CN106966617B - Easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker method - Google Patents
Easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker method Download PDFInfo
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- CN106966617B CN106966617B CN201710213779.9A CN201710213779A CN106966617B CN 106966617 B CN106966617 B CN 106966617B CN 201710213779 A CN201710213779 A CN 201710213779A CN 106966617 B CN106966617 B CN 106966617B
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- raw material
- sulphur
- belite
- aluminium sulfate
- ferrous aluminate
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- 239000004568 cement Substances 0.000 title claims abstract description 54
- 239000005864 Sulphur Substances 0.000 title claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 46
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 37
- 239000004411 aluminium Substances 0.000 title claims abstract description 36
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 33
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 21
- 239000010440 gypsum Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 74
- 235000012241 calcium silicate Nutrition 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910001570 bauxite Inorganic materials 0.000 claims description 16
- 239000002893 slag Substances 0.000 claims description 11
- 239000003818 cinder Substances 0.000 claims description 8
- 229910052683 pyrite Inorganic materials 0.000 claims description 8
- 239000011028 pyrite Substances 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 6
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 235000019738 Limestone Nutrition 0.000 abstract description 5
- 239000006028 limestone Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 13
- 238000005303 weighing Methods 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 4
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- -1 sulphur ferrous aluminate Chemical class 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IKRJXOIEFBYOAX-UHFFFAOYSA-L [O-]S([O-])(=O)=O.OS(O)(=O)=O.S.[Fe+2] Chemical compound [O-]S([O-])(=O)=O.OS(O)(=O)=O.S.[Fe+2] IKRJXOIEFBYOAX-UHFFFAOYSA-L 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- PZIBOVBPVADPBS-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Si+4].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Si+4].S(=O)(=O)([O-])[O-] PZIBOVBPVADPBS-UHFFFAOYSA-J 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/40—Dehydrating; Forming, e.g. granulating
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of firing belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker methods, include the following steps: step a, industrial residue is mixed with industrial gypsum, it is 0.3~0.5 plus water mixing by the ratio of mud, slurry is poured into mold after 15~60min of grinding, it is demoulded after molding, obtains sample.Step b, by said sample thermostatic curing, curing temperature is 60~150 DEG C, and curing time is 3~9h；80~130 DEG C of curing temperature in the step b, curing time are 3~6h.Step c takes out calcined sample then at 60~120min is calcined at 800~1150 DEG C from high temperature furnace, cooling rapidly；Product is obtained after grinding.Calcination condition is preferred: calcination temperature is 1050 DEG C, calcination time 120min.The present invention does not use lime stone, will not generate a large amount of carbon dioxide, increases environmental pressure, another aspect calcination temperature is low, and then low energy consumption.Therefore the present invention is a kind of low-carbon, green preparation method.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of easy fired belite-aluminium sulfate-sulphur iron aluminium
Hydrochlorate-sulphur calcium silicate cement clinker preparation method and its product.
Background technique
The world today is developing rapidly, and people become more concerned with us and rely while material life is improved
The earth of existence, as the maximum construction material of dosage --- cement plays emphatically progress of human society and socio-economic development
While acting on, the high energy and resource consumption and greenhouse gas emission, usual normal portland cement, oxidation are also produced
Calcium content is about 66%, and 50~70% alite mineral, i.e. about 1450 DEG C of the formation temperature of tricalcium silicate are accounted in clinker.It should
Mineral contain calcium oxide up to 73.7%, CaCO3It decomposes energy consumption and accounts for 46% or so of clinker theory heat consumption, lead to common portland cement
The energy consumption of sinter leaching is high；Belite mineral, i.e. dicalcium silicate, temperature be higher than 1250 DEG C at can quickly be formed, therefore can compared with
It is formed under low kiln temperature, in addition, belite is 65.1% containing CaO, the CaO content lower than in alite 73.7%, then institute
Lime stone amount is needed to reduce, caused energy consumption and carbon emission also accordingly reduce therefrom, and early hydration rate is low；Anhydrous sulphur aluminium
Hydrochlorate mineral (3CaO3SiO2·CaSO4), CaO content low (36.8%) and formation temperature are low (1300 DEG C) in composition, and with
C2S-sample has energy conservation and low CO2The characteristics of discharge, and the mineral have the characteristics that raising is early strong, due toCrystal structure
In there are multiple ducts, mineral have biggish solid solution capacity, and aluminium can replace to form sulphur ferrous aluminate by iron, can reduce aluminum-containing mineral
Usage amount start both at home and abroad to reduce energy consumption in cement production process and carbon dioxide gas discharge
Research to low aluminium or high silicon sulphate aluminium cement.
In recent years, people have studied calcium ion in calcium sulphoaluminate and are replaced by barium and strontium ion, and what aluminium was replaced by iron ion
Research is very few, and the formation of sulphur calcium aluminoferrite is generally at 1200 DEG C or more.The existing method for preparing sulphur calcium silicates, such as application number
For 201510066039.8 Chinese patent application, a kind of sulphate aluminium cement is disclosed, calcination temperature and guarantor according to setting
The warm time need to carry out secondary clacining；Application No. is 201510066040.0 Chinese patent applications, disclose a kind of sulphur calcium silicates
Preparation method, calcination temperature be 1100~1250 DEG C, keep the temperature 2~8h.It is secondary that aforesaid way has the following deficiencies that (1) need to carry out
Calcining, program is complicated, and calcination temperature is high for the first time；(2) soaking time needed for is long, and energy consumption is big.It can develop a kind of primary
The cement containing sulphur calcium silicates and sulphur ferrous aluminate of low temperature synthesis can not only overcome above-mentioned technique in the prior art multiple
Deficiency miscellaneous, energy consumption is high, and can be realized being effectively treated for waste residue, it is the project for being worth this field research.
Summary of the invention
Goal of the invention: an easy fired belite-aluminium sulfate-sulphur iron aluminic acid-sulphur calcium silicate cement of the invention is ripe
Material solves environmental problem caused by high energy consumption and industrial residue in existing cement production process are accumulated.
Technical solution: firing belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker of the present invention
Method, include the following steps:
Step a mixes industrial residue with industrial gypsum, is 0.3~0.5 plus water mixing by the ratio of mud, and grinding 15~
Slurry is poured into mold after 60min, is demoulded after molding, sample is obtained.
Step b, by said sample thermostatic curing, curing temperature is 60~150 DEG C, and curing time is 3~9h；The step
80~130 DEG C of curing temperature in b, curing time are 3~6h.
Step c takes out calcined sample then at 60~120min is calcined at 800~1150 DEG C from high temperature furnace,
It is cooling rapidly；Product is obtained after grinding.Calcination condition is preferred: calcination temperature is 1050 DEG C, calcination time 120min.
The present invention is there are also a kind of alternative solution: the step a, step b being replaced are as follows: by industrial residue, industry
Gypsum is mixed with waste material containing hydrated product, by 0.1~0.2 plus water mixing, is uniformly mixed molding, is obtained sample, then subsequent steps
c。
Specifically, the industrial gypsum is desulfurized gypsum or ardealite for above two scheme.
The industrial residue includes sa raw material, calcareous raw material, ferriferous raw material, iron aluminum raw material；Wherein sa
Raw material is gangue；Aluminum raw material is tailing bauxite；Calcareous raw material is carbide slag, lime dewatered sludge；Ferriferous raw material is sulphur
Iron ore slag；Iron aluminum raw material is red mud.
The waste material containing hydrated product is silico-calcium aluminum raw material, such as residual slurry of tubular pile and discarded concrete fines.
More specifically, in above-mentioned steps raw material proportion are as follows: sa raw material or silicon calcareous raw material: iron aluminum raw material: aluminium
Matter raw material: industrial gypsum: calcareous raw material=9.74~20.69%:4.35~4.99%:27.88~41.77%:9.43~
13.68%:27.07~45.39%.
Grinding in above-mentioned steps, being milled to specific surface area is 350~420m2/kg。
It is found in research, hydro-thermal presoma of the present invention is larger to cement products Effect on Mechanical Properties, the present invention
The hydro-thermal reaction is that the sample after demoulding carries out thermostatic curing, optimal curing condition are as follows: curing temperature is 60~150
DEG C, curing time is 3~9h.Optimal calcination condition are as follows: calcination temperature is 1050 DEG C, calcination time 120min.
The utility model has the advantages that low temperature preparation belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker of the invention
Method belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker burning is reduced by preparatory hydro-thermal reaction
Temperature processed, reduces energy consumption, passes through the property suitably with when process improving belite-aluminium sulfate-sulphur ferrous aluminate cement
Can, realize the belite-aluminium sulfate for preparing low-carbon at low temperature -- sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
Invention is directly to make raw material using industrial residue, industrial gypsum, bauxite or tailing bauxite, industry
Contain CaO, SiO in waste residue2、Al2O3、Fe2O3And SO3, so raw material does not need modified or other processing, save processing cost
While the utilization rate of raw material that improves.Preceding period cost is greatly reduced, while solving environmental problem caused by industrial residue.
Also, the present invention does not use lime stone, will not generate a large amount of carbon dioxide, increases environmental pressure, another aspect calcination temperature
It is low, and then low energy consumption.Therefore the present invention is a kind of low-carbon, green preparation method.
Specific embodiment:
The present invention will be further described combined with specific embodiments below, and the component of raw material used in the present embodiment is such as
Shown in table 1.
1 raw material main chemical compositions (%) of table
| CaO | SiO2 | Al2O3 | Fe2O3 | SO3 | |
| Carbide slag | 65.57 | 4.27 | 2.56 | —— | 1.20 |
| Lime dewatered sludge | 50.48 | 6.10 | 1.45 | 0.67 | —— |
| Gangue | 1.44 | 58.00 | 17.66 | 5.23 | 1.70 |
| Desulfurized gypsum | 30.90 | 2.50 | 2.73 | 3.03 | 44.00 |
| Ardealite | 28.67 | 4.11 | 0.62 | —— | 40.53 |
| Red mud | 7.00 | 9.00 | 17.00 | 39.00 | —— |
| Pyrite cinder | 0.60 | 5.75 | 1.19 | 38.36 | 0.60 |
| Tailing bauxite | 0.48 | 8.30 | 39.05 | 0.54 | —— |
| Residual slurry of tubular pile | 28.93 | 21.38 | 3.00 | —— | —— |
Embodiment 1
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 2.
Table 2: 1 raw material proportioning of embodiment and water consumption
| Embodiment 1 | Red mud | Gangue | Tailing bauxite | Desulfurized gypsum | Carbide slag | Water |
| Quality/g | 49.9 | 138.6 | 313.8 | 107.5 | 390.2 | 500 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 30min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) hydrothermal synthesis: said sample being placed in have warmed up to the pressure that set temperature is 130 DEG C and is steamed in kettle, thermostatic curing 3h
Cooling is taken out afterwards；
3) it calcines: after blocky sample after cooling is crushed, then being placed in high temperature furnace, calcine 120min at 1050 DEG C,
Chilling is taken out, ball mill grinding to specific surface area is 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur
Calcium silicate cement clinker.
It is as shown in table 3 to measure each performance of cement.
Table 3: belite-aluminium sulfate made from embodiment 1-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 2
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 4.
Table 4: 2 raw material proportioning of embodiment and water consumption
| Embodiment 2 | Pyrite cinder | Residual slurry of tubular pile | Tailing bauxite | Ardealite | Lime dewatered sludge | Water |
| Quality/g | 43.5 | 189.8 | 341.4 | 100 | 325.3 | 150 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 15min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) it calcines: blocky sample is placed in high temperature furnace again, 120min is calcined at 950 DEG C, take out chilling, ball mill powder
Being milled to specific surface area is 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 5 to measure each performance of cement.
Table 5: belite-aluminium sulfate made from embodiment 2-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 3
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 6.
Table 6: 3 raw material proportioning of embodiment and water consumption
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 40min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) hydrothermal synthesis: said sample is placed in and has warmed up the digital display constant temperature stirring circulatory maintenance for being 60 DEG C to set temperature
In case, cooling is taken out after thermostatic curing 9h；
3) it calcines: after blocky sample after cooling is crushed, then being placed in high temperature furnace, calcine 90min at 800 DEG C, take
Chilling out, ball mill grinding to specific surface area are 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur silicon
Sour calcium clinker.
It is as shown in table 7 to measure each performance of cement.
Table 7: belite-aluminium sulfate made from embodiment 3-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 4
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 8.
Table 8: 4 raw material proportioning of embodiment and water consumption
| Embodiment 4 | Pyrite cinder | Residual slurry of tubular pile | Tailing bauxite | Desulfurized gypsum | Carbide slag | Water |
| Quality/g | 47.9 | 125.9 | 417.7 | 123 | 285.5 | 200 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 60min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) it calcines: blocky sample is placed in high temperature furnace, 120min is calcined at 1000 DEG C, take out chilling, ball mill powder
Being milled to specific surface area is 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 9 to measure each performance of cement.
Table 9: belite-aluminium sulfate made from embodiment 4-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 5
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 10.
Table 10: 5 raw material proportioning of embodiment and water consumption
| Embodiment 5 | Pyrite cinder | Residual slurry of tubular pile | Tailing bauxite | Desulfurized gypsum | Carbide slag | Water |
| Quality/g | 47.4 | 206.9 | 372 | 100.4 | 273.3 | 100 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 30min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) it calcines: blocky sample is placed in high temperature furnace, 90min is calcined at 1050 DEG C, take out chilling, ball mill grinding
It is 390m to specific surface area2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 11 to measure each performance of cement.
Table 11: belite-aluminium sulfate made from embodiment 5-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 6
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 12.
Table 12: 6 raw material proportioning of embodiment and water consumption
| Embodiment 6 | Residual slurry of tubular pile | Pyrite cinder | Tailing bauxite | Ardealite | Carbide slag | Water |
| Quality/g | 205.2 | 47 | 369 | 108.1 | 270.7 | 150 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 30min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) it calcines: blocky sample is placed in high temperature furnace, 120min is calcined at 1150 DEG C, take out chilling, ball mill powder
Being milled to specific surface area is 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 13 to measure each performance of cement.
Table 13: belite-aluminium sulfate made from embodiment 6-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 7
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 14.
Table 14: 7 raw material proportioning of embodiment and water consumption
| Embodiment 7 | Gangue | Pyrite cinder | Tailing bauxite | Desulfurized gypsum | Lime dewatered sludge | Water |
| Quality/g | 97.4 | 44 | 339.1 | 112.9 | 406.6 | 500 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 15min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) hydrothermal synthesis: said sample being placed in have warmed up to the pressure that set temperature is 130 DEG C and is steamed in kettle, thermostatic curing 3h
After take out；
3) it calcines: sample is placed in high temperature furnace, 120min is calcined at 1050 DEG C, take out chilling, ball mill grinding is extremely
Specific surface area is 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 13 to measure each performance of cement.
Table 15: belite-aluminium sulfate made from embodiment 7-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 8
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 16.
Table 16: 8 raw material proportioning of embodiment and water consumption
| Embodiment 8 | Gangue | Red mud | Tailing bauxite | Ardealite | Carbide slag | Water |
| Quality/g | 108.7 | 48.3 | 357.4 | 136.8 | 348.8 | 500 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 15min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) hydrothermal synthesis: said sample being placed in have warmed up to the pressure that set temperature is 120 DEG C and is steamed in kettle, thermostatic curing 3h
After take out；
3) it calcines: blocky sample is placed in high temperature furnace, 90min is calcined at 1100 DEG C, take out chilling, ball mill grinding
It is 390m to specific surface area2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 17 to measure each performance of cement.
Table 17: belite-aluminium sulfate made from embodiment 8-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 9
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 18.
Table 18: 9 raw material proportioning of embodiment and water consumption
| Embodiment 9 | Gangue | Pyrite cinder | Tailing bauxite | Desulfurized gypsum | Lime dewatered sludge | Water |
| Quality/g | 121.7 | 44.6 | 294.5 | 94.3 | 444.9 | 500 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 15min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) hydrothermal synthesis: said sample being placed in have warmed up to the pressure that set temperature is 130 DEG C and is steamed in kettle, thermostatic curing 3h
After take out；
3) it calcines: blocky sample is placed in high temperature furnace, 120min is calcined at 1000 DEG C, take out chilling, ball mill powder
Being milled to specific surface area is 390m2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 19 to measure each performance of cement.
Table 19: belite-aluminium sulfate made from embodiment 9-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance table
Embodiment 10
Raw material proportioning and water consumption designed by the present embodiment are as shown in table 20.
Table 20: 10 raw material proportioning of embodiment and water consumption
| Embodiment 10 | Gangue | Red mud | Tailing bauxite | Desulfurized gypsum | Lime dewatered sludge | Water |
| Quality/g | 124.2 | 44.7 | 28.1 | 96.2 | 453.9 | 500 |
Specific implementation step is as follows:
1) mixing: weighing raw material according to the ratio and be placed in planetary mills, adds water, grinds 15min, slurry is poured into mold after taking-up
In, it is demoulded after molding, obtains blocky sample；
2) hydrothermal synthesis: said sample is placed in and has warmed up the digital display constant temperature stirring circulatory maintenance for being 80 DEG C to set temperature
In case, taken out after thermostatic curing 3h；
3) it calcines: blocky sample is placed in high temperature furnace, 120min is calcined at 900 DEG C, take out chilling, ball mill grinding
It is 390m to specific surface area2/ kg obtains belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker.
It is as shown in table 21 to measure each performance of cement.
Table 21: belite-aluminium sulfate made from embodiment 10-sulphur ferrous aluminate-sulphur calcium silicate cement clinker performance
Table
Comparative example
Using conventional method in the prior art, belite aluminium sulfate water is prepared using low aluminium slag and low-grade bauxite
Mud.Each specific ingredient of raw material is as shown in table 22.
The chemical component of 22 raw material of table
| Title | Loss on ignition | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | SO3 | K2O | Na2O | TiO2 |
| Lime stone | 43.4 | 0.21 | 0.18 | 0.03 | 55.22 | 0.3 | —— | —— | —— | —— |
| Bauxite | 20.7 | 31.84 | 46.08 | 1.95 | 0.74 | 0.34 | 0.13 | 0.53 | 0.06 | 3.08 |
| Ca-Al slag | 11.1 | 0.54 | 9.42 | 0.06 | 47.99 | 0.71 | 26.76 | 1.37 | 0.06 | —— |
| Gypsum | 20.7 | 9.56 | 2.34 | 0.79 | 36.29 | 2.25 | 39.10 | 0.55 | 0.37 | 0.13 |
Introduce basicity factor Cm, alumina silica ratio P and aluminium-sulfur ratio n carry out raw meal proportioning, are computed, list of ingredients is as shown in table 23.
Table 23 tests proportion scheme and clinker mineral composition
Weighing raw material, which is matched, by design 60min is kept the temperature at 1320 DEG C, effect is most through mixing, granulation, drying, calcining
It is good, chilling is taken out, cement is made by 92:8 mass mixing grinding in clinker and the natural gypsum.
The physical and mechanical property for measuring cement is as shown in table 24.
The physical and mechanical property of 24 cement of table
It can be seen that the present invention has very big advantage, present invention preparation side from 1~embodiment of embodiment 10 and comparative example
Method reduces calcination temperature, reduces energy consumption especially with hydro-thermal presoma containing hydrated calcium silicate and aquation aluminium sulfate
Advantage；Furthermore the present invention, without using raw mineral materials such as lime stone, clays, has saved resource, has promoted using industrial residue as raw material
The sustainable development of cement.
Claims (8)
1. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement clinker method, feature exist
In including the following steps:
Step a mixes industrial residue with industrial gypsum, is 0.3~0.5 plus water mixing by the ratio of mud, after grinding 15~60min
Slurry is poured into mold, is demoulded after molding, sample is obtained；
Step b, by said sample thermostatic curing, curing temperature is 60~150 DEG C, and curing time is 3~9h；
Step c takes out calcined sample, rapidly then at 60~120min is calcined at 800~1150 DEG C from high temperature furnace
It is cooling；Product is obtained after grinding；
The industrial residue includes sa raw material, calcareous raw material, ferriferous raw material, iron aluminum raw material；
The proportion of raw material in above-mentioned steps are as follows: sa raw material or silicon calcareous raw material: ferriferous raw material or iron aluminum raw material: aluminum
Raw material: industrial gypsum: calcareous raw material=9.74~20.69%:4.35~4.99%:27.88~41.77%:9.43~
13.68%:27.07~45.39%；
80~130 DEG C of curing temperature in the step b, curing time are 3~6h.
2. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement according to claim 1
The method of clinker, it is characterised in that replace the step a, step b are as follows: produce industrial residue, industrial gypsum with containing aquation
The mixing of object waste material is uniformly mixed molding, is obtained sample, then subsequent steps c by 0.1~0.2 plus water mixing；Described contains aquation
Product waste material is silico-calcium aluminum raw material.
3. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement according to claim 2
The method of clinker, it is characterised in that the silico-calcium aluminum raw material is residual slurry of tubular pile and discarded concrete fines.
4. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicates water according to claim 1 or 2
The method of mud clinker, it is characterised in that the industrial gypsum is desulfurized gypsum or ardealite.
5. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicates water according to claim 1 or 2
The method of mud clinker, it is characterised in that wherein sa raw material is gangue；Aluminum raw material is tailing bauxite；Calcareous raw material is
Carbide slag, lime dewatered sludge；Ferriferous raw material is pyrite cinder；Iron aluminum raw material is red mud.
6. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicate cement according to claim 2
The method of clinker, it is characterised in that the silico-calcium aluminum raw material is residual slurry of tubular pile or discarded concrete fines.
7. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicates water according to claim 1 or 2
The method of mud clinker, it is characterised in that the grinding in above-mentioned steps, being milled to specific surface area is 350~420m2/kg。
8. easy fired belite-aluminium sulfate-sulphur ferrous aluminate-sulphur calcium silicates water according to claim 1 or 2
The method of mud clinker, it is characterised in that calcination temperature is 1050 DEG C in the step c, calcination time 120min.
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| CN1868954A (en) * | 2006-06-01 | 2006-11-29 | 武汉理工大学 | Composite gelling material and its preparation method |
| CN104609434A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Preparation method and application method of calcium sulphosilicate mineral |
| CN104609750A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Sulphoaluminate cement and preparation method thereof |
| CN105060745A (en) * | 2015-08-14 | 2015-11-18 | 盐城工学院 | Belite-sulphoaluminate-ferrous aluminate cement and preparation method thereof |
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| CN1868954A (en) * | 2006-06-01 | 2006-11-29 | 武汉理工大学 | Composite gelling material and its preparation method |
| CN104609434A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Preparation method and application method of calcium sulphosilicate mineral |
| CN104609750A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Sulphoaluminate cement and preparation method thereof |
| CN105060745A (en) * | 2015-08-14 | 2015-11-18 | 盐城工学院 | Belite-sulphoaluminate-ferrous aluminate cement and preparation method thereof |
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