CN106431031A - Phosphogypsum sulphoaluminate cement sulfuric acid coproduction method - Google Patents
Phosphogypsum sulphoaluminate cement sulfuric acid coproduction method Download PDFInfo
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- CN106431031A CN106431031A CN201610842991.7A CN201610842991A CN106431031A CN 106431031 A CN106431031 A CN 106431031A CN 201610842991 A CN201610842991 A CN 201610842991A CN 106431031 A CN106431031 A CN 106431031A
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- Prior art keywords
- sulphate aluminium
- ardealite
- cement
- sulfuric acid
- aluminium cement
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a phosphogypsum sulphoaluminate cement sulfuric acid coproduction method; wherein, phosphogypsum replacing completely limestone and natural gypsum, after being ground and homogenized with bauxite and anthracite culm, at 1250-1300 DEG C, calcinating and resulting in the sulphoaluminate cement. The exploitation rate of phosphogypsum in the method is increased to a large extent; high concentration of sulfur dioxide tail gas through absorption is prepared into sulfuric acid. The hardening speed of sulphoaluminate cement clinker is quick, the intensity of sulphoaluminate cement is high during the former and later phase, performance test shows that the mechanical strength of the sulphoaluminate cement prepared by the method accords with the standard of sulphoaluminate cement.
Description
Technical field：
The invention belongs to the technical field of cement material, is related to prepare sulfur with phosphorous chemical industry trade waste ardealite as raw material
The method of aluminate cement.
Background technology：
With the modernization of engineering technology, to the technical requirements of special cement also more and more higher.Including special engineering
All there are special requirement, the such as connection construction of cement pipeline to rapid condensation with the speed that hardens and each phase hardness during construction,
Construction of the Foundation Fieldbus field of Large-Scale Equipment etc..Although but application and the continuous expansion of selling market, because product cost relatively
High and be restricted, so that more users is unable to reach.On the other hand, as three big production of phosphate fertilizer states in the world it
One, restricted by ardealite impurity index and application technology, it is difficult to realize large utilization, huge phosphate fertilizer industry leaves 300,000,000
Ton industrial by-product ardealite, about 70,000,000 tons of annual discharge capacity, about 17,000,000 tons of utilization, utilization rate less than 30%,
Become the bottleneck of phosphate ＆ compound fertilizer industry sustainable development.How sulphate aluminium cement is prepared using by-product ardealite, have become as
One of emphasis of domestic and international researcher research.
Chinese patent document CN1401604A discloses a kind of processing technology of quick hardening sulphoaluminate cement, and this technique is with life
Material proportioning is dehydrated phosphogypsum 17-20%, limestone 45-52%, Alumina 31-35%, and this technique is successfully using waste material phosphorus stone
Cream instead of the natural gypsum in raw-meal ingredient, can partly reduce the cost of sulphate aluminium cement, but ardealite in technique
Usage amount only accounts for the 17-20% of raw-meal ingredient, in addition it is also necessary to the limestone of 45-52%, does not reach effectively utilizes ardealite
Purpose, in addition in technique, the decomposition of ardealite can discharge sulfur dioxide, improper conduct oneself well to comprehend cause environmental pollution.
Chinese patent document CN103304170A discloses a kind of method for producing sulphate aluminium cement, by limestone, phosphorus
Gypsum Fibrosum, low-grade bauxite and coke are configured to cement slurry by a certain percentage, calcine at high temperature, forge after grinding is mixed
By promoting ardealite decomposition as much as possible during burning, decompose the calcium oxide for generating and replace part limestone, sulfur dioxide
Gas can be collected and prepare sulphuric acid, and this processing compound is limestone 30-60 part, ardealite 25-55 part, low-grade bauxite 15-45
Part, successfully the natural gypsum can be instead of using waste material ardealite, suitably reduce the cost of cement.But ardealite is not taken completely
For limestone, in raw-meal ingredient, still there is the limestone of up to 30-60 part, the carbon dioxide that decomposition of limestone is generated can be significantly dilute
Release the concentration of sulfur dioxide so that the cost of preparing sulfuric acid by using sulfur dioxide and difficulty increase.
Chinese patent document CN101481222A discloses a kind of ardealite Partial Conversion sulphate aluminium cement by-product sulfur
The method of sour ammonium, key step include ardealite conversion, conversion product be separated by filtration, the neutralization of conversional solution, ammonium sulfate dense
Contracting crystallizing and drying, the drying of filter cake and aluminum vanadine, raw meal proportioning and homogenizing, clinker burning and cooling, grog are quenched, grinding and all
Change, calcine vent gas treatment etc..Sulphate aluminium cement is met by the ardealite Partial Conversion to being not required to pretreatment and produces institute
The compound of dispensing requirements is needed, additional limestone is not required to again, expanded the range of application of ardealite.But this technique is needed first by phosphorus stone
Cream is converted into Calcium Carbonate and then carries out raw-meal ingredient and calcining again, and equipment needed thereby and technological process are all complex, production cost
High.
Content of the invention：
For problem present in the preparation of current sulphate aluminium cement, the present invention is provided one kind and can be taken using ardealite completely
For the natural gypsum and limestone, and can be by the aluminium sulfate production method of recovery tail gas co-producing sulfuric acid, and process route is simple,
Low production cost, with good economy and environmental benefit.
Summary of the invention
The present invention is with ardealite, bauxite, anthracite as raw material, and high-temperature calcination after dispensing, grinding, homogenizing is made ripe
Material, gained grog can add the natural gypsum or limestone prepares different types of sulphate aluminium cement, also can not additional natural stone
Cream, directly obtains sulphate aluminium cement.
Detailed description of the invention
Technical scheme is as follows：
A kind of method of utilization ardealite sulphate aluminium cement co-producing sulfuric acid is as follows including step：
A. the preparation of cement slurry：
Dispensing is carried out according to following mass parts：Ardealite is 65-80 part, bauxite 20-32 part, anthracite 3-5 part；Will be each
Component is mixed, and obtains cement slurry after grinding homogenizing；
B. the preparation of clinker：
By the cement slurry of step a preparation in 1250～1300 DEG C, 30-40 minute is calcined, clinker is obtained, calcined
The SO 2 tail gas for producing in journey send into sulphuric acid preparation system after collecting, and prepare sulphuric acid；
C. the preparation of cement：
By clinker regrinding obtained in step b, that is, obtain sulphate aluminium cement.
, according to the invention it is preferred to, in step a, after each component grinding, fineness is 120-180 mesh；
Preferably, Al in described bauxite2O3Mass fraction is 50-60%, further preferred 55%；
Preferably, described ardealite is half water ardealite.
, according to the invention it is preferred to, dispensing is carried out according to following mass parts in step a：Ardealite is 70-75 part, aluminum vitriol
Native 18-25 part, anthracite 3-4 part.
, according to the invention it is preferred to, the calcining described in step b is carried out in rotary kiln, shaft kiln or tunnel cave, further
It is preferred that carrying out in rotary kiln.SO 2 tail gas collection is prepared the process of sulphuric acid, by prior art.
, according to the invention it is preferred to, in step c, clinker is ground to specific surface area for 300～400m2/ kg, further
It is preferred that 350m2/kg.
According to the present invention, the clinker that step b is obtained can add the natural gypsum as requested, make different types of sulfur
Aluminate cement.
The amount of allocating of the natural gypsum is calculated as follows：
CG=0.13*M*AC/S
CGThe mass fraction ratio of clinker (natural gypsum with) that the natural gypsum is mixed, if clinker be；
ACIn clinkerMass fraction；
SO in the S natural gypsum3Mass fraction；
M natural gypsum coefficient, natural gypsum dosage difference in different sulphate aluminium cements, M value difference, M value
Scope is between 0-4.
In different sulphate aluminium cements, M value is as follows：
Early strong, high-strength sulphate aluminium cement M value：0-1；Intumescent sulphate aluminium cement M value：1-2；Seif-citing rate type
Sulphate aluminium cement M value：2-4；Low alkalinity type sulphate aluminium cement M value：2.5-3.0.
The present invention is substituted the natural gypsum and limestone completely with ardealite, passes through by adjusting cement raw mix proportioning mode
Calcium sulfate in ardealite is reduced into sulfur dioxide and calcium oxide by anthracite, and sulfur dioxide is oxidized to absorb Sulphuric acid product,
The calcium oxide of production, bauxite and unreduced calcium sulfate make sulphate aluminium cement through high temperature sintering.
Cement slurry of the present invention is in high-temperature burning process, and most of ardealite is decomposed under anthracite effect, point
Solution rate is 70-85%, and the calcium sulfate decomposition generation calcium oxide for wherein participating in decomposition reaction can all replace limestone, decompose and produce
Concentration of SO 2 gas be 7-9%, can be used for produce sulphuric acid；Remaining undecomposed ardealite is converted after high-temperature calcination
For high temperature Gypsum Fibrosum, the natural gypsum of outer admixture needed for alternative grog product.
Main chemical reactions of the present invention are as follows：
300 DEG C of raw material dehydration of room temperature, including mechanical water and water of crystallization；
300 DEG C of 450 DEG C of ardealites are changed into anhydrous gypsum；
450 DEG C of 600 DEG C of bauxites are decomposed to form α-Al2O3, in material, there is α-SiO2And Fe2O3；
600℃—900℃ α-Al2O3、α-SiO2And Fe2O3Continue to increase；
900 DEG C of 1150 DEG C of ardealites reduction generate CaO and SO2, 3CaO 3Al2O3·CaSO4With 2CaO Al2O3·
SiO2Formed and progressively accumulate；The absorbance of free calcium oxide reaches 1/2, α-Al2O3、α-SiO2And CaSO4Content reduce rapidly；
1150℃—1250℃ 3CaO·3Al2O3·CaSO4Continue to increase, free CaO and 2CaO Al2O3·SiO2Disappear
Lose, 4CaO 2SiO CaSO occur at 1250 DEG C4Mineral, the now mineral composition of sample is mainly 3CaO 3Al2O3·
CaSO4、4CaO·2SiO·CaSO4、β-2CaO·SiO2, Free Ca SO4With a small amount of iron phase；
1250℃—1300℃ 4CaO·2SiO·CaSO4Disappear, resolve into α -2CaO SiO2With Free Ca SO4, this
When grog essential mineral 3CaO 3Al2O3·CaSO4, 2CaO SiO2And calcium sulfate, also a small amount of iron phase, common aluminium sulfate
Clinker is formed completely；
1300 DEG C 1400 DEG C clinker no significant changes；
The solid slag that heretofore described ardealite is produced when referring in phosphoric acid production with sulfuric acid treating phosphorite, different
The ardealite that technique is obtained is used equally to the present invention.
The invention has the advantages that：
1st, other method that using ardealite prepare sulphate aluminium cement is compared, and in the present invention, ardealite can substitute stone completely
Lime stone and the natural gypsum carry out clinkersintering, greatly improve the utilization rate of ardealite, it is achieved that ardealite recycling, and
Effectively reduce the cost of sulphate aluminium cement.
2nd, in raw material, anthracite is added to promote the decomposition reaction of most of calcium sulfate in ardealite, undecomposed ardealite
The sulphate component that a part is formed as calcium sulphoaluminate in cement clinker mineral, another part can be used to replace outside clinker
The natural dihydrate gypsum component that mixes, can be directly produced sulphate aluminium cement.
3. due to not using limestone in dispensing, so the concentration of SO 2 gas height that decomposing ardealite is produced, can
Meet requirement of the acid making system to sulfur dioxide concentration, make sulfur dioxide effectively utilizes, it is to avoid the pollution problem of sulfur dioxide.
4. the sulphoaluminate cement clinker that the present invention is obtained can be applicable to produce the differences such as hard soon, high-strength, expansion, low alkalinity
The sulphate aluminium cement of species.
Specific embodiment：
With reference to specific embodiment, the present invention is described in further detail, but not limited to this.
In following embodiment, ardealite is taken from big two water of Nuo Taier Chemical Co., Ltd., the half water law Wetting of Nintaus
The semi-hydrated gypsum of phosphoric acid by-product, its main component is shown in Table 1, and bauxite takes from Guizhou, and its main component is shown in Table 2.
Table 1：The main component and content of ardealite
| Component | CaO | SO3 | Fe2O3 | Al2O3 | SiO2 |
| Content % | 36.96 | 52.63 | 0.15 | 0.57 | 1.97 |
Table 2：The main composition of bauxite and content
| Component | CaO | Fe2O3 | SiO2 | Al2O3 | SO3 |
| Content % | 3.84 | 9.86 | 21.28 | 55.45 | / |
Embodiment 1：
Dispensing is carried out according to following mass fraction：65 parts of ardealite, 32 parts of bauxite, 3 parts of anthracite；Again by each component powder
It is 120 mesh, to obtain cement slurry that mill is mixed to fineness；The cement slurry for preparing is placed in rotary kiln and is calcined at 1300 DEG C
30 minutes, clinker is obtained, the tail gas after calcining containing sulfur dioxide send sulphuric acid preparation system, prepares sulphuric acid；The cement for burning till
Grog regrinding is to 350m2After/Kg, you can obtain sulphate aluminium cement product, the mechanical property of gained sulphate aluminium cement
It is shown in Table 3.
Embodiment 2：
Dispensing is carried out according to following mass fraction：68 parts of ardealite, 28 parts of bauxite, 4 parts of anthracite；Again by each component powder
It is 150 mesh, to obtain cement slurry that mill is mixed to fineness；The cement slurry for preparing is placed in rotary kiln and is calcined at 1300 DEG C
40 minutes, clinker is obtained, the tail gas after calcining containing sulfur dioxide send sulphuric acid preparation system, prepares sulphuric acid；The cement for burning till
Grog regrinding is to 350m2After/Kg, you can obtain sulphate aluminium cement product, the mechanical property of gained sulphate aluminium cement
It is shown in Table 3.
Embodiment 3：
Dispensing is carried out according to following mass fraction：73 parts of ardealite, 22 parts of bauxite, 5 parts of anthracite；Again by each component powder
It is 180 mesh, to obtain cement slurry that mill is mixed to fineness；The cement slurry for preparing is placed in rotary kiln and is calcined at 1300 DEG C
30 minutes, clinker is obtained, the tail gas after calcining containing sulfur dioxide send sulphuric acid preparation system, prepares sulphuric acid；The cement for burning till
To 350m after grog regrinding2/ Kg, you can obtain sulphate aluminium cement product, the mechanical property of gained sulphate aluminium cement
It is shown in Table 3.
Embodiment 4：
Dispensing is carried out according to following mass fraction：80 parts of ardealite, 20 parts of bauxite, 5 parts of anthracite；Again by each component powder
It is 180 mesh, to obtain cement slurry that mill is mixed to fineness；The cement slurry for preparing is placed in rotary kiln and is calcined at 1250 DEG C
40 minutes, clinker is obtained, the tail gas after calcining containing sulfur dioxide send sulphuric acid preparation system, prepares sulphuric acid；The cement for burning till
To 350m after grog regrinding2/ Kg, you can obtain sulphate aluminium cement product, the mechanical property of gained sulphate aluminium cement
It is shown in Table 3.
Embodiment 1-4 result：
Understand from data table 3, met using the mechanical property of the sulphate aluminium cement of the inventive method sintering
The standard of sulphate aluminium cement in GB20472-2006.
Table 3：Sulphate aluminium cement glue sand mechanical property
Claims (10)
1. a kind of method of utilization ardealite sulphate aluminium cement co-producing sulfuric acid, as follows including step：
A. the preparation of cement slurry：
Dispensing is carried out according to following mass parts：Ardealite is 65-80 part, bauxite 20-32 part, anthracite 3-5 part；By each component
Mix, after grinding homogenizing, obtain cement slurry；
B. the preparation of clinker：
By the cement slurry of step a preparation in 1250～1300 DEG C, 30-40 minute is calcined, clinker is obtained, in calcination process
The SO 2 tail gas of generation send into sulphuric acid preparation system after collecting, and prepare sulphuric acid；
C. the preparation of cement：
By clinker regrinding obtained in step b, that is, obtain sulphate aluminium cement.
2. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
In rapid a, after each component grinding, fineness is 120-180 mesh.
3. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
Al in bauxite described in rapid a2O3Mass fraction is 50-60%.
4. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
Al in bauxite described in rapid a2O3Mass fraction is 55%.
5. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
Ardealite described in rapid a is half water ardealite.
6. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
Dispensing is carried out according to following mass parts in rapid a：Ardealite is 70-75 part, bauxite 18-25 part, anthracite 3-4 part.
7. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
Calcining described in rapid b is carried out in rotary kiln, shaft kiln or tunnel cave.
8. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
In rapid c, clinker is ground to specific surface area for 300～400m2/kg.
9. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 1, it is characterised in that step
The clinker that rapid b is obtained makes different types of sulphate aluminium cement according to the amount of allocating interpolation natural gypsum is required as follows；
The amount of allocating of the natural gypsum is calculated as follows：
CG=0.13*M*AC/S
CGThe mass fraction ratio of clinker (natural gypsum with) that the natural gypsum is mixed, if clinker be；
ACIn clinkerMass fraction；
SO in the S natural gypsum3Mass fraction；
M natural gypsum coefficient, M span is between 0-4.
10. the method for utilization ardealite sulphate aluminium cement co-producing sulfuric acid according to claim 9, it is characterised in that
In different sulphate aluminium cements, M value is as follows：
Early strong, high-strength sulphate aluminium cement M value：0-1；Intumescent sulphate aluminium cement M value：1-2；Seif-citing rate type sulfur aluminum
Acid salt cement M value：2-4；Low alkalinity type sulphate aluminium cement M value：2.5-3.0.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107056102A (en) * | 2017-03-17 | 2017-08-18 | 山东卓联环保科技有限公司 | A kind of system and method for utilization desulfurated plaster and aluminium ash production sulphate aluminium cement coproduction sulphur |
| CN108485517A (en) * | 2018-07-03 | 2018-09-04 | 贵州大学 | A kind of technique of red mud and ardealite relieving haperacidity coproduction heat resistant powder coating |
| CN112358212A (en) * | 2020-11-02 | 2021-02-12 | 荆州三迪建筑科技有限公司 | Comprehensive utilization method of phosphogypsum |
| CN115010334A (en) * | 2022-07-01 | 2022-09-06 | 武汉理工大学 | Method for dealkalizing red mud by using phosphogypsum |
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| CN103304170A (en) * | 2013-06-28 | 2013-09-18 | 重庆大学 | Method for producing sulphate aluminum cement |
| CN105129744A (en) * | 2015-07-21 | 2015-12-09 | 湖北湖大天沭新能源材料工业研究设计院有限公司 | Pre-heating decomposition method of producing sulfuric acid from phosphogypsum with co-production of cement |
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| CN103304170A (en) * | 2013-06-28 | 2013-09-18 | 重庆大学 | Method for producing sulphate aluminum cement |
| CN105129744A (en) * | 2015-07-21 | 2015-12-09 | 湖北湖大天沭新能源材料工业研究设计院有限公司 | Pre-heating decomposition method of producing sulfuric acid from phosphogypsum with co-production of cement |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056102A (en) * | 2017-03-17 | 2017-08-18 | 山东卓联环保科技有限公司 | A kind of system and method for utilization desulfurated plaster and aluminium ash production sulphate aluminium cement coproduction sulphur |
| CN107056102B (en) * | 2017-03-17 | 2020-01-24 | 山东卓联环保科技有限公司 | System and method for producing sulphoaluminate cement and co-producing sulfur by utilizing desulfurized gypsum and aluminum ash |
| CN108485517A (en) * | 2018-07-03 | 2018-09-04 | 贵州大学 | A kind of technique of red mud and ardealite relieving haperacidity coproduction heat resistant powder coating |
| CN112358212A (en) * | 2020-11-02 | 2021-02-12 | 荆州三迪建筑科技有限公司 | Comprehensive utilization method of phosphogypsum |
| CN115010334A (en) * | 2022-07-01 | 2022-09-06 | 武汉理工大学 | Method for dealkalizing red mud by using phosphogypsum |
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