in the state compulsory standard.
(5) filtration cakes torrefaction
The calcining tail gas (500～600 ℃) of filter cake after above-mentioned steps (2) filtering separation and the washing and the discharge of step (8) rotary calciner is carried out heat exchange drying (can preferably adopt the countercurrent flow drying) to filter cake in drying plant; Wherein free-water and partial crystallization water are removed, obtained filter cake dry powder; Its chemical constitution (mass percent) mainly comprises:
CaO:42～50%, SO
3: 3～12.5%, water-soluble P
2O
5: 0～0.1%, insoluble P
2O
5: 0～2%, Fe
2O
3: 0～3%, Al
2O
3: 0～6%, SiO
2%::0～5%, MgO:0～0.5%.
The calcining tail gas of discharging through drying machine in this step can be calcined vent gas treatment by following step (10).
(6) bauxitic clay is dry
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) gets in the drying plant, with bauxitic clay heat exchange dry (can preferably adopt countercurrent flow dry), removes its free-water, dried bauxitic clay;
(7) raw meal proportioning and homogenizing
By the chemical constitution in the sulphoaluminate cement clinker (mass percent) is Al
2O
3: SiO>=31.0%,
2% :≤10.5% to form (mass percent) with essential mineral be C
2S:20～40%, C
4A
3S:50～75%; Satisfy above-mentioned condition simultaneously and carry out raw meal proportioning and homogenizing; The filter cake dry powder and the dried bauxitic clay of step (6) of phosphogypsum dry powder (referring to raw material phosphogypsum convection drying gained), above-mentioned steps (5) gained are pressed (0～13): (52～70): (30～35) (mass ratio) is mixed; And the entering grinding machine grinds; Powder after this grinding is the raw material powder, send the raw material homogenizing storehouse to carry out homogenizing (can adopt the air-flow stirring mixing method to carry out homogenizing) in the raw material powder, the raw material powder after the homogenizing; Its chemical constitution (mass percent) mainly comprises:
CaO:29.5～31.0%, SO
3: 6.0～9.0%, total phosphorus P
2O
5: 0～1.5%, Fe
2O
3: 1.5～3.0%, Al
2O
3: 22.5～23.5%, SiO
2: 4.5～6.0%, MgO:0～0.5%, TiO
2: 0.5～2.5%, loss on ignition (1000 ℃): 23.5～27.5%.
(8) clinker burning and cooling
Raw material powder after the homogenizing that above-mentioned steps (7) is made is sent in the rotary calciner and is calcined; Calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln; The material for making clothes calcining (the main reaction region temperature is 1250～1350 ℃) of not being clamminess down of control fire point, the assurance material is at the main reaction region residence time 40～60min; After reaction finishes,, obtain grog through chilled air cools, fragmentation;
Chemical composition in the grog mainly comprises (mass percent):
CaO:38.0～40.5%, SO
3: 8.0～11.5%, total phosphorus P
2O
5: 0～2%, Fe
2O
3: 2.0～4.0%, Al
2O
3: 30.0～32.0%, SiO
2: 8.0～10.5%, MgO:0～0.5%, TiO
2: 0.5～3.5%;
Mineralogical composition in the grog mainly comprises (mass percent):
C
2S：20.0～40.0％，C
4A
3S：55.0～75.0％。
The calcining tail gas (500～600 ℃) that rotary calciner is discharged in this step can feed in the drying plant of step (5) and is used for filter cake is carried out the heat exchange drying;
Be used for bauxitic clay is carried out the heat exchange drying in the drying plant of the waste hot gas entering step (6) that when chilled air cools, produces.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) obtains, add through dry modified modified phosphogypsum dry powder (CaSO wherein
42H
2The O mass percent is not less than 92%, and the free-water mass percent is not more than 0.5%; When to be mixed with mass percent be 1% the aqueous solution with it, its PH was 6.5～8.0) carry out that modified (mass ratio is a grog: modified phosphogypsum dry powder=85～95: 5～15), and in homogenizing storehouse, carry out homogenizing, promptly become the quick hardening sulphoaluminate cement finished product.
Each item performance of gained quick hardening sulphoaluminate cement finished product satisfies " aluminosulfate cement " (GB20472-2006) technical requirement of middle quick hardening sulphoaluminate cement.
(10) calcining vent gas treatment
The calcining tail gas that comes out from the drying plant of above-mentioned steps (5) is through the laggard water wash column processing of lowering the temperature of going into of gathering dust; The control air outlet temperature is 30～50 ℃; Gas after cooling gets in the ammonia absorption carbonating tower and carries out combination reaction with strong aqua; It is 35～40 ℃ that control ammonia absorbs the interior liquidus temperature of carbonating tower, and ammonium carbon ratio (mol ratio) is n (NH in the liquid phase
4 +): n (CO
2)=1.7～2.2: 1, reaction obtains carbide ammonia solution after finishing, and allocates in the allotment dashpot of this carbide ammonia solution entering step (1); The ammonia-contaminated gas that goes out ammonia absorption carbonating tower gets in the washing tower, removes a small amount of gas ammonia wherein, emptying then with phosphoric acid by wet process or the washing of other acidic liq; Raw materials for production that can be used as phosphoric acid salt or phosphate fertilizer or other corresponding salt by the phosphoric acid by wet process of part ammonification or other acidic liq etc. utilize again.
Compared with prior art, the invention has the beneficial effects as follows:
1, through being met calcium carbonate, the gypsum matter compound that aluminosulfate cement is produced required batching requirement to not needing pretreated phosphogypsum partly to be converted; Production process does not need to add Wingdale again, has reached phosphogypsum in the purpose of aluminosulfate cement production as main raw material; Not only expanded the range of application of high ferro, aluminium foreign matter content phosphogypsum; Also simplify flow process and converting apparatus, widened the red-tape operati elasticity of conversion reaction conditions to greatest extent, reduced ammonia consumption and operation easier; Practice thrift cost, stopped the discharge of secondary pollutant.
2, the high-temp waste gas of calcining out (calcining tail gas) is introduced into the phosphogypsum drying system and reclaims its waste heat; And make its temperature be reduced to the into technic index requirement of ammonia absorption carbonating tower, again after ammonia is inhaled the carbonic acid gas in the carbonating tower recovery waste gas and is removed other sour gas; At last remove exhaust gas evacuation behind the wherein contained ammonia by the phosphoric acid by wet process washing, phosphoric acid by wet process then gets into phosphate fertilizer or phosphate production system.Because heat energy and carbonic acid gas to waste gas is taken out of are recycled, and have effectively reduced energy consumption, have practiced thrift cost.
3, this method is less demanding to the phosphogypsum foreign matter content, has the characteristics strong to adaptability to raw material.
Description of drawings
Fig. 1 is the process flow diagram of the method for phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.
But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
The chemical constitution of used phosphogypsum, bauxitic clay (mass percent) is respectively as follows in the present embodiment:
Phosphogypsum (butt does not contain the phosphogypsum of free-water):
CaO:30.78%, SO
3: 40.25%, water-soluble P
2O
5: 0.36%, insoluble P
2O
5: 1.45%,
Fe
2O
3：1.90％，Al
2O
3：4.01％，SiO
2：3.52％， MgO：0.20％，
Crystal water: 14.98%.
Bauxitic clay (butt does not contain the bauxitic clay of free-water):
CaO：1.18％，SO
3：0.65％，Fe
2O
3：2.25％，Al
2O
3：64.56％，
SiO
2: 6.58% MgO:0.34%, TiO
2: 2.21%, loss on ignition (1000 ℃): 12.75%.
The method of present embodiment phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting comprises following key step shown in the process flow diagram of Fig. 1:
(1) phosphogypsum transforms
The carbonated aqueous ammonia that is absorbed carbonating tower by step (10) calcining vent gas treatment operation ammonia is introduced in the allotment dashpot, with solid carbonic acid ammonium and ammoniumsulphate soln and tap water, is adjusted to its mass percent and consists of: NH
4 +Content is 8.35%, CO
2Content is: SO 9.40%,
3Content is: 4.05%, the carbonated aqueous ammonia after regulating and phosphogypsum (in butt) are carried out the phosphogypsum conversion reaction by 2.19: 1 mass ratio in conversion tank; The control conversion reaction time is 60min, 30～40 ℃ of temperature of reaction; Reaction finishes, and must transform slip, and the sulfate radical transformation efficiency is 77.32% in the phosphogypsum.
(2) conversion product filtering separation
Adopt diaphragm filter press that the conversion slip of above-mentioned steps (1) gained is carried out solid-liquid separation, get filter cake and conversion fluid respectively; With water filter cake is carried out unidirectional washing, measure SO in the scrub stream fluid
3Content (mass percent) is 0.42% o'clock, stops washing, discharging.
(3) neutralization of conversion fluid
The pH value that above-mentioned steps (2) is separated the conversion fluid of back gained with a small amount of sulfuric acid is adjusted to 4.3, obtains to contain (NH
4)
2SO
4The ammoniumsulphate soln of 28.07% (mass percent).
(4) the concentrating of ammoniumsulphate soln, crystallization, drying
The ammoniumsulphate soln that above-mentioned steps (3) neutralization is obtained carries out that economic benefits and social benefits concentrate, vacuum crystallization, fluidized drying, nitrogen (N) content be the fertilizer grade ammonium sulfate product of 20.84% (mass percent).
(5) filtration cakes torrefaction
500～600 ℃ calcining tail gas of filter cake after above-mentioned steps (2) filtering separation and the washing and the discharge of step (8) rotary calciner is carried out the countercurrent flow drying to filter cake in drying machine; Wherein free-water and partial crystallization water are removed; Obtain filter cake dry powder, its chemical constitution (mass percent) mainly comprises:
CaO:41.78%, SO
3: 12.27%, water-soluble P
2O
5: 0.05%, insoluble P
2O
5: 1.95%, Fe
2O
3: 2.55%, Al
2O
3: 5.39%, SiO
2%:3.78%, MgO:0.27%, loss on ignition (1000 ℃): 28.26%.
The calcining tail gas of discharging through drying machine in this step is handled by following step (10).
(6) bauxitic clay is dry
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) gets in the dryer, and is dry with the bauxitic clay countercurrent flow, removes its free-water, dried bauxitic clay.
(7) raw meal proportioning and homogenizing
The filter cake dry powder and the bauxitic clay of phosphogypsum dry powder, above-mentioned steps (5) gained are mixed by 0: 70: 30 (mass ratio); And the entering grinding machine grinds; Powder after this grinding is the raw material powder, send the raw material homogenizing storehouse to carry out homogenizing in the raw material powder, the raw material powder after the homogenizing; Its chemical constitution (mass percent) mainly comprises:
CaO:29.67%, SO
3: 8.79%, total phosphorus P
2O
5: 1.36%, Fe
2O
3: 2.46%, Al
2O
3: 23.14%, SiO
2: 4.62%, MgO:0.29%, TiO
2: 0.66%, loss on ignition (1000 ℃): 23.61%.
(8) clinker burning and cooling
Raw material powder after the homogenizing that above-mentioned steps (7) is made is sent in the rotary calciner and is calcined, and calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln, and the main reaction region temperature is 1250～1350 ℃, and material is at main reaction region residence time 45min; Reaction finishes after chilled air cools, fragmentation obtain grog, and its chemical composition (mass percent) mainly comprises:
CaO:37.74%, SO
3: 11.04%, total phosphorus P
2O
5: 1.71%, Fe
2O
3: 3.41%,
Al
2O
3：30.20％，SiO
2：8.22％，MgO：0.37％， TiO
2：0.83％；
Essential mineral mainly comprises (mass percent):
C
4A
3S：60.09％，C
2S：23.58％，C
2F：5.80％，CT：1.42％，Sf：3.23％
Cf：0.54％。
In this step, be used for filter cake is carried out the countercurrent flow drying in the drying machine of the calcining tail gas feeding step (5) that rotary calciner is discharged;
Be used for bauxitic clay is carried out the countercurrent flow drying in the dryer of the waste hot gas entering step (6) that when chilled air cools, produces.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) makes, add through dry modified modified phosphogypsum dry powder (CaSO
42H
2The O mass percent is not less than 92%, and the free-water mass percent is not more than 0.5%; 1% solution ph 6.5～8.0) carries out that modified (mass ratio is a grog: modified phosphogypsum dry powder=94: 6), and in homogenizing storehouse, carry out homogenizing, promptly become the quick hardening sulphoaluminate cement finished product.
Each item performance of gained quick hardening sulphoaluminate cement finished product satisfies " aluminosulfate cement " (GB20472-2006) technical requirement of middle quick hardening sulphoaluminate cement (52.5 strength grade), and it is following specifically to detect index:
Specific surface area: 362m
2/ kg the presetting period: 35min final setting time: 80min
Ultimate compression strength: 1d 42MPa 3d 53.5MPa 28d 61.4MPa
Folding strength: 1d 6.8MPa 3d 7.2MPa 28d 8.3MPa
(10) calcining vent gas treatment
The calcining tail gas that comes from the drying machine of above-mentioned steps (5) is through the laggard water wash column processing of lowering the temperature of going into of gathering dust; Controlling out temperature is 40～45 ℃; Get into ammonia through the gas of lowering the temperature and absorb carbonating tower, it is 35～40 ℃ that control ammonia absorbs the interior temperature of carbonating tower, and ammonium carbon ratio (mol ratio) is n (NH in the liquid phase
4 +): n (CO
2)=1.8: 1, reaction obtains carbide ammonia solution after finishing, and allocates in the allotment dashpot of this carbide ammonia solution entering step (1); The ammonia-contaminated gas that goes out carbonating tower gets in the washing tower, removes a small amount of gas ammonia wherein with the phosphoric acid by wet process washing, emptying then (raw materials for production etc. that can be used as phosphoric acid salt or phosphate fertilizer by the phosphoric acid by wet process of part ammonification utilize again).
Embodiment 2
The chemical constitution (mass percent) of the used phosphogypsum of present embodiment, bauxitic clay is as follows:
Phosphogypsum (butt does not contain the phosphogypsum of free-water):
CaO:31.33% SO
3: 42.05% water-soluble P
2O
5: 0.15% insoluble P
2O
5: 0.85%
Fe
2O
3：1.20％ Al
2O
3：2.77％ SiO
2：4.37％ MgO：0.20％
Crystal water: 15.40%
Bauxitic clay (butt does not contain the bauxitic clay of free-water):
CaO：1.18％，?SO
3：0.65％，Fe
2O
3：2.25％，?Al
2O
3：64.56％，
SiO
2: 6.58% MgO:0.34%, TiO
2: 2.21%, loss on ignition (1000 ℃): 12.75%.
The method of present embodiment phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting comprises following key step shown in the process flow diagram of Fig. 1:
(1) phosphogypsum transforms
The carbonated aqueous ammonia that is absorbed carbonating tower by step (10) calcining vent gas treatment operation ammonia is introduced in the allotment dashpot, with solid carbonic acid ammonium and ammoniumsulphate soln and tap water, is adjusted to its mass percent and consists of: NH
4 +Content is 10.25%, CO
2Content is: SO 11.85%,
3Content is: 3.02%, the carbonated aqueous ammonia after regulating and phosphogypsum (in butt) are carried out conversion reaction by 1.89: 1 mass ratio in conversion tank; The control conversion reaction time is 100min, 40～50 ℃ of temperature of reaction; Reaction finishes, and must transform slip, and the sulfate radical transformation efficiency is 84.08% in the phosphogypsum.
(2) conversion product filtering separation
Adopt diaphragm filter press that the conversion slip of above-mentioned steps (1) gained is carried out solid-liquid separation, and filter cake is carried out unidirectional washing, measure SO in the scrub stream fluid with water
3Content (mass percent) is 0.38% o'clock, stops washing, discharging.
(3) neutralization of conversion fluid
The pH value that above-mentioned steps (2) is separated the conversion fluid of back gained with a small amount of sulfuric acid is adjusted to 4.5, obtains to contain (NH
4)
2SO
4The ammoniumsulphate soln of 32.64% (mass percent).
(4) the concentrating of ammoniumsulphate soln, crystallization, drying
The ammoniumsulphate soln that above-mentioned steps (3) neutralization is obtained carries out that economic benefits and social benefits concentrate, vacuum crystallization, fluidized drying, nitrogen (N) content be the fertilizer grade ammonium sulfate product of 20.97% (mass percent).
(5) filtration cakes torrefaction
500～600 ℃ calcining tail gas of filter cake after above-mentioned steps (2) filtering separation and the washing and the discharge of step (8) rotary calciner is carried out the countercurrent flow drying to filter cake in drying machine; Wherein free-water and partial crystallization water are removed; Obtain filter cake dry powder, its chemical constitution (mass percent) mainly comprises:
CaO:44.58%, SO
3: 9.41%, water-soluble P
2O
5: 0.02%, insoluble P
2O
5: 1.19%, Fe
2O
3: 1.69%, Al
2O
3: 3.89%, SiO
2%:4.91%, MgO:0.28%, loss on ignition (1000 ℃): 31.44%.
The calcining tail gas of discharging through drying machine in this step is handled by following step (10).
(6) bauxitic clay is dry
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) gets in the dryer, and is dry with the bauxitic clay countercurrent flow, removes its free-water, dried bauxitic clay.
(7) raw meal proportioning and homogenizing
The filter cake dry powder and the bauxitic clay of phosphogypsum dry powder, above-mentioned steps (5) gained are mixed by 1.2: 66.5: 32.3 (mass ratio); And the entering grinding machine grinds; Powder after this grinding is the raw material powder, send the raw material homogenizing storehouse to carry out homogenizing in the raw material powder, the raw material powder after the homogenizing; Its chemical constitution (mass percent) mainly comprises:
CaO:30.40%, SO
3: 6.97%, total phosphorus P
2O
5: 0.81%, Fe
2O
3: 1.86%, Al
2O
3: 23.47%, SiO
2: 5.44%, MgO:0.30%, TiO
2: 0.71%, loss on ignition (1000 ℃): 25.21%.
(8) clinker burning and cooling
Raw material powder after the homogenizing that above-mentioned steps (7) is made is sent in the rotary calciner and is calcined, and calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln, and the main reaction region temperature is 1250～1350 ℃, and material is at main reaction region residence time 45min; Reaction finishes after chilled air cools, fragmentation obtain grog, and its chemical composition (mass percent) mainly comprises:
CaO:39.50%, SO
3: 8.95%, total phosphorus P
2O
5: 1.25%, Fe
2O
3: 3.77%,
Al
2O
3：31.27％，SiO
2：9.45％，?MgO：0.39％， TiO
2：0.92％；
Essential mineral mainly comprises (mass percent):
C
4A
3S：62.24％，C
2S：27.11％，C
2F：4.62％，CT：1.56％，Sf：0.86％
Cf：1.48％。
In this step, be used for filter cake is carried out the countercurrent flow drying in the drying machine of the calcining tail gas feeding step (5) that rotary calciner is discharged;
Be used for bauxitic clay is carried out the countercurrent flow drying in the dryer of the waste hot gas entering step (6) that when chilled air cools, produces.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) makes, add through dry modified modified phosphogypsum dry powder (CaSO
42H
2The O mass percent is not less than 92%, and the free-water mass percent is not more than 0.5%; 1% solution ph 6.5～8.0) carries out that modified (mass ratio is a grog: modified phosphogypsum dry powder=89: 11), and in homogenizing storehouse, carry out homogenizing, promptly become the quick hardening sulphoaluminate cement finished product.
Each item performance of gained quick hardening sulphoaluminate cement finished product satisfies the technical requirement of quick hardening sulphoaluminate cement (52.5 strength grade) in " aluminosulfate cement " (GB20472 2006), and it is following specifically to detect index:
Specific surface area: 360m
2/ kg the presetting period: 38min final setting time: 75min
Ultimate compression strength: 1d 43MPa 3d 54.2MPa 28d 63.5MPa
Folding strength: 1d 6.6MPa 3d 7.4MPa 28d 8.8MPa
(10) calcining vent gas treatment
The calcining tail gas that comes from the drying machine of above-mentioned steps (5) is through the laggard water wash column processing of lowering the temperature of going into of gathering dust; The control air outlet temperature is 40～45 ℃; Gas after cooling gets into ammonia and absorbs carbonating tower, and temperature is 35～40 ℃ in the control ammonia absorption carbonating tower, and ammonium carbon ratio (mol ratio) is n (NH in the liquid phase
4 +): n (CO
2)=1.92: 1, reaction obtains carbide ammonia solution after finishing, and allocates in the allotment dashpot of this carbide ammonia solution entering step (1); The ammonia-contaminated gas that goes out carbonating tower gets in the washing tower, removes a small amount of gas ammonia wherein with the phosphoric acid by wet process washing, emptying then (raw materials for production etc. that can be used as phosphoric acid salt or phosphate fertilizer by the phosphoric acid by wet process of part ammonification utilize again).
Embodiment 3
The chemical constitution (mass percent) of the used phosphogypsum of present embodiment, bauxitic clay is as follows:
Phosphogypsum (butt, do not contain free-water phosphogypsum):
CaO:32.28%SO
3: 43.08% water-soluble P
2O
5: 0.08% insoluble P
2O
5: 0.68%Fe
2O
3: 1.15%Al
2O
3: 2.15% SiO
2: 3.88% MgO:0.14%
Crystal water: 16.32%
Bauxitic clay (butt does not contain the bauxitic clay of free-water):
CaO:2.39% SO
3: 0.67% Fe
2O
3: 3.21% Al
2O
3: 60.20% SiO
2: 7.51% MgO:0.40%TiO
2: 3.38% loss on ignition (1000 ℃): 13.20%
The method of present embodiment phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting comprises following key step shown in the process flow diagram of Fig. 1:
(1) phosphogypsum transforms
The carbonated aqueous ammonia that is absorbed carbonating tower by step (10) calcining vent gas treatment operation ammonia is introduced in the allotment dashpot, with solid carbonic acid ammonium and ammoniumsulphate soln and tap water, is adjusted to its mass percent and consists of: NH
4 +Content is 11.65%, CO
2Content is: SO 14.36%,
3Content is: 1.08%, the carbonated aqueous ammonia after regulating and phosphogypsum (in butt) are carried out conversion reaction by 1.87: 1 mass ratio in conversion tank; The control conversion reaction time is 120min, 50～60 ℃ of temperature of reaction; Reaction finishes, and must transform slip, and the sulfate radical transformation efficiency is 94.56% in the phosphogypsum.
(2) conversion product filtering separation
Adopt diaphragm filter press that the conversion slip of above-mentioned steps (1) gained is carried out solid-liquid separation, and filter cake is carried out unidirectional washing, measure SO in the scrub stream fluid with water
3Content (mass percent) is 0.22% o'clock, stops washing, discharging.
(3) neutralization of conversion fluid
The pH value that above-mentioned steps (2) is separated the conversion fluid of back gained with a small amount of sulfuric acid is adjusted to 4.5, obtains to contain (NH
4)
2SO
4The ammoniumsulphate soln of 34.18% (mass percent).
(4) the concentrating of ammoniumsulphate soln, crystallization, drying
The ammoniumsulphate soln that above-mentioned steps (3) neutralization is obtained carries out that economic benefits and social benefits concentrate, vacuum crystallization, fluidized drying, nitrogen (N) content be the fertilizer grade ammonium sulfate product of 20.96% (mass percent).
(5) filtration cakes torrefaction
500～600 ℃ calcining tail gas of filter cake after above-mentioned steps (2) filtering separation and the washing and the discharge of step (8) rotary calciner is carried out the countercurrent flow drying to filter cake in drying machine; Wherein free-water and partial crystallization water are removed; Obtain filter cake dry powder, its chemical constitution (mass percent) mainly comprises:
CaO:49.10%, SO
3: 3.54%, water-soluble P
2O
5: 0.01%, insoluble P
2O
5: 1.03%, Fe
2O
3: 1.74%, Al
2O
3: 3.24%, SiO
2%:4.68%, MgO:0.21%, loss on ignition (1000 ℃): 35.74%.
The calcining tail gas of discharging through drying machine in this step is handled by following step (10).
(6) bauxitic clay is dry
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) gets in the dryer, and is dry with the bauxitic clay countercurrent flow, removes its free-water, dried bauxitic clay.
(7) raw meal proportioning and homogenizing
The filter cake dry powder and the bauxitic clay of phosphogypsum dry powder, above-mentioned steps (5) gained are mixed by 13: 52: 35 (mass ratio); And the entering grinding machine grinds; Powder after this grinding is the raw material powder, send the raw material homogenizing storehouse to carry out homogenizing in the raw material powder, the raw material powder after the homogenizing; Its chemical constitution (mass percent) mainly comprises:
CaO:30.56%, SO
3: 7.67%, total phosphorus P
2O
5: 0.63%, Fe
2O
3: 2.18%, Al
2O
3: 23.04%, SiO
2: 5.57%, MgO:0.27%, TiO
2: 1.18%, loss on ignition (1000 ℃): 25.37%.
(8) clinker burning and cooling
Raw material powder after the homogenizing that above-mentioned steps (7) is made is sent in the rotary calciner and is calcined, and calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln, and the main reaction region temperature is 1250～1350 ℃, and material is at main reaction region residence time 45min; Reaction finishes after chilled air cools, fragmentation obtain grog, and its chemical composition (mass percent) mainly comprises:
CaO:39.78%, SO
3: 9.87%, total phosphorus P
2O
5: 0.81%, Fe
2O
3: 3.12%,
Al
2O
3：30.77％，SiO
2：9.63％，MgO：0.35％， TiO
2：1.52％；
Essential mineral mainly comprises (mass percent):
C
4A
3S：61.25％，C
2S：27.63％，C
2F：5.32％，CT：2.59％，Sf：1.91％
Cf：0.26％。
In this step, be used for filter cake is carried out the countercurrent flow drying in the drying machine of the calcining tail gas feeding step (5) that rotary calciner is discharged;
Be used for bauxitic clay is carried out the countercurrent flow drying in the dryer of the waste hot gas entering step (6) that when chilled air cools, produces.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) makes, add through dry modified modified phosphogypsum dry powder (CaSO
42H
2The O mass percent is not less than 92%, and the free-water mass percent is not more than 0.5%; 1% solution ph 6.5～8.0) carries out that modified (mass ratio is a grog: modified phosphogypsum dry powder=86.5: 13.5), and in homogenizing storehouse, carry out homogenizing, promptly become the quick hardening sulphoaluminate cement finished product.
Each item performance of gained quick hardening sulphoaluminate cement finished product satisfies the technical requirement of quick hardening sulphoaluminate cement (52.5 strength grade) in " aluminosulfate cement " (GB20472 2006), and it is following specifically to detect index:
Specific surface area: 368m
2/ kg the presetting period: 38min final setting time: 75min
Ultimate compression strength: 1d 44.2MPa 3d 58.4MPa 28d 62.8MPa
Folding strength: 1d 7.1MPa 3d 7.8MPa 28d 9.3MPa
(10) calcining vent gas treatment
The calcining tail gas that comes from the drying machine of above-mentioned steps (5) is through the laggard water wash column processing of lowering the temperature of going into of gathering dust; The control air outlet temperature is 40～45 ℃; Gas after cooling gets into ammonia and absorbs carbonating tower, and temperature is 35～40 ℃ in the control ammonia absorption carbonating tower, and ammonium carbon ratio (mol ratio) is n (NH in the liquid phase
4 +): n (CO
2)=2.2: 1, reaction obtains carbide ammonia solution after finishing, and allocates in the allotment dashpot of this carbide ammonia solution entering step (1); The ammonia-contaminated gas that goes out carbonating tower gets in the washing tower, removes a small amount of gas ammonia wherein with the phosphoric acid by wet process washing, emptying then (raw materials for production etc. that can be used as phosphoric acid salt or phosphate fertilizer by the phosphoric acid by wet process of part ammonification utilize again).
Mentioned each ratio or percentage etc. when being not specifically noted, all are meant mass ratio or mass percent among the present invention.
Claims (6)
1. the method for phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting, key step comprise that the condensing crystal of neutralization, ammoniumsulphate soln of phosphogypsum conversion, conversion product filtering separation, conversion fluid is dry, the modified grinding of drying, raw meal proportioning and homogenizing, clinker burning and cooling, grog of filter cake and aluminium vanadine and homogenizing, calcining vent gas treatment;
Described calcining vent gas treatment; Be that the calcining tail gas that the clinker burning process produces is recycled; The calcining tail gas that goes out rotary calciner is introduced in the drying plant filter cake is carried out the heat exchange drying; After reclaiming the heat cooling, get into ammonia again and absorb in the carbonating tower, carry out combination reaction with strong aqua and obtain carbide ammonia solution; Go out carbide ammonia solution that ammonia absorbs carbonating tower and meet the carbide ammonia solution that requires that feeds intake and participate in the phosphogypsum conversion reaction again, meet the carbonated aqueous ammonia that requires that feeds intake and be meant: NH wherein through being deployed into
4 +, CO
2, SO
3Mass percentage content be respectively: NH
4 +Content 8～12%, CO
2Content: 9～15%, SO
3Content: 0.5～5%; Go out ammonia-contaminated gas emptying after phosphoric acid by wet process or the washing of other acidic liq of ammonia absorption carbonating tower, utilized again by the phosphoric acid by wet process of part ammonification or other acidic liq;
Described each key step is specific as follows:
(1) phosphogypsum transforms
The carbonated aqueous ammonia that is absorbed carbonating tower by step (10) calcining vent gas treatment operation ammonia is introduced in the allotment dashpot; Be adjusted to its composition with volatile salt or bicarbonate of ammonia, ammonium sulfate, water and meet the carbonated aqueous ammonia that feeds intake and require, meet the carbonated aqueous ammonia that requires that feeds intake and be meant: NH wherein
4 +, CO
2, SO
3Mass percentage content be respectively: NH
4 +Content 8～12%, CO
2Content: 9～15%, SO
3Content: 0.5～5%, the carbonated aqueous ammonia after regulating and phosphogypsum butt are carried out the phosphogypsum conversion reaction, conversion reaction time 60～120min, 30～60 ℃ of temperature of reaction by the mass ratio of 1.7～2.2:1 in conversion tank; Reaction finishes, and must transform slip;
(2) conversion product filtering separation
Conversion slip to above-mentioned steps (1) gained carries out solid-liquid separation, gets filter cake and conversion fluid respectively; With water filter cake is carried out unidirectional or two-way washing, SO to the effluent
3Mass percentage content≤0.5%;
(3) neutralization of conversion fluid
With sulfuric acid with above-mentioned steps (2) filtering separation after the pH value of conversion fluid of gained be adjusted to 4.3～4.6, obtain ammoniumsulphate soln;
(4) the concentrating of ammoniumsulphate soln, crystallization, drying
The ammoniumsulphate soln that above-mentioned steps (3) neutralization is obtained concentrates, crystallization, drying, promptly gets the fertilizer grade ammonium sulfate product;
(5) filtration cakes torrefaction
The calcining tail gas of filter cake after above-mentioned steps (2) filtering separation and the washing and the discharge of step (8) rotary calciner is carried out the heat exchange drying to filter cake in drying plant, obtain filter cake dry powder;
Calcining tail gas after the cooling of discharging through drying plant and dust collection device in this step, vent gas treatment is calcined in (10) set by step;
(6) bauxitic clay is dry
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) gets in the drying plant, and is dry with the bauxitic clay heat exchange, dried bauxitic clay;
(7) raw meal proportioning and homogenizing
According to the chemical constitution in the sulphoaluminate cement clinker; The filter cake dry powder and the dried bauxitic clay of step (6) of phosphogypsum dry powder, above-mentioned steps (5) gained are mixed; And the entering grinding machine grinds; Powder after this grinding is the raw material powder, send the raw material homogenizing storehouse to carry out homogenizing in the raw material powder, the raw material powder after the homogenizing;
(8) clinker burning and cooling
Raw material powder after the homogenizing that above-mentioned steps (7) is made is sent in the rotary calciner and is calcined; Calcination process is controlled out 500～600 ℃ of calcining kiln calcining exhaust temperatures; The main reaction region temperature is 1250～1350 ℃, and material is at the main reaction region residence time 40～60min; After reaction finishes,, obtain grog through chilled air cools, fragmentation;
The calcining tail gas that rotary calciner is discharged in this step is used for filter cake is carried out the heat exchange drying in the drying plant of feeding step (5);
Be used for bauxitic clay is carried out the heat exchange drying in the drying plant of the waste hot gas entering step (6) that when chilled air cools, produces;
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) obtains, adding through dry modified modified phosphogypsum dry powder is grog by mass ratio: modified phosphogypsum dry powder=85～95:5～15 are carried out modified, and in homogenizing storehouse, carry out homogenizing, promptly become the quick hardening sulphoaluminate cement finished product;
(10) calcining vent gas treatment
The calcining tail gas that comes out from the drying plant of above-mentioned steps (5) is laggardly gone into the water wash column cooling and is handled through gathering dust; The control air outlet temperature is 30～50 ℃; Gas after cooling gets in the ammonia absorption carbonating tower and carries out combination reaction with strong aqua; It is 35～40 ℃ that control ammonia absorbs the interior liquidus temperature of carbonating tower, and ammonium carbon mol ratio is n (NH in the liquid phase
4 +): n (CO
2)=1.7～2.2:1, reaction obtains carbide ammonia solution after finishing, and allocates in the allotment dashpot of this carbide ammonia solution entering step (1); The ammonia-contaminated gas that goes out ammonia absorption carbonating tower gets in the washing tower, with phosphoric acid by wet process or other acidic liq washing back emptying, is utilized by the phosphoric acid by wet process of part ammonification or other acidic liq again.
2. the method for phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting, key step comprise that the condensing crystal of neutralization, ammoniumsulphate soln of phosphogypsum conversion, conversion product filtering separation, conversion fluid is dry, the modified grinding of drying, raw meal proportioning and homogenizing, clinker burning and cooling, grog of filter cake and aluminium vanadine and homogenizing, calcining vent gas treatment;
Described calcining vent gas treatment; Be that the calcining tail gas that the clinker burning process produces is recycled; The calcining tail gas that goes out rotary calciner is introduced in the drying plant filter cake is carried out the heat exchange drying; After reclaiming the heat cooling, get into ammonia again and absorb in the carbonating tower, carry out combination reaction with strong aqua and obtain carbide ammonia solution; Go out carbide ammonia solution that ammonia absorbs carbonating tower and meet the carbide ammonia solution that requires that feeds intake and participate in the phosphogypsum conversion reaction again, meet the carbonated aqueous ammonia that requires that feeds intake and be meant: NH wherein through being deployed into
4 +, CO
2, SO
3Mass percentage content be respectively: NH
4 +Content 8～12%, CO
2Content: 9～15%, SO
3Content: 0.5～5%; Go out ammonia-contaminated gas emptying after phosphoric acid by wet process or the washing of other acidic liq of ammonia absorption carbonating tower, utilized again by the phosphoric acid by wet process of part ammonification or other acidic liq;
Described each key step is specific as follows:
(1) phosphogypsum transforms
The carbonated aqueous ammonia that is absorbed carbonating tower by step (10) calcining vent gas treatment operation ammonia is introduced in the allotment dashpot; Be adjusted to its composition with volatile salt or bicarbonate of ammonia, ammonium sulfate, water and meet the carbonated aqueous ammonia that feeds intake and require, meet the carbonated aqueous ammonia that requires that feeds intake and be meant: NH wherein
4 +, CO
2, SO
3Mass percentage content be respectively: NH
4 +Content 8～12%, CO
2Content: 9～15%, SO
3Content: 0.5～5%, the carbonated aqueous ammonia after regulating and phosphogypsum butt are carried out the phosphogypsum conversion reaction, conversion reaction time 60～120min, 30～60 ℃ of temperature of reaction by the mass ratio of 1.7～2.2:1 in conversion tank; Reaction finishes, and must transform slip;
(2) conversion product filtering separation
Conversion slip to above-mentioned steps (1) gained carries out solid-liquid separation, gets filter cake and conversion fluid respectively; With water filter cake is carried out unidirectional or two-way washing, SO to the effluent
3Mass percentage content≤0.5%;
(3) neutralization of conversion fluid
With sulfuric acid with above-mentioned steps (2) filtering separation after the pH value of conversion fluid of gained be adjusted to 4.3～4.6, obtain ammoniumsulphate soln;
(4) the concentrating of ammoniumsulphate soln, crystallization, drying
The ammoniumsulphate soln that above-mentioned steps (3) neutralization is obtained concentrates, crystallization, drying, promptly gets the fertilizer grade ammonium sulfate product;
(5) filtration cakes torrefaction
The calcining tail gas of filter cake after above-mentioned steps (2) filtering separation and the washing and the discharge of step (8) rotary calciner is carried out the heat exchange drying to filter cake in drying plant, obtain filter cake dry powder;
Calcining tail gas after the cooling of discharging through drying plant and dust collection device in this step, vent gas treatment is calcined in (10) set by step;
(6) bauxitic clay is dry
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) gets in the drying plant, and is dry with the bauxitic clay heat exchange, dried bauxitic clay;
(7) raw meal proportioning and homogenizing
According to the chemical constitution in the sulphoaluminate cement clinker; Is (0～13) with the filter cake dry powder and the dried bauxitic clay of step (6) of phosphogypsum dry powder, above-mentioned steps (5) gained by mass ratio: (52～70): (30～35) are mixed; And the entering grinding machine grinds; Powder after this grinding is the raw material powder, send the raw material homogenizing storehouse to carry out homogenizing in the raw material powder, the raw material powder after the homogenizing;
(8) clinker burning and cooling
Raw material powder after the homogenizing that above-mentioned steps (7) is made is sent in the rotary calciner and is calcined; Calcination process is controlled out 500～600 ℃ of calcining kiln calcining exhaust temperatures; The main reaction region temperature is 1250～1350 ℃, and material is at the main reaction region residence time 40～60min; After reaction finishes,, obtain grog through chilled air cools, fragmentation;
The calcining tail gas that rotary calciner is discharged in this step is used for filter cake is carried out the heat exchange drying in the drying plant of feeding step (5);
Be used for bauxitic clay is carried out the heat exchange drying in the drying plant of the waste hot gas entering step (6) that when chilled air cools, produces;
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) obtains, adding through dry modified modified phosphogypsum dry powder is grog by mass ratio: modified phosphogypsum dry powder=85～95:5～15 are carried out modified, and in homogenizing storehouse, carry out homogenizing, promptly become the quick hardening sulphoaluminate cement finished product;
(10) calcining vent gas treatment
The calcining tail gas that comes out from the drying plant of above-mentioned steps (5) is laggardly gone into the water wash column cooling and is handled through gathering dust; The control air outlet temperature is 30～50 ℃; Gas after cooling gets in the ammonia absorption carbonating tower and carries out combination reaction with strong aqua; It is 35～40 ℃ that control ammonia absorbs the interior liquidus temperature of carbonating tower, and ammonium carbon mol ratio is n (NH in the liquid phase
4 +): n (CO
2)=1.7～2.2:1, reaction obtains carbide ammonia solution after finishing, and allocates in the allotment dashpot of this carbide ammonia solution entering step (1); The ammonia-contaminated gas that goes out ammonia absorption carbonating tower gets in the washing tower, with phosphoric acid by wet process or other acidic liq washing back emptying, is utilized by the phosphoric acid by wet process of part ammonification or other acidic liq again.
3. method according to claim 1 and 2 is characterized in that: in the described step (2), adopt diaphragm filter press that the conversion slip of step (1) gained is carried out press filtration, thereby make solid-liquid separation.
4. method according to claim 1 and 2 is characterized in that: in the described step (4), adopt that economic benefits and social benefits concentrate, the method for vacuum crystallization, fluidized drying, the ammoniumsulphate soln that neutralization obtains to step (3) concentrates, crystallization, drying.
5. method according to claim 1 and 2 is characterized in that: in the described step (5), adopt the countercurrent flow desiccating method in drying plant, filter cake to be carried out the heat exchange drying.
6. method according to claim 1 and 2 is characterized in that: in the described step (6), adopt the countercurrent flow desiccating method in drying plant, bauxitic clay to be carried out the heat exchange drying.
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| CN102303874B (en) * | 2011-08-08 | 2013-09-25 | 云南省化工研究院 | Method for preparing ammonium sulfate by conversion of phosphogyspum with polycrystalline method |
| CN103395803A (en) * | 2013-08-01 | 2013-11-20 | 瓮福（集团）有限责任公司 | Production method for powdery ammonium sulfate |
| CN106348316A (en) * | 2016-08-25 | 2017-01-25 | 太仓市新星轻工助剂厂 | Preparation method of ammonium sulfate |
| CN106365478B (en) * | 2016-09-23 | 2019-02-19 | 金正大生态工程集团股份有限公司 | A method of utilizing ardealite calcine by steps sulphate aluminium cement co-producing sulfuric acid |
| CN106430132A (en) * | 2016-11-04 | 2017-02-22 | 湖北三宁化工股份有限公司 | Method for preparing monopotassium phosphate and co-product ammonium sulfate by circulation method |
| CN109780856A (en) * | 2019-01-04 | 2019-05-21 | 贵州芭田生态工程有限公司 | A method of calcining phosphorus ore kiln exhaust gas is for drying phosphorus concentrate powder |
| CN112225228B (en) * | 2020-09-29 | 2024-07-19 | 长沙中硅环保科技有限公司 | Method and system for preparing ammonium sulfate by using cement kiln tail waste gas and phosphogypsum |
| CN112279276B (en) * | 2020-10-13 | 2023-06-09 | 宜兴市宏丰化肥有限公司 | Agricultural harmless treatment process for industrial byproduct potassium salt |
| CN115949949B (en) * | 2022-12-29 | 2023-10-20 | 广东广业投资集团有限公司 | System and method for cooperatively drying and incinerating sludge by using household garbage |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258640A (en) * | 1998-12-30 | 2000-07-05 | 湖南化工研究院 | Gypsum process of producing potassium sulfate and cement |
| CN1279223A (en) * | 2000-07-19 | 2001-01-10 | 张民乾 | Process for preparing ammonium sulfate and CO2 gas fertilizer from plaster in small N-fertilizer plant |
| CN101302001A (en) * | 2008-05-23 | 2008-11-12 | 河南未来铝业（集团）有限公司 | Production method of producing sulfuric acid cogeneration concrete using flur-gypsum |
-
2009
- 2009-02-28 CN CN2009103006174A patent/CN101481222B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258640A (en) * | 1998-12-30 | 2000-07-05 | 湖南化工研究院 | Gypsum process of producing potassium sulfate and cement |
| CN1279223A (en) * | 2000-07-19 | 2001-01-10 | 张民乾 | Process for preparing ammonium sulfate and CO2 gas fertilizer from plaster in small N-fertilizer plant |
| CN101302001A (en) * | 2008-05-23 | 2008-11-12 | 河南未来铝业（集团）有限公司 | Production method of producing sulfuric acid cogeneration concrete using flur-gypsum |
Non-Patent Citations (1)
| Title |
|---|
| 宋廷寿等.用磷石膏烧成硫铝酸盐水泥的研究.《水泥》.1999,(第4期),1-4. * |
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