CN101481222A - 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 PDF

Info

Publication number
CN101481222A
CN101481222A CNA2009103006174A CN200910300617A CN101481222A CN 101481222 A CN101481222 A CN 101481222A CN A2009103006174 A CNA2009103006174 A CN A2009103006174A CN 200910300617 A CN200910300617 A CN 200910300617A CN 101481222 A CN101481222 A CN 101481222A
Authority
CN
China
Prior art keywords
drying
ammonia
phosphogypsum
homogenizing
calcining
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2009103006174A
Other languages
Chinese (zh)
Other versions
CN101481222B (en
Inventor
杨守明
陈维贵
蒲中云
张勇
谢素龙
钟显刚
罗万林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN HONGDA CO Ltd
Original Assignee
SICHUAN HONGDA CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SICHUAN HONGDA CO Ltd filed Critical SICHUAN HONGDA CO Ltd
Priority to CN2009103006174A priority Critical patent/CN101481222B/en
Publication of CN101481222A publication Critical patent/CN101481222A/en
Application granted granted Critical
Publication of CN101481222B publication Critical patent/CN101481222B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)

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

The method of phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting
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 main component 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: 14.518%.
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 diaspore, volume density 2.23.2g/cm 3, its chemical constitution (mass percent) generally includes: 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 the 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 the selected quality that enters the production system phosphogypsum with raising, could guarantee higher phosphogypsum transformation efficiency and quality product, increased 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 carry out metathetical and must be used for the multiple fertile required intermediates Zhao potassium-ammonium sulfate solution and the flow process of ammonium chloride solution of producing of NPK with Repone K, its weak point: after 1. phosphogypsum need be handled through rinsing, enter 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 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 solution used in the present invention is as follows:
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, be carbonated and a small amount of sulphur that the clinker burning process is produced, the waste gas of oxynitride etc. (promptly calcining tail gas) 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 the cooling of recovery heat is gathered dust, enter the water wash column purification of further lowering the temperature, entering ammonia again absorbs 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 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 and absorb ammonia-contaminated gas emptying after phosphoric acid by wet process or the washing of other acidic liquid of carbonating tower, recycling by the phosphoric acid by wet process of part ammonification or other acidic liquid, 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 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, 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%), carbonated aqueous ammonia after regulating and phosphogypsum butt (the phosphogypsum butt is meant the phosphogypsum that does not contain free-water) are carried out the phosphogypsum conversion reaction by the mass ratio of 1.7～2.2:1 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 by following formula:
X two (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 liquid 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 byproduct 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 by drying machine in this step can be calcined vent gas treatment by following step (10).
(6) bauxitic clay drying
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) enters in the drying plant, with bauxitic clay heat exchange drying (can preferably adopt the countercurrent flow drying), 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% and essential mineral to form (mass percent) 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 enter grinding machine and grind, 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;
The waste hot gas that produces when chilled air cools enters in the drying plant of step (6) and is used for bauxitic clay is carried out the heat exchange drying.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) obtains, add the modified modified phosphogypsum dry powder of drying (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 carry out homogenizing in homogenizing storehouse, promptly become the quick hardening sulphoaluminate cement finished product.
Every 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 enters 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 obtains carbide ammonia solution after reaction finishes, and this carbide ammonia solution enters in the allotment dashpot of step (1) and allocates; The ammonia-contaminated gas that goes out ammonia absorption carbonating tower enters in the washing tower, washs a small amount of gas ammonia of removing wherein, emptying then with phosphoric acid by wet process or other acidic liquid; Raw materials for production that be 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 liquid etc. utilize again.
Compared with prior art, the invention has the beneficial effects as follows:
1, by 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, save 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 enters phosphate fertilizer or phosphate production system.Because heat energy and carbonic acid gas that waste gas is taken out of are recycled, effectively reduced energy consumption, saved 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
The present invention is described in further detail below in conjunction with embodiment.
But this should 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 as follows respectively 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 the mass ratio of 2.19:1 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, SO3 content (mass percent) is 0.42% o'clock in the mensuration scrub stream fluid, 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 by drying machine in this step is handled by following step (10).
(6) bauxitic clay drying
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) enters in the dryer, with bauxitic clay countercurrent flow drying, 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 enter grinding machine and grind, 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, calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln, 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;
The waste hot gas that produces when chilled air cools enters in the dryer of step (6) and is used for bauxitic clay is carried out the countercurrent flow drying.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) makes, add the modified modified phosphogypsum dry powder (CaSO of drying 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 carry out homogenizing in homogenizing storehouse promptly becomes the quick hardening sulphoaluminate cement finished product.
Every 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 as follows specifically to detect index:
Specific surface area: 362m 2/ kg the presetting period: 35min final setting time: 80min
Ultimate compression strength: 1d42MPa 3d 53.5MPa 28d 61.4MPa
Folding strength: 1d6.8MPa 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 ℃, gas through cooling enters ammonia absorption carbonating tower, and 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 obtains carbide ammonia solution after reaction finishes, and this carbide ammonia solution enters in the allotment dashpot of step (1) and allocates; The ammonia-contaminated gas that goes out carbonating tower enters in the washing tower, removes wherein a small amount of gas ammonia with phosphoric acid by wet process washing, emptying then (raw materials for production etc. that be 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 the mass ratio of 1.89:1 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 by drying machine in this step is handled by following step (10).
(6) bauxitic clay drying
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) enters in the dryer, with bauxitic clay countercurrent flow drying, 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 enter grinding machine and grind, 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, calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln, 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;
The waste hot gas that produces when chilled air cools enters in the dryer of step (6) and is used for bauxitic clay is carried out the countercurrent flow drying.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) makes, add the modified modified phosphogypsum dry powder (CaSO of drying 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 carry out homogenizing in homogenizing storehouse promptly becomes the quick hardening sulphoaluminate cement finished product.
Every 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 as follows specifically to detect index:
Specific surface area: 360m 2/ kg the presetting period: 38min final setting time: 75min
Ultimate compression strength: 1d43MPa 3d 54.2MPa 28d 63.5MPa
Folding strength: 1d6.6MPa 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 enters ammonia and absorbs 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)=1.92:1 obtains carbide ammonia solution after reaction finishes, and this carbide ammonia solution enters in the allotment dashpot of step (1) and allocates; The ammonia-contaminated gas that goes out carbonating tower enters in the washing tower, removes wherein a small amount of gas ammonia with phosphoric acid by wet process washing, emptying then (raw materials for production etc. that be 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 the mass ratio of 1.87:1 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 by drying machine in this step is handled by following step (10).
(6) bauxitic clay drying
The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) enters in the dryer, with bauxitic clay countercurrent flow drying, 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 enter grinding machine and grind, 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, calcination process is controlled out 500～600 ℃ of the calcining exhaust temperatures of calcining kiln, 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;
The waste hot gas that produces when chilled air cools enters in the dryer of step (6) and is used for bauxitic clay is carried out the countercurrent flow drying.
(9) modified, grinding of grog and homogenizing
In the grog that above-mentioned steps (8) makes, add the modified modified phosphogypsum dry powder (CaSO of drying 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 carry out homogenizing in homogenizing storehouse promptly becomes the quick hardening sulphoaluminate cement finished product.
Every 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 as follows specifically to detect index:
Specific surface area: 368m 2/ kg the presetting period: 38min final setting time: 75min
Ultimate compression strength: 1d44.2MPa 3d 58.4MPa 28d 62.8MPa
Folding strength: 1d7.1MPa 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 enters ammonia and absorbs 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)=2.2:1 obtains carbide ammonia solution after reaction finishes, and this carbide ammonia solution enters in the allotment dashpot of step (1) and allocates; The ammonia-contaminated gas that goes out carbonating tower enters in the washing tower, removes wherein a small amount of gas ammonia with phosphoric acid by wet process washing, emptying then (raw materials for production etc. that be 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 per-cent etc. when being not specifically noted, all are meant mass ratio or mass percent among the present invention.

Claims (8)

  1. The method of [claim 1] phosphogypsum preparing sulphoaluminate cement by-product ammonia sulfate by partly converting, key step comprise the modified grinding of drying, raw meal proportioning and homogenizing, clinker burning and cooling, grog of condensing crystal drying, filter cake and aluminium vanadine of neutralization, ammoniumsulphate soln of phosphogypsum conversion, conversion product filtering separation, conversion fluid and homogenizing, calcining vent gas treatment;
    Described calcining vent gas treatment, 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, entering ammonia again absorbs 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 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 liquid of ammonia absorption carbonating tower, recycling by the phosphoric acid by wet process of part ammonification or other acidic liquid.
  2. [claim 2] method according to claim 1 is characterized in that:
    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, carbonated aqueous ammonia after regulating and phosphogypsum butt are carried out the phosphogypsum conversion reaction by the mass ratio of 1.7～2.2:1 in conversion tank, conversion reaction time 60～120min, 30～60 ℃ of temperature of reaction; 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, mass percentage content≤0.5% of SO3 to the effluent liquid;
    (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 by drying plant and dust collection device in this step, (10) calcine vent gas treatment set by step;
    (6) bauxitic clay drying
    The waste hot gas that produces when the chilled air cools high temperature chamotte from step (8) enters in the drying plant, with bauxitic clay heat exchange drying, 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 enter grinding machine and grind, 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);
    The waste hot gas that produces when chilled air cools enters in the drying plant of step (6) and is used for bauxitic clay is carried out the heat exchange drying;
    (9) modified, grinding of grog and homogenizing
    Adding the modified modified phosphogypsum dry powder of drying in the grog that above-mentioned steps (8) obtains is grog by mass ratio: modified phosphogypsum dry powder=85～95:5～15 are carried out modified, and carry out homogenizing in homogenizing storehouse, 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 enters 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, ammonium carbon mol ratio is n (NH4+): n (CO2)=1.7～2.2:1 in the liquid phase, obtain carbide ammonia solution after reaction finishes, this carbide ammonia solution enters in the allotment dashpot of step (1) and allocates; The ammonia-contaminated gas that goes out ammonia absorption carbonating tower enters in the washing tower, and is with phosphoric acid by wet process or other acidic liquid washing back emptying, recycling by the phosphoric acid by wet process of part ammonification or other acidic liquid.
  3. [claim 3] method according to claim 2, it is characterized in that: in the described step (1), meet the carbonated aqueous ammonia that requires that feeds intake and be meant: wherein the mass percentage content of NH4+, CO2, SO3 is respectively: NH4+ content 8～12%, CO2 content: 9～15%, SO3 content: 0.5～5%.
  4. [claim 4] method according to claim 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.
  5. [claim 5] method according to claim 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.
  6. [claim 6] method according to claim 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.
  7. [claim 7] method according to claim 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.
  8. [claim 8] method according to claim 2, it is characterized in that: in the described step (7), be (0～13) with the filter cake dry powder and the dried bauxitic clay of step (6) of phosphogypsum dry powder, step (5) gained by mass ratio: (52～70): (30～35) are mixed.
CN2009103006174A 2009-02-28 2009-02-28 Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum Expired - Fee Related CN101481222B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009103006174A CN101481222B (en) 2009-02-28 2009-02-28 Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009103006174A CN101481222B (en) 2009-02-28 2009-02-28 Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum

Publications (2)

Publication Number Publication Date
CN101481222A true CN101481222A (en) 2009-07-15
CN101481222B CN101481222B (en) 2012-03-14

Family

ID=40878539

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009103006174A Expired - Fee Related CN101481222B (en) 2009-02-28 2009-02-28 Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum

Country Status (1)

Country Link
CN (1) CN101481222B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303874A (en) * 2011-08-08 2012-01-04 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
CN106365478A (en) * 2016-09-23 2017-02-01 金正大生态工程集团股份有限公司 Method for simultaneously producing sulphate aluminum cement and sulfuric acid through segmented calcination of phosphorus gypsum
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
CN112225228A (en) * 2020-09-29 2021-01-15 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
CN112279276A (en) * 2020-10-13 2021-01-29 宜兴市宏丰化肥有限公司 Agricultural harmless treatment process for industrial byproduct potassium salt
CN115949949A (en) * 2022-12-29 2023-04-11 广东广业投资集团有限公司 System and method for household garbage collaborative drying incineration of sludge

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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
CN1176049C (en) * 2000-07-19 2004-11-17 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

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303874A (en) * 2011-08-08 2012-01-04 云南省化工研究院 Method for preparing ammonium sulfate by conversion of phosphogyspum with polycrystalline method
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
CN106365478A (en) * 2016-09-23 2017-02-01 金正大生态工程集团股份有限公司 Method for simultaneously producing sulphate aluminum cement and sulfuric acid through segmented calcination of phosphorus gypsum
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
CN112225228A (en) * 2020-09-29 2021-01-15 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
CN112279276A (en) * 2020-10-13 2021-01-29 宜兴市宏丰化肥有限公司 Agricultural harmless treatment process for industrial byproduct potassium salt
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
CN115949949A (en) * 2022-12-29 2023-04-11 广东广业投资集团有限公司 System and method for household garbage collaborative drying incineration of sludge
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

Also Published As

Publication number Publication date
CN101481222B (en) 2012-03-14

Similar Documents

Publication Publication Date Title
CN101481222B (en) Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum
CN107056102B (en) System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash
CN103771734B (en) A kind of mass-producing calcination processing utilizes the method for electrolytic manganese residues
TWI567048B (en) A method for producing a cement composition
CN106904849A (en) The system and method that a kind of utilization Industrial Solid Waste produces sulphate aluminium cement co-producing sulfuric acid
CN100595154C (en) Method for extracting aluminum oxide from fly ash and coproducing cement by carbide slag or cyanamide slag
CN101028935B (en) Method for extracting aluminum hydrate or alumina from coal gangue and method for producing cement from fag end
CN101434403A (en) Novel method for processing calx sodica sintered alumina by dry method
CN103466661B (en) One kind utilizes potassium feldspar calcium sulfate mineralising CO2The method of co-producing sulfuric acid potassium
CN103738988B (en) Industrial waste residue resource is utilized to prepare the method for slag making sweetening agent
CN211770962U (en) System for preparing sulphoaluminate cement by using all solid wastes of aluminum ash pretreatment
CN110803878A (en) Device and method for producing II type anhydrous gypsum by using phosphogypsum
CN108821686A (en) A kind of preparation method and product of aluminium calcium carbonate composite gelled material
CN111233356A (en) Method and system for preparing sulphoaluminate cement from all solid waste of aluminum ash pretreatment
CN112570419B (en) Aluminum ash recycling method, harmless aluminum ash and application of harmless aluminum ash
CN109809456A (en) A kind of system and method for coal gasification collaboration gypsum calcining coproduction calcium oxide and sulphur
CN105130220B (en) With discarded concrete and the method for sludge eco-cement and active sand
CN106669962B (en) A kind of application method for the beneficiation method of the siliceous phosphorus ore of calcareous or calcium, ore-sorting system and ore-sorting system
CN105217986A (en) By the method for novel dry-process rotary kiln line process waste gypsum producing building terra alba
CN109160744A (en) Red mud magnetizing roast utilization system and technique
CN115286266B (en) Carbon-negative clinker prepared from phosphogypsum and preparation method of carbon-negative clinker
CN110963721B (en) Method for producing active admixture by utilizing dry-process cement plant transformation treatment manganese slag
CN106630701A (en) Method for preparing sulphoaluminate cement by calcining ardealite by steps
US2528103A (en) Method of producing sulfuric acid and hydraulic cement from gypsum
CN103880044A (en) Method for preparing potassium carbonate by adopting potash feldspar powder

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120314

Termination date: 20180228

CF01 Termination of patent right due to non-payment of annual fee