WO2015124044A1 - 快凝快硬高贝利特硫铝酸盐水泥熟料、应用及其生产工艺 - Google Patents

快凝快硬高贝利特硫铝酸盐水泥熟料、应用及其生产工艺 Download PDF

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WO2015124044A1
WO2015124044A1 PCT/CN2015/070457 CN2015070457W WO2015124044A1 WO 2015124044 A1 WO2015124044 A1 WO 2015124044A1 CN 2015070457 W CN2015070457 W CN 2015070457W WO 2015124044 A1 WO2015124044 A1 WO 2015124044A1
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cement
clinker
fast
cement clinker
setting
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PCT/CN2015/070457
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French (fr)
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张振秋
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唐山北极熊建材有限公司
张振秋
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Priority to EP15752713.6A priority Critical patent/EP3081546B1/en
Priority to KR1020167026463A priority patent/KR101917017B1/ko
Priority to US15/119,688 priority patent/US9822036B2/en
Publication of WO2015124044A1 publication Critical patent/WO2015124044A1/zh

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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
    • C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
    • C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/06—Oxides, Hydroxides
    • C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/10—Acids or salts thereof containing carbon in the anion
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/12—Acids or salts thereof containing halogen in the anion
    • C04B22/124—Chlorides of ammonium or of the alkali or alkaline earth metals, e.g. calcium chloride
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C04B28/065—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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
    • C04B28/186—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
    • C04B28/188—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0658—Retarder inhibited mortars activated by the addition of accelerators or retarder-neutralising agents
    • 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
    • C04B7/006—Cement-clinker used in the unground state in mortar - or concrete compositions
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • 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
    • C04B7/48—Clinker treatment
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/12—Set accelerators
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the field of building materials, and particularly relates to a quick-solidification high-hard belite sulphoaluminate cement clinker, an application of the clinker and a process of industrial production thereof.
  • High belite sulphoaluminate cement can absorb a large variety of industrial waste residue, and it is a very creative direction to use bauxite ore beneficiation as a raw material for aluminum and then use its industrial waste to prepare new cement materials. This will further enrich and improve the scope of application of its raw materials and the variety of high belite sulphoaluminate cement products, and has far-reaching significance.
  • Sulphoaluminate cement is a kind of special cement independently invented in China. Its main mineral is anhydrous calcium sulphoaluminate (C 4 A 3). And the dicalcium silicate (C 2 S), the former accounts for about 60-70%, the latter accounts for about 20-30%, because it has excellent early strength, high strength, micro-expansion, anti-freeze, impermeability, corrosion resistance, etc.
  • high belite sulphoaluminate cement Another important advantage of high belite sulphoaluminate cement is the ability to largely consume industrial waste such as fly ash and desulfurization gypsum, but the production of sulphoaluminate cement requires the use of high quality natural gypsum and bauxite. With the rapid development of China's industry, a large amount of industrial waste generated is put on hold or piled up, which not only seriously pollutes the environment, but also causes waste of resources. The potential of using these industrial wastes to prepare new high belite sulphoaluminate cement is great. For the energy saving and low-carbon production of the cement industry, it not only brings new development opportunities, but also has far-reaching effects.
  • Sulphoaluminate cement was invented by China Building Materials Science Research Institute and has a history of nearly 40 years.
  • the conventional sulphoaluminate cement clinker chemical composition Al 2 O 3 accounts for about 30%, and S i O 2 accounts for about 10%.
  • S i O 2 accounts for about 10%.
  • the intensity of the three days was reduced by about 10 MPa. It directly reflects the decrease of Al 2 O 3 content in clinker and the decrease of strength when S i O 2 increases. That is to say, the use of high-alumina low-silicon high-quality bauxite is the most high-quality sulphoaluminate cement.
  • Sulphoaluminate cement has the characteristics of early strength and high strength, but the late strength growth is not significant, and a large amount of high-quality bauxite, limestone and other natural resources are needed.
  • High belite sulphoaluminate cement can reduce bauxite and limestone.
  • Such natural resource quality indicators have the possibility of utilizing waste slag, but they are close to the performance of Portland cement, and do not have the excellent characteristics of quick-solidification, fast strength, early strength and high strength of sulphoaluminate cement.
  • the industrial production is a dream that the cement and construction industry at home and abroad have long expected and has not realized, and it is also a major technical problem in the field of cement industry at home and abroad.
  • the object of the present invention is to provide a quick-solidification fast hard high belite sulphoaluminate cement clinker, application and production process thereof.
  • f-CaO and CaSO 4 breaks through the bondage of the sulphoaluminate cement clinker ratio at home and abroad, and plays f-CaO, C 4 A 3
  • a new type of fast-setting, high-hard belite sulphoaluminate cement clinker with compressive strength of 2h23.5MPa, 4h 27.6MPa, 28d 73MPa, and mutual clinking effect of C 2 S and CaSO 4 Designing fast-solidifying and fast-hardening high-belite sulphoaluminate cement and its production process to reduce energy consumption and cost, reduce emissions, promote the development of circular economy, and produce high-energy, low-cost high-strength, fast-solid, fast-hardening Lit sulphoaluminate cement products.
  • a further technical problem to be solved in the application of the present invention is based on the activity in the clinker component and by means of f-CaO, C 4 A 3 in the hydration process.
  • the mutual excitation of CaSO 4 and the effective component of the post-added filler are strongly excited, so that the compressive strength of the prepared cement can reach 2h 25.6MPa, 7d 58.6MPa, 28d 92.7MPa, so that fast setting and fast hardening Performance, late strength, workability, antifreeze, corrosion resistance, impermeability and other high performance are fully utilized.
  • the invention relates to the correspondence between the Chinese name of the mineral composition and the chemical symbol: anhydrous calcium sulphoaluminate (C 4 A 3 ), dicalcium silicate (C 2 S), tetracalcium aluminoferrite (C 4 AF), perovskite (CT), free calcium oxide (f-CaO), feldspar (C 2 AS), lauric acid Twelve calcium (C 12 A 7 ).
  • w(f-CaO) w(CaO)-0.55[w(Al 2 O 3 )-0.64w(Fe 2 O 3 )]-1.87w(SiO 2 )-1.4w(Fe 2 O 3 )-0.7[ w(TiO 2 )+w(SO 3 )]
  • the technical means adopted by the present invention include the following contents:
  • the above clinker has the following mineral composition by weight: 20 to 35% C 4 A 3 3 to 9% C 4 AF, 37 to 47% C 2 S, 0.5 to 4.6% f-CaO, 14 to 26.3% CaSO 4 , and the balance is a mixed mineral component.
  • the balance of the above clinker is mineral content ⁇ 7%.
  • the balance of the mineral component in the above clinker includes MgO, or CaO.TiO 2 , or Na 2 SO 3 , or K 2 SO 3 , or a mixture of two or more of them.
  • the above cement clinker has the following chemical composition of weight percentage: 12.9 to 16.1% SiO 2 , 12 to 19% Al 2 O 3 , 1 to 3% Fe 2 O 3 , 49 to 54% CaO, and 12 to 18.43% SO. 3 , the balance is a mixed chemical composition.
  • the remaining chemical components in the above cement clinker include MgO, or TiO 2 , or Na 2 O, or K 2 O, or a mixture of two or more thereof.
  • the method includes the following steps:
  • Raw material prefabrication the raw material prepared in (1) is ground and homogenized to obtain a raw material of a prescribed fineness;
  • part or all of the limestone component raw materials are alkali slag, or steel slag, or calcium carbide slag, or a mixture of two or more of them, and the principle to be controlled is the CaO content in the clinker. Must be equivalent to 49 to 54%.
  • part or all of the fly ash component is bauxite, or bauxite tailings, or coal gangue, or kaolin, or boiling slag, or clay or both of them and two
  • the principle to be controlled is that the Al 2 O 3 content in the clinker must be equivalent to 12 to 19%.
  • desulfurized gypsum is natural anhydrite, or natural dihydrate gypsum, or desulfurized gypsum, or hemihydrate gypsum, or phosphogypsum, or aluminum sulfate or gypsum-rich industrial waste or two or two of them.
  • the principle to be controlled is that the SO 3 content in the mixture clinker is equivalent to 12 to 18.43%.
  • cement clinker selects fast-solidifying high-hard belite sulphoaluminate cement clinker, adjusts the coagulation, promotes the strength component to select anhydrite, and the filler selects slag;
  • the clinker used in cement includes the following mineral composition by weight: 20 to 35% C 4 A 3 3 to 9% C 4 AF, 37 to 47% C 2 S, 0.5 to 4.6% f-CaO, and 14 to 26.3% CaSO 4 .
  • the clinker used in cement includes the following chemical composition of weight percentage: 12.9 to 16.1% SiO 2 , 12 to 19% Al 2 O 3 , 1 to 3% Fe 2 O 3 , 49 to 54% CaO. , 12 ⁇ 18.43SO 3 .
  • the anhydrite component may be replaced in whole or in part by desulfurization gypsum, or natural dihydrate gypsum, or hemihydrate gypsum, or phosphogypsum, or fluorogypsum, or by replacing two or more mixtures of the above gypsums.
  • desulfurization gypsum or natural dihydrate gypsum, or hemihydrate gypsum, or phosphogypsum, or fluorogypsum, or by replacing two or more mixtures of the above gypsums.
  • disulfide in the alternative are the same.
  • slag can be used fly ash, or steel slag, or iron tailings sand, or limestone, or dolomite, or sandstone, or they The mixture is replaced in whole or in part, the principle of substitution being that the corresponding equivalents of dicalcium silicate and aluminum oxide in the alternative are the same.
  • the raw material of the kiln obtained in step 1 is calcined in a rotary kiln at 1300 ⁇ 50 ° C to obtain cement clinker, the mineral component comprises 0.5 ⁇ 4.6% f-CaO;
  • Preparation of cement According to the cement labeling requirements, select the clinker standard sample, according to the mixed batching test sheet, and refer to the proportion of step 2 in the above cement ratio grinding to formulate the small grinding fitting scheme, after the proportioning and small grinding experiments, according to The empirical data is used to weigh anhydrite, slag and cement clinker, and the mixture is ground to a specific surface area of ⁇ 450 m 2 /Kg to make cement.
  • citric acid is added to prolong the setting time and increase the late strength.
  • the lithium carbonate added to the above cement may be replaced by lithium hydroxide or lithium chloride in whole or in part.
  • the citric acid added to the above cement may be replaced by sodium citrate or sodium gluconate in whole or in part.
  • the inventor is constantly reducing the pressure of the cement based on the quick-setting and fast-hardening high-belite sulphoaluminate cement clinker, which is made up of cement clinker, condensate, strong component and filler.
  • the ratio of clinker usage it was found that the ratio of rapid setting, fast hardening and early strength of the cement in the initial phase did decrease, but it was formed by appropriate adjustment of the ratio of the condensing, strengthening and filler components.
  • the late strength of cement products has increased significantly.
  • the clinker cement with low clinker configuration should also be regarded as one of the application results of the present invention.
  • the quick-setting high-hard belite sulphoaluminate cement clinker selected in the compounding and grinding is 5%-12%, anhydrite 17%-18%, slag 71%-78%;
  • initial setting time is not more than 43 minutes
  • final setting time is not more than 53 minutes
  • 28 days bending strength 11.9-12.8Mpa
  • 28 days compressive strength 79-82.5Mpa
  • 28 days free expansion rate 0.10-0.12 %
  • 21 days expansion rate in air 0.001% - 0.002%
  • 28 days in water The expansion ratio is 0.017%-0.022%.
  • C 4 A 3 there are a large number of highly active C 4 A 3 in ordinary sulphoaluminate clinker.
  • the content is between 60% and 70%, and a small amount of f-CaO is enough to make the cement hydration harden too fast and quickly lose fluidity.
  • C 4 A 3 only 20% to 35% of the cement clinker minerals are C 4 A 3 .
  • C 2 S with very poor early strength is as high as 37 to 47%, and the promotion of f-CaO mineral is required to make the fast setting and fast performance of cement meet the application needs; on the other hand, a small amount of f- in the cement clinker of the invention
  • CaO mineral is calcined at a low temperature of 1300 ⁇ 50°C.
  • the crystal is fine, the structure is loose, and the activity is high. It will be fully hydrated during the hydration process, especially the small amount of f-CaO mineral hydration will be faster, so it does not exist. Late volume instability and poor stability; cement grinding with slag, or fly ash, or steel slag and other silicon-aluminum source materials, in the hydration reaction, f-CaO and slag, powder in cement clinker ash, Al slag provided 2 O 3, Fe 2 O 3 , SiO 2 and SO 3 in the raw cement clinker and gypsum is added after the reaction of SO 3 calcium sulfoaluminate hydrate, alumina gel, silica Calcium acid gel stimulates the activity of slag, fly ash and steel slag, improves the early strength of cement, and absorbs the expansion caused by f-CaO.
  • the cement produced by the above technical scheme shows a lot of experimental data: freedom Expansion rate 28d 0.11% ⁇ 0.37%, the fluctuation range is small; limit expansion The rate is 7d 0.005% ⁇ 0.040%, 28d 0.009% ⁇ 0.055%, and the air is -0.003 ⁇ 0.033% in 21d.
  • the expansion value is not large, the shrinkage value is small, and the difference between the water expansion and the dry shrinkage in the dry air is small; It is said that the cement has small volume deformation and excellent crack resistance and impermeability.
  • the present invention is the first to use calcium sulfate as one of the main minerals of cement clinker in industrial production.
  • calcium sulfate minerals contain 14% to 26.3%.
  • More CaSO 4 can improve the burnability of raw materials and reduce the firing temperature of clinker.
  • CaSO 4 will exist in liquid state at high temperature, increasing the liquid amount of cement clinker at firing temperature and enhancing the composition.
  • the relative diffusion speed between the other minerals makes the chemical reaction of the other minerals more rapid and thorough; the clinker is calcined in the dicalcium silicate and the tetracalcium iron aluminate to dissolve the sulfur trioxide to form a mineral solid solution, so that the silicic acid
  • the early activity of dicalcium and tetracalcium iron aluminate is greatly improved; calcium sulfate itself can be hydrated to form calcium sulfate dihydrate, which can also be coagulated and hardened; calcium sulfate can also be combined with another major mineral in the clinker, anhydrous sulphoaluminate. Calcium and water continue to react to form the early major hydration product ettringite, which enhances the fast-hardening performance of the cement.
  • the specific surface area of the cement is 450-500 m 2 /kg, and a large amount of conventional physical properties, durability, admixture adaptability, concrete, dry-mixed mortar and the like are applied and performance tests are performed, and the application range thereof is
  • the currently widely used sulphoaluminate cements are basically the same; compared with ordinary sulphoaluminate cements, the cement quick-solidification and fast-hardening characteristics of the present invention are more remarkable, such as compressive strength, "sulfur aluminate cement” GB 20472-2006 Only the 1-day-old compressive strength standard is proposed.
  • the actual test data given by the present invention proves that the cement can reach 25.6 MPa in 2 h; the micro-expansion and low-drying performance are more excellent; the coagulation hardening is fast, and the workability is good.
  • the surface layer does not have sand.
  • the beneficial effects produced by the above technical solutions are as follows: (1) The clinker selected for cement provided by the present invention breaks through the domestic and foreign sulphoaluminate cement clinker by creatively introducing more than the conventional limited amount of f-CaO and CaSO 4 .
  • the combination of mineral composition and ratio of raw materials provides a theoretical basis for the utilization of low-grade raw materials with high silicon and low aluminum, and for the manufacture of fast-setting, fast-hardening, early-strength, high-strength, high-strength, high-strength sulphoaluminate cement clinker;
  • the clinker burning temperature is lowered, the process temperature is lowered by 50 ° C, the energy consumption is reduced, the emission is reduced, and the production process environment is improved; (3) the cement produced by the clinker is in the hydration process.
  • the cement is quick-setting, fast, early strength, high expansion, micro-expansion, low-drying, anti-freezing, anti-seepage, anti-seawater corrosion performance; (4) cement clinker prepared by the technology and A large amount of waste residue is used in the cement process, and the utilization rate of waste residue is as high as 30% or more; (5) The raw material cost is low.
  • the continuation experiment proves that although the proportion of clinker is obviously reduced, although the early strength is affected by some effects, the compressive strength of the cement prepared by processing 28d can still reach 79-81Mpa, and the hydration exotherm is obviously low during the experiment.
  • the seawater has strong corrosion resistance and small dimensional change rate, which is very suitable for marine engineering applications and has strong market competitiveness.
  • the cement product produced by the above technical means does not need to be mixed with any admixture in the application, and only adopts the standardized process steps to adjust the cement clinker, adjust the coagulation, promote the strong component, and mix the filler to obtain various high marks.
  • Performance of the Bailey-type special sulphoaluminate cement Due to the mature production process control process, the equipment and sulfur-fixing process proved to be effective, the sintering temperature is significantly reduced, which is beneficial to reduce energy consumption, and the large-scale use of industrial waste is beneficial to the development of circular economy and the society that reduces costs. Benefits, indicating that the present invention is a major technological breakthrough in the field.
  • Figure 1 is a flow chart of a fast setting fast hard high belite sulphoaluminate cement clinker, cement, and its production process.
  • the production of clinker is based on 33-62% limestone, 10.5-28% fly ash and 19-45% desulfurization gypsum.
  • the mixing and grinding of cement is based on clinker 26%-97%. , anhydrite 3%-19%, slag 0%-55% for reference.
  • Examples 1 to 6 are raw material ratios.
  • the fly ash and the desulfurized gypsum do not enter the raw material mill, and directly enter the classifier, which greatly improves the production time of the raw material grinding system, and greatly reduces the power consumption and the ball consumption.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 6 limestone(%) 62.0 33.0 35.0 55.3 52.0 62.0
  • Fly ash (%) 13.5 24.0 20.0 25.7 28.0 10.5
  • Desulfurization gypsum (%) 24.5 43.0 45.0 19.0 20.0 27.5
  • step 2 Preparation of clinker:
  • the raw material obtained in step 1 is calcined at 1300 ⁇ 50° C. in a kiln decomposition kiln to obtain cement clinker.
  • a small amount of sulfur dioxide generated by the reducing atmosphere rises to the cyclone preheater with the flue gas, and further reacts with the incoming raw material to avoid the escape of sulfur dioxide.
  • the formation and emission of nitrogen oxides are reduced, which meets environmental protection requirements.
  • the initial setting time of the prepared clinker is less than 16min
  • the final setting time is no more than 40min
  • the early 2 hours compressive strength reaches 20.5Mpa, which has the property of fast setting and fast hardening, compressive strength and flexural strength ratio.
  • the sulphoaluminate cement clinker is higher.
  • the fast-hardening high-hard belite sulphoaluminate cement clinker contains C 4 A 3 as a mineral component.
  • C 4 AF, C 2 S, CaSO 4 the key is that the sulphoaluminate cement clinker also contains 0.5 to 4.6% f-CaO in the mineral component.
  • the mineral composition (wt%), chemical composition (wt%), batching p and Cm ratio values and physical properties of the cement clinker in the present embodiment are shown in Table 4, Table 5 and Table 6, respectively.
  • the compressive strength of cement clinker 28d prepared in this example reached 73 MPa, and no relevant reports were reported in the study of high belite sulphoaluminate cement clinker with low aluminum and high silicon composition.
  • Examples 17 to 35 give specific data on the composition of the fast setting fast hard high belite sulphoaluminate cement, and enumerate the main indicators in the technical performance test report of this example, forming a table 9-table 11.
  • the embodiment is based on the physical properties of the fast-setting fast-hardening high belite sulphoaluminate cement clinker.
  • the clinker of the embodiment 7 in Table 6 is used as the clinker of the cement of the examples 17 to 35, and according to the above cement production process Made of cement products.
  • step 3 slag and anhydrite or their substitute materials are added.
  • the chemical compositions of various gypsum and mixed materials used are shown in Table 7.
  • the cement ratio and physical properties of each example are shown in Table 8, Table 9, and Table. 10.
  • each table of Table 8, Table 9, and Table 10 is divided into left and right parts, and the top and bottom are arranged in order.
  • the test standard for limiting the expansion ratio is referred to "Concrete Expansion Agent” GB 23439-2009.
  • Table 8-A and Table 8-B are combined into Table 8 for a table of examples of fast setting fast hard high belite sulphoaluminate cement. Among them, Examples 20, 24, and 30 were separately added to the cement component as an additive.
  • Table 9-A and Table 9-B are combined into Table 9. Examples of the effect of cement on the technical properties of fast-hardening high-hard belite sulphoaluminate cement with the aid of admixtures, including coagulants or/and retarders table.
  • the influences formed by adding and mixing the admixtures respectively are combined and shown in Table 9. It can be seen that the present invention, if used in combination with an admixture, can produce unexpected technical effects. See the table below for details.
  • Table 10-A is combined with Table 10-B to form Table 10: Table of extended embodiment of fast setting fast hard high belite sulphoaluminate cement.
  • Table 10 Table of extended embodiment of fast setting fast hard high belite sulphoaluminate cement.
  • the proportions of the examples 33, 34, and 35 in the cement clinker application are significantly reduced.
  • the technical indicators of the early fast-setting quick-response have a significant influence, the strength of the cement in the late stage is remarkably improved, and the addition is not added.
  • the flexural strength can reach 11.9-12.8Mpa, and the compressive strength can reach 79.0-82.5Mpa.
  • the expansion expansion rate experiment proves that the late micro-expansion characteristics of the cement are still maintained. This leaves an opportunity to further expand the product variety and promote the application.
  • the anhydrite component may be replaced in whole or in part by desulfurization gypsum, or natural dihydrate gypsum, or hemihydrate gypsum, or phosphogypsum, or fluorogypsum, or by using two or more mixtures of the above gypsum;
  • the slag may be replaced in whole or in part by fly ash or steel slag, or iron tailings sand, or limestone, or dolomite, or sandstone or a mixture thereof.
  • the key issue is to have a substantial role in the application of different materials.
  • the equivalent of the equivalent component, the substitute for the gypsum is the equivalent of the condensed and promoted components, and the filler is considered the potential active ingredient.
  • the quick-setting and fast-hardening high belite sulphoaluminate cement can be added with lithium carbonate of not more than 0.30% to shorten the setting time and improve the early strength, and the added lithium carbonate can be used for all the hydrogen chloride and lithium chloride. Or partial replacement; a quick-setting fast hard high belite sulphoaluminate cement, which can be added with not more than 0.5% citric acid to prolong the setting time, improve the late strength, the added citric acid, can be used sodium citrate, Sodium gluconate is replaced in whole or in part.

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Abstract

一种快凝快硬高贝利特硫铝酸盐水泥熟料，涉及到快凝快硬高贝利特硫铝酸盐水泥熟料、应用及其生产工艺。该水泥熟料所含矿物组份中包括20～35％C4A3 s̅，3～9％C4AF，37～47％C2S，0.5～4.6％f-CaO，14～26.3％CaSO4；重量百分比的化学成分组成为：12.9～16.1％SiO2，12～19％Al2O3，1～3％Fe2O3，49～54％CaO，12～18.43％SO3；具体采用重量百分比为33～62％的石灰石、10.5～28％粉煤灰和19～45％脱硫石膏、在1300±50℃回转窑中煅烧而成。借助以上熟料26％-97％、硬石膏3％-19％、矿渣0％-55％混合研磨成各种标号的快硬、高强水泥产品。

Description

快凝快硬高贝利特硫铝酸盐水泥熟料、应用及其生产工艺 技术领域
本发明属于建筑材料领域，具体涉及快凝快硬高贝利特硫铝酸盐水泥熟料、该熟料的应用及其工业化生产的工艺过程。
背景技术
近几十年来，将早强较高的硫铝酸盐与C2S结合的高贝利特硫铝酸盐水泥由于同时具有低能耗、低碳排放、高性能的优点，成为目前研究的热点，国内很多大专院校、科研院所、生产企业对高贝利特硫铝酸盐水泥进行了大量的研究，取得了大量研究成果，但未见厂家大规模生产的报道。查阅国内的研究资料，以高贝利特硫铝酸盐水泥熟料中按照氧化物成分来看，Al2O3多在10％左右，SiO2多在20％左右，早期、晚期抗压强度均大大低于常规的硫铝酸盐水泥熟料。分析原因，这是由于高贝利特硫铝酸盐水泥熟料配料时，完全照搬了国内硫铝酸盐水泥熟料的配料理论，未能脱开碱度系数Cm＝1.0、铝硫比P＝3.82这两个理论率值的束缚。自然也难以采用高硅低铝之低品位原材料来生产出高强度高贝利特硫铝酸盐水泥熟料。然而，随着我国工业的快速发展，产生的大量工业废渣被搁置或者堆存，不仅严重污染环境，也造成资源的浪费。高贝利特硫铝酸盐水泥能够大量地消纳各种工业废渣，以铝土矿选矿尾矿用作铝制原料，再利用其工业废渣制备新型水泥材料实在是一个很有创意的方向。这对拓展其原料适用范围及高贝利特硫铝酸盐水泥产品品种上能起到进一步丰富和完善、具有意义深远。
另一方面，节能减排是国家的重要国策。建筑行业实现住宅产业化迫在眉睫，建筑住宅产业化核心技术之一是建筑的主要零部件梁、板、柱实现标准化设计和工厂化预制生产。预制构件生产中常规的作法是采用普通硅酸盐水泥，沿用蒸汽锅炉养护工艺，高能耗、高污染，工人劳动强度大，生产效率低。取消蒸养，尤其是以燃煤作燃料的蒸汽锅炉养护，实现建筑构件工厂自动化生产，提高生产效率，节能减排，实现建筑业的可持续发展，迫切需要一种低成本快凝快硬水泥。
硫铝酸盐水泥是我国自主发明的一种特种水泥，其主要矿物是无水硫铝酸钙(C4A3
Figure PCTCN2015070457-appb-000001
)和硅酸二钙(C2S)，前者约占60-70％，后者约占20-30％，因为其具有早强、高强、微膨胀、抗冻、抗渗、抗腐蚀等优异特性，在特种建筑材料、混凝土制品等特殊领域有独特应用，但生产硫铝酸盐水泥需要使用优质天然石膏和铝矾土，铝矾土的资源越来越稀缺，使得这种水泥成本和价格很高，在大型建筑工程中应用日益减少，很多硫铝酸盐水泥厂家经营 非常困难，这与国家提高特种水泥产量，大力发展特种水泥的战略方针相矛盾，因此研发生产低成本高性能硫铝酸盐水泥已经成为当前一项紧迫任务。近年来，高贝利特硫铝酸盐水泥由于具有低能耗、低碳排放等优点，成为目前研究的热点。高贝利特硫铝酸盐水泥的另一重要优势就是能够大量地消纳粉煤灰、脱硫石膏等工业废渣，但生产硫铝酸盐水泥需要使用优质天然石膏和铝矾土。随着我国工业的快速发展，所产生的大量工业废渣被搁置或者堆存，不仅严重污染环境，也造成资源的浪费，利用这些工业废渣制备新型高贝利特硫铝酸盐水泥的潜力很大，对于水泥工业的节能降耗、低碳生产，不仅带来了新的发展契机，而且必将产生深远的影响。
硫铝酸盐水泥由中国建材科学研究院发明，至今已有近40年历史。常规的硫铝酸盐水泥熟料化学成分Al2O3占30％左右，SiO2占10％左右。根据中国建材研究院水泥研究所的研究结果：对于C4A3
Figure PCTCN2015070457-appb-000002
/β-C2S比值80:20、60:40和40:60三组试样，三天强度大约依次降低了10MPa。直接体现了熟料中Al2O3成份减少、SiO2增加时，强度的成比例急剧下降，也就是说，采用高铝低硅优质铝矾土是生产优质硫铝酸盐水泥的最主要的技术途径，很多硫铝酸盐水泥厂家的长期生产数据也完全符合这个研究结果。研究采用低铝高硅铝矾土生产性能较好的硫铝酸盐水泥，多年来早已成为水泥界的热门课题，这种水泥由于β-C2S含量较高，业内称为高贝利特硫铝酸盐水泥。查阅国内的研究资料，高贝利特硫铝酸盐水泥熟料早期、晚期抗压强度均大大低于常规的硫铝酸盐水泥熟料，性能更接近于硅酸盐水泥，即不具备硫铝酸盐水泥快凝快硬特性。这是由于高贝利特硫铝酸盐水泥熟料配料时，完全照搬了国内硫铝酸盐水泥熟料的配料理论，未能脱开矿物成分组成和碱度系数Cm＝1.0、铝硫比P＝3.82这两个率值的束缚，自然也难以用高硅低铝低品位铝矾土生产出高强度高贝利特硫铝酸盐水泥熟料；缺乏成熟理论的支持导致长期以来对这方面的应用研究止步不前。因此，只有突破以上传统理论的束缚，才能实现以废渣和低品位原材料生产出优质的硫铝酸盐水泥的梦想变成现实。
美国的P.K.Mehta所研究的熟料在1980年5月的期刊“World CementTechnology”第166～177页和1978年7月/8月的期刊“World Cement Technology”第144～160页中披露：其组成基于硫铝酸钙C4A3
Figure PCTCN2015070457-appb-000003
“yee’limite”,含有20％的C4A3
Figure PCTCN2015070457-appb-000004
“yee’limite”、20％无水石膏、45％C2S和15％铁铝酸四钙C4AF，游离氧化钙f-CaO小于0.5％。该熟料与“TCS系列”，即中国的硫铝酸盐水泥的主要差别在于它们熟料组分中非常高的无水石膏，引用的熟料#5参考物也似乎符合CO2低工业排放的要求，且性能大致为现代波特兰水泥的那些性能，但Mehta所述的熟料从未在市场上出售，也没有任何实现产业化的相关报道。
法国拉法尔热公司在公布号为CN102745918A的专利中公布了一种高贝利特含量的硫铝酸盐熟料，以5-25％C2AXF(1-X)、15-35％C4A3
Figure PCTCN2015070457-appb-000005
40-75％C2S为主要矿物组成，同时在熟料煅烧时加入一些微量元素作为添加剂以确保水泥熟料的性能，以使部分C2S以α-C2S形态存在，从专利中提供的胶结料数据看，早期强度较低，晚期强度也不高。在性能指标上距高性能还是有较大的差距。
硫铝酸盐水泥具有早强高强等特性，但晚期强度增长不显著，又需要大量的优质铝矾土、石灰石等天然资源；高贝利特硫铝酸盐水泥虽然可以降低铝矾土、石灰石等天然资源品质指标，有利用废渣的可能性，但和硅酸盐水泥性能接近，不具备硫铝酸盐水泥快凝快硬、早强高强等优异特性。研发一种大量利用废渣、以低成本、低能耗、低排放、比硫铝酸盐水泥凝结更快、早期强度和晚期强度更高更具有实用价值的高性能高贝利特硫铝酸盐水泥的工业化生产，是国内外水泥及建筑界长期以来期待而没有实现的梦想，也是国内外水泥专业领域的一个重大的技术难题。
发明内容
本发明的目的在于提供一种快凝快硬高贝利特硫铝酸盐水泥熟料、应用及其生产工艺。借助创造性的在水泥熟料中引入适量的f-CaO和CaSO4，突破国内外硫铝酸盐水泥熟料配料率值的束缚，发挥f-CaO、C4A3
Figure PCTCN2015070457-appb-000006
C2S和CaSO4的相互激发作用，制备抗压强度2h23.5MPa、4h 27.6MPa、28d 73MPa的一种新型快凝快硬高贝利特硫铝酸盐水泥熟料，并进而借助熟料设计出快凝快硬高贝利特硫铝酸盐水泥及其生产工艺，实现降低能耗及成本、减少排放，促进循环经济发展，生产高新能、低成本的高强度快凝快硬高贝利特硫铝酸盐水泥产品。
本发明中在应用中进一步要解决的技术问题是，基于熟料成分中活性、并借助在水化过程中f-CaO、C4A3
Figure PCTCN2015070457-appb-000007
和CaSO4的相互激励、以及后加入的填充料中有效组分被强烈激发的作用，使制备的水泥的抗压强度能够达到2h 25.6MPa、7d 58.6MPa、28d 92.7MPa，使快凝快硬性能、晚期强度、和易性、抗冻、抗腐蚀、抗渗性等一切高优性能得以充分发挥。
本发明涉及矿物组成中文名称与化学符号的对应：无水硫铝酸钙(C4A3
Figure PCTCN2015070457-appb-000008
)、硅酸二钙(C2S)、铁铝酸四钙(C4AF)、钙钛矿(CT)、游离氧化钙(f-CaO)、钙黄长石(C2AS)、七铝酸十二钙(C12A7)。
本发明中矿物成份组成计算公式：
Figure PCTCN2015070457-appb-000009
w(C2S)＝2.87w(SiO2)
w(C4AF)＝3.04w(Fe2O3)
Figure PCTCN2015070457-appb-000010
w(CT)＝1.7w(TiO2)
w(f-CaO)＝w(CaO)－0.55[w(Al2O3)－0.64w(Fe2O3)]－1.87w(SiO2)－1.4w(Fe2O3)－0.7[w(TiO2)+w(SO3)]
本发明中配料系数及计算公式：
碱度系数
Figure PCTCN2015070457-appb-000011
铝硫比
Figure PCTCN2015070457-appb-000012
为解决上述技术问题，本发明采用的技术手段包括以下内容：
(一)关于熟料
快凝快硬高贝利特硫铝酸盐水泥熟料，所含矿物成份中包括C4A3
Figure PCTCN2015070457-appb-000013
C4AF，C2S、CaSO4，关键在于该硫铝酸盐水泥熟料所含矿物组份中包括0.5～4.6％f-CaO。
上述熟料有如下重量百分比的矿物组成：20～35％C4A3
Figure PCTCN2015070457-appb-000014
3～9％C4AF，37～47％C2S，0.5～4.6％f-CaO，14～26.3％CaSO4,余量为混杂矿物成分。
上述熟料中余量混杂矿物成分≤7％。
上述熟料中余量混杂矿物成分包括MgO、或CaO·TiO2、或Na2SO3、或K2SO3，或其中的两种或两种以上的混合物。
上述的水泥熟料具有如下重量百分比的化学成分组成：12.9～16.1％SiO2，12～19％Al2O3，1～3％Fe2O3，49～54％CaO，12～18.43％SO3，余量为混杂化学成分。
上述熟料中余量化学成分≤4％。
上述水泥熟料中余量化学成份包括MgO、或TiO2、或Na2O、或K2O、或其中两种或两种以上的混合物。
(二)关于熟料的制备方法
所述方法包括以下步骤：
(1)制备毛料：称取质量百分比为33～62％的石灰石、10.5～28％粉煤灰和19～45％脱硫石膏；
(2)生料预制：将(1)中制备的毛料经粉磨、均化得到规定细度的生料；
(3)煅烧：将步骤(2)所得的水泥生料在回转窑中经1300±50℃下煅烧，得到水泥熟 料。
在上述(1)毛料制备中，石灰石组份原料部分或全部为碱渣、或钢渣、或电石渣、或他们的两种或两种以上的混合物，所需要控制的原则是熟料中CaO含量必须等效于49～54％。
在上述(1)毛料制备中，粉煤灰组份中部分或全部为铝矾土、或铝矾土尾矿、或煤矸石、或高岭土、或沸腾炉渣、或粘土或他们的两种以及两种以上的混合物，所需要控制的原则是熟料中Al2O3含量必须等效于12～19％。
在上述脱硫石膏部分或全部为天然无水石膏、或天然二水石膏、或脱硫石膏、或半水石膏、或磷石膏、或硫酸铝或富含石膏成分的工业废料或他们的两种或两种以上的混合物，所需要控制的原则是混合物熟料中SO3含量等效于12～18.43％。
(三)熟料的应用之快凝快硬高贝利特硫铝酸盐水泥
1、由水泥熟料，调凝、促强组分，填料所配制、并均混研磨而成，关键在于：
①水泥熟料选择快凝快硬高贝利特硫铝酸盐水泥熟料，调凝、促强组分选择硬石膏，填料选择矿渣；
②按照下述重量百分比的混配、研磨成水泥：快凝快硬高贝利特硫铝酸盐水泥熟料26％-97％、硬石膏3％-19％、矿渣0％-55％；
③借助上述比例，在小磨实验数据基础上调整快凝快硬高贝利特硫铝酸盐水泥熟料、硬石膏、矿渣的配比，使得经研磨而成的水泥技术指标控制为：
初凝时间：9-30分钟、终凝时间：11-40分钟、2小时抗折强度：1.8-4.6Mpa、2小时抗压强度：4.9-25.6Mpa、28天抗折强度：6.3-11.8Mpa、28天抗压强度：45.1-92.7Mpa、28天自由膨胀率：0.012％-0.078％，限制膨胀率：21天空气中0.01％-0.033％、水中28天膨胀率0.009％-0.055％。
2、水泥中所采用的熟料包括如下重量百分比的矿物组成：20～35％C4A3
Figure PCTCN2015070457-appb-000015
3～9％C4AF，37～47％C2S，0.5～4.6％f-CaO，14～26.3％CaSO4。
3、水泥这种所采用的熟料包括下述重量百分比的化学成分组成：12.9～16.1％SiO2，12～19％Al2O3，1～3％Fe2O3，49～54％CaO，12～18.43SO3。
4、硬石膏组分可全部或部分用脱硫石膏、或天然二水石膏、或半水石膏、或磷石膏、或氟石膏替代，或者用上述石膏的两种或两种以上混合物替代，替代的原则是替代物中三氧化二硫的当量相同。
5、矿渣可用粉煤灰、或钢渣、或铁尾矿砂、或石灰石、或白云石、或砂岩、或他们 的混合物全部或部分替代，替代的原则是替代物中的硅酸二钙和三氧化二铝的对应当量相同。
(四)快凝快硬高贝利特硫铝酸盐水泥生产工艺
1、包括以下工艺步骤：
①生料的制备：称取质量百分比为33～62％的石灰石在生料磨粉磨，然后与10.5～28％粉煤灰和19～45％脱硫石膏经风选、均化，得入窑生料；
②熟料的制备：将步骤①所得入窑生料在回转窑中经1300±50℃煅烧，得到水泥熟料，所含矿物组份中包括0.5～4.6％f-CaO；
③水泥的制备：按照水泥标号要求选取熟料标样、根据混配料化验单、并参照上述水泥配比研磨中的步骤②比例拟定小磨适配方案，进行配比和小磨实验后，根据经验数据称取硬石膏、矿渣以及水泥熟料，混合粉磨至比表面积≥450m2/Kg，制成水泥。
2、上述的步骤③的水泥的制备中、混合粉磨前，加入0.1-0.3％的碳酸锂以缩短凝结时间，提高早期强度。
3、上述水泥，加入0.2-0.5％柠檬酸以延长凝结时间，提高晚期强度。
4、上述水泥中加入的碳酸锂可以用氢氧化锂、氯化锂全部或部分替代。
5、上述水泥中加入的柠檬酸，可用柠檬酸钠、葡萄糖酸钠全部或部分替代。
(五)熟料的应用之后期增强高贝利特硫铝酸盐水泥
基于快凝快硬高贝利特硫铝酸盐水泥熟料的水泥，由水泥熟料，调凝、促强组分，填料所混配研磨而成的试验过程中，发明人在不断缩减相关熟料用量比例的情况下，发现配比成的水泥在初期的快凝、快硬和早期强度指标确实有所下降，但是通过对调凝、促强组分和填料成分比例的适当调整所形成的水泥产品后期强度却明显提高。这展示出快凝快硬高贝利特硫铝酸盐水泥熟料中新生活性材料的引导激励作用，以及调凝、促强组分及填料潜在活性成分互相激发产生的作用是巨大的，所启迪的更加重大的作用应当引起我门足够的重视。
所以熟料低配置的硫铝酸盐水泥也应当视为本发明的应用成果之一。
混配、研磨中所选择的快凝快硬高贝利特硫铝酸盐水泥熟料为5％-12％、硬石膏17％-18％、矿渣71％-78％；
按设计标号在5％-12％范围内选择水泥熟料重量百分比，在小磨实验数据基础上、在上述划定的范围内调整硬石膏、矿渣的配比，经研磨而成的水泥控制技术指标达到：初凝时间不大于43分钟、终凝时间不大于53分钟，28天抗折强度：11.9-12.8Mpa、28天抗压强度：79-82.5Mpa、28天自由膨胀率：0.10-0.12％、空气中21天膨胀率：0.001％-0.002％、水中28天 膨胀率0.017％-0.022％。
本发明上述技术方案中，将少量f-CaO作为一种必要的矿物组成设计于熟料中，是主要的、关键的创新突破点。现有的理论认为：普通硅酸盐水泥熟料中，为了形成更多的硅酸三钙允许f-CaO不超过1.5％，否则会引起水泥安定性潜在威胁；普通硫铝酸盐水泥熟料中f-CaO最高含量不超过0.2％，过多的f-CaO会影响凝固过程的稳定性，甚至造成急凝。传统理论则认为以上两种水泥中f-CaO的存在均对性能不利，而本发明的水泥熟料中含0.5％～4.6％的f-CaO矿物，远远超出理论的禁区、并被实验证实这种存在是有益的。首先，足够的游离钙的存在避免了在熟料烧制过程中由于缺钙而产生低活性矿物，如钙黄长石(C2AS)；其次，少量f-CaO在水泥水化初期可以促进无水硫铝酸钙的水化，使早期凝结硬化加快，这与游离氧化钙在普通硫铝酸盐熟料中的作用是一致的、并不矛盾。只不过普通硫铝酸盐熟料中有大量的高活性C4A3
Figure PCTCN2015070457-appb-000016
含量在60％～70％之间，少量的f-CaO就足以使其水泥水化硬化过快，迅速失去流动性。而本发明中，水泥熟料矿物中只有20％～35％的C4A3
Figure PCTCN2015070457-appb-000017
早强性能极差的C2S高达37～47％，需要f-CaO矿物的促进作用才能使水泥的快凝快硬性能满足应用需要；另一方面，本发明水泥熟料中少量的f-CaO矿物是在1300±50℃低温下煅烧的，晶体细小、结构疏松、活性较高，水化过程中会全部水化，尤其是少量的f-CaO矿物水化反应将更快，所以不存在后期的体积不稳定和安定性不良问题；水泥粉磨时加入了矿渣、或粉煤灰、或钢渣等硅铝源材料，在水化反应中，水泥熟料中的f-CaO与矿渣、粉煤灰、钢渣中所提供的Al2O3、Fe2O3、SiO2及原水泥熟料中SO3和后加入的石膏中的SO3反应生成水化硫铝酸钙、铝胶、硅酸钙凝胶，激发了矿渣、粉煤灰、钢渣的活性，提高了水泥的早期强度，吸收了f-CaO所带来的膨胀；采用上述技术方案制造的水泥，经大量试验数据表明：自由膨胀率28d 0.11％～0.37％，波动范围较小；限制膨胀率7d 0.005％～0.040％，28d 0.009％～0.055％，21d空气中-0.003～0.033％，膨胀值不大、收缩值很小，水中膨胀和干空中的干缩值两者落差很小；总体说该水泥体积变形很小，抗裂抗渗性能极为优异。
本发明首次在工业生产中将硫酸钙作为水泥熟料的主矿物之一使用。在水泥熟料中，硫酸钙矿物含有14％～26.3％。较多的CaSO4能改善生料的易烧性，降低熟料烧成温度；CaSO4在高温下会以液态存在，增加了水泥熟料在烧成温度下的液相量，增强了各成份之间的相对扩散速度，使形成熟料的其他矿物的化学反应更快速和彻底；熟料烧成中硅酸二钙和铁铝酸四钙固溶三氧化硫，形成矿物固溶体，使硅酸二钙和铁铝酸四钙的的早期活性大大提高；硫酸钙本身可以水化形成二水硫酸钙，也可以凝结硬化；硫酸钙还可与熟料中的另一主要矿物无水硫铝酸钙和水继续反应形成早期主要水化产物钙矾石，使水泥快凝快硬性能 加强。
上述技术方案中水泥的比表面积为450～500m2/kg，并且已经做了大量的水泥常规物理性能、耐久性、外加剂适应性、混凝土、干混砂浆等应用和性能检验，其应用范围与目前普遍应用的硫铝酸盐水泥基本相同；与普通硫铝酸盐水泥比较，本发明的水泥快凝快硬特性更为显著，如抗压强度，《硫铝酸盐水泥》GB 20472—2006只提出了1天龄期的抗压强度标准，本发明给出的实际测试数据证明：水泥2h可以达到25.6MPa；微膨胀、低干缩性能更为优异；凝结硬化快，且和易性好、面层不起砂。
采用上述技术方案产生的有益效果还在于：(1)本发明提供的水泥所选用熟料,通过创造性的引入超出常规限量的f-CaO和CaSO4，突破了国内外硫铝酸盐水泥熟料矿物成分组成和配料率值的束缚，给高硅低铝的低品位原材料的利用、并制造出快凝快硬早强高强高贝利特硫铝酸盐水泥熟料提供了理论依据；(2)在熟料煅烧中实现了降低熟料烧成温度，降低工艺温度50℃，降低了能耗，减少了排放，生产工艺环境得到改善；(3)该熟料制作的水泥在水化过程中，发挥了f-CaO、C4A3
Figure PCTCN2015070457-appb-000018
和CaSO4的相互激发作用，制作的水泥快凝快硬、早强高强、微膨胀、低干缩、抗冻、抗渗、抗海水腐蚀性能优异；(4)本技术所制备水泥熟料及水泥工艺中采用了大量废渣，废渣利用率高达30％以上；(5)原料成本低。延续实验证明：明显降低熟料用量比例后，虽然早期强度受到某些影响，但是加工制备出水泥28d抗压强度仍可达到79—81Mpa，且实验过程中明显的表现出水化放热低、抗海水腐蚀能力极强、尺寸变化率小，非常适合海洋工程的应用，具有极强的市场竞争能力。
采用上述技术手段所生产的水泥产品，应用中无需掺加任何外加剂，仅仅采用规范化工艺步骤将上述水泥熟料，调凝、促强组分，填料均混研磨即可以获得各种标号的高性能的贝利型特硫铝酸盐水泥。由于生产工艺控制过程成熟、所采用的设备和固硫工艺被证明环保效果明显、烧结温度明显降低有利于降低能耗、加上可以大规模使用工业废渣有利于循环经济的发展和降低成本的社会效益，说明本发明属于本领域内的重大技术突破。
附图说明
图1是快凝快硬高贝利特硫铝酸盐水泥熟料、水泥、及其生产工艺的流程图。
图中的流程中熟料的生产是以33～62％的石灰石、10.5～28％粉煤灰和19～45％脱硫石膏为参考，水泥的混配和研磨是以熟料26％-97％、硬石膏3％-19％、矿渣0％-55％为参考。
具体实施方式
下面结合实施例进一步说明本发明的目的是如何实现的。
实施例1～实施例6是生料料方配比
①生料的制备：按照表2中的生料料方配比，称取化学成分如表1所示的石灰石，放入生料磨粉磨，随后进入生料磨磨尾提升机中；同时按照表2中的生料料方配比，称取化学成分如表1所示的粉煤灰和脱硫石膏，与粉磨后的石灰石同步输送到生料磨磨尾提升机，随后3种物料输送到选粉机，经选粉机风选后合格生料输送到生料均化库，不合格生料送回生料磨继续粉磨；均化后得入窑生料。
该步骤中，粉煤灰、脱硫石膏不进生料磨，直接进入选粉机，大大提高了生料粉磨***台时产量，大幅度降低了电耗和球耗。
表1 原料的化学成分
Figure PCTCN2015070457-appb-000019
表2 快凝快硬高贝利特硫铝酸盐水泥熟料制作中生料料方中各成分的重量百分比
配料 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
石灰石(％) 62.0 33.0 35.0 55.3 52.0 62.0
粉煤灰(％) 13.5 24.0 20.0 25.7 28.0 10.5
脱硫石膏(％) 24.5 43.0 45.0 19.0 20.0 27.5
②熟料的制备：将步骤①所得生料在窑外分解窑中经1300±50℃煅烧，得到水泥熟料。在回转窑煅烧中由于还原气氛产生的少量二氧化硫，随烟气上升到旋风预热器中，与进入的生料进一步反应，避免了二氧化硫的逸出。同时由于降低了煅烧温度和降低了煤耗，从而减少了氮氧化物的形成和排放，符合环保要求。
③水泥的制备：按照配比称取硬石膏、矿渣以及步骤②中所得的水泥熟料，混合粉磨至比表面积≥450m2/Kg，制成水泥。
具体的工艺流程参见附图1。
按照《硫铝酸盐水泥》GB 20472-2006检验其流动度、标准稠度用水量(％)、凝结时间及抗折抗压强度等物理性能。所得熟料的物理性能见表3。
表3 实施例1～实施例6所制备的水泥熟料的物理性能
Figure PCTCN2015070457-appb-000020
从表中可见所制备的熟料初凝时间均小于16min，终凝时间均不大于40min，早期2小时抗压强度达到20.5Mpa，具有快凝快硬的性质，抗压强度及抗折强度比硫铝酸盐水泥熟料更高。
实施例7～16中数据来自于熟料样品的组分的实验分析。
本发明中快凝快硬高贝利特硫铝酸盐水泥熟料所含矿物成份中包括C4A3
Figure PCTCN2015070457-appb-000021
C4AF、C2S、CaSO4，关键在于该硫铝酸盐水泥熟料所含矿物组份中还包括0.5～4.6％f-CaO。具体的，本实施例中水泥熟料的矿物组成(wt％)、化学成分(wt％)、配料p和Cm率值及物理性能，分别见表4、表5及表6。
表4 快凝快硬高贝利特硫铝酸盐水泥熟料的矿物组成成份(％)
Figure PCTCN2015070457-appb-000022
表5 快凝快硬高贝利特硫铝酸盐水泥熟料的化学成分(％)
Figure PCTCN2015070457-appb-000023
表6 快凝快硬高贝利特硫铝酸盐水泥熟料的物理性能
Figure PCTCN2015070457-appb-000024
本实施例中所制备的水泥熟料28d抗压强度达到73MPa，在低铝高硅组成成份的高贝利特硫铝酸盐水泥熟料研究中未见相关报道。
实施例17～35给出了关于快凝快硬高贝利特硫铝酸盐水泥组分的具体数据，并列举了该实施例的技术性能试验报告中的主要指标，形成了表9-表11。实施例是以快凝快硬高贝利特硫铝酸盐水泥熟料的物理性能表6中实施例7的熟料作为实施例17～35水泥的入选熟料，并按照上述水泥制作工艺方法所制成水泥产品。其中步骤③中加入了矿渣和硬石膏、或它们的替代材料，所采用的各种石膏和混合材料的化学成分见表7，各个实施例水泥配比及物理性能见表8、表9、表10。因为表中罗列项目过多，表8、表9、表10每个表分为左、右两部分，上、下依次排列。限制膨胀率的试验标准参考《混凝土膨胀剂》GB 23439—2009。
表7 硬石膏及其矿渣替代材料化学成份
Figure PCTCN2015070457-appb-000025
表8-A
Figure PCTCN2015070457-appb-000026
表8-B
Figure PCTCN2015070457-appb-000027
表8-A与表8-B组合成表8快凝快硬高贝利特硫铝酸盐水泥实施例表。其中实施例20、24、30因水泥组分中另加入了外加剂单列为表9。
表9-A与表9-B组合成表9快凝快硬高贝利特硫铝酸盐水泥中再借助外加剂，包括促凝剂或/和缓凝剂时对水泥的技术性能的影响实例表。其中实施例20、24、30实施例分中分别加入及混合加入了外加剂后所形成的影响单列合并后为表9。可以看出本发明如果结合外加剂使用，可以产生意想不到的技术效果。具体可以参看下表。
进一步的实验证明虽然在配比、研磨加工中，继续减少水泥熟料的比例，使得水泥的早期性能会受到一定的影响，但后期的强度不但没有负面影响，反而有大幅度的提升。这表明本发明中所展现出来的创新意义，还待进一步挖掘。
表9-A
Figure PCTCN2015070457-appb-000028
表9-B
Figure PCTCN2015070457-appb-000029
表10-A与表10-B组合成表10：快凝快硬高贝利特硫铝酸盐水泥扩展实施例表。其中实施例33、34、35在水泥熟料应用中比例重量显著地减少，虽然在早期快凝快应的技术指标上产生明显的影响，但水泥后期的强度显著地提高，在并没有增添外加剂的情况下，抗折强度可以达到11.9-12.8Mpa，抗压强度可以达到79.0-82.5Mpa.限制膨胀率实验证明，水泥的后期微膨胀特性任然保持。这给进一步扩展产品品种和推广应用留下了机会。
表10-A
Figure PCTCN2015070457-appb-000030
表10-B
Figure PCTCN2015070457-appb-000031
上述实施例中，硬石膏组分可以全部或部分用脱硫石膏、或天然二水石膏、或半水石膏、或磷石膏、或氟石膏替代，或者用上述石膏的两种以上混合物替代；所述矿渣可用粉煤灰或钢渣、或铁尾矿砂、或石灰石、或白云石、或砂岩或他们的混合物全部或部分替代，其关键的问题是在应用不同种原料时要掌握实质上起到作用的等效成分，再石膏的替代品上关键是等效的调凝、促强的成分，填料则考虑的是潜在活性成分。所述的一种快凝快硬高贝利特硫铝酸盐水泥，可以加入不大于0.30％的碳酸锂缩短凝结时间，提高早期强度,加入的碳酸锂可以用氢氧化里、氯化锂全部或部分替代；所述的一种快凝快硬高贝利特硫铝酸盐水泥，可以加入不大于0.5％柠檬酸延长凝结时间，提高晚期强度,所加入的柠檬酸，可用柠檬酸钠、葡萄糖酸钠全部或部分替代。

Claims (20)

  1. 一种快凝快硬高贝利特硫铝酸盐水泥熟料，所含矿物成份中包括
    Figure PCTCN2015070457-appb-100001
    C4AF、C2S、CaSO4，其特征在于该硫铝酸盐水泥熟料所含矿物组份中包括0.5～4.6％f-CaO。
  2. 根据权利要求1所说的快凝快硬高贝利特硫铝酸盐水泥熟料，其特征在于上述熟料有如下重量百分比的矿物组成：20～35％
    Figure PCTCN2015070457-appb-100002
    3～9％C4AF，37～47％C2S，0.5～4.6％f-CaO，14～26.3％CaSO4,余量为混杂矿物成分。
  3. 根据权利要求2所说的快凝快硬高贝利特硫铝酸盐水泥熟料，其特征在于上述熟料中余量混杂矿物成分≤7％。
  4. 根据权利要求2或3所述的快凝快硬高贝利特硫铝酸盐水泥熟料，其特征在于上述熟料中余量混杂矿物成分包括MgO、或CaO·TiO2、或Na2SO3、或K2SO3，或其中的两种或两种以上的混合物。
  5. 根据权利要求2所述的快凝快硬高贝利特硫铝酸盐水泥熟料，其特征在于所述的熟料具有如下列重量百分比的化学成分组成：12.9～16.1％SiO2，12～19％Al2O3，1～3％Fe2O3，49～54％CaO，12～18.43％SO3，余量为混杂化学成分。
  6. 根据权利要求5所说的快凝快硬高贝利特硫铝酸盐水泥熟料，其特征在于上述熟料中混杂化学成分≤4％。
  7. 根据权利要求5或6所述的一种快凝快硬高贝利特硫铝酸盐水泥熟料，其特征在于所述水泥熟料中混杂化学成份包括MgO、或TiO2、或Na2O、或K2O、或其中两种或两种以上的混合物。
  8. 一种快凝快硬高贝利特硫铝酸盐水泥熟料的制备方法，其特征在于所述方法包括以下步骤：
    (1)制备毛料：依据权利要求1所述的配比计算所需各原料用量，称取质量百分比为33～62％的石灰石、10.5～28％粉煤灰和19～45％脱硫石膏；
    (2)生料预制：将(1)中制备的毛料经粉磨、均化得到规定细度的生料；
    (3)煅烧：将步骤(2)所得的水泥生料在回转窑中经1300±50℃下煅烧，得到水泥熟料。
  9. 根据权利要求8所述的制备方法，其特征在于所述(1)制备毛料中，石灰石组份原料部分或全部为碱渣、或钢渣、或电石渣、或他们的两种或两种以上的混合物，所需要控制的原则是熟料中CaO含量必须等效于49～54％。
  10. 根据权利要求8所述的制备方法，其特征在于所述(1)制备毛料中，粉煤灰组份中部分或全部为铝矾土、或铝矾土尾矿、或煤矸石、或高岭土、或沸腾炉渣、或粘土或他们的两 种以及两种以上的混合物，所需要控制的原则是熟料中Al2O3含量必须等效于12～19％。
  11. 根据权利要求8所述的制备方法，其特征在于所述(1)制备毛料中，脱硫石膏部分或全部为天然无水石膏、或天然二水石膏、或脱硫石膏、或半水石膏、或磷石膏、或硫酸铝或富含石膏成分的工业废料，或他们两种或两种以上的混合物，所需要控制的原则是混合物熟料中SO3含量等效于12％～18.43％。
  12. 一种快凝快硬高贝利特硫铝酸盐水泥，包括水泥熟料，调凝、促强组分，填料所配制、并均混研磨而成，其特征在于：
    ①选择权利要求1所说的水泥熟料，加配调凝、促强组分选择硬石膏，填料选择矿渣；
    ②按照下述重量百分比的混配、研磨成水泥：快凝快硬高贝利特硫铝酸盐水泥熟料26％-97％、硬石膏3％-19％、矿渣0％-55％；
    ②按设计标号在26％-97％范围内选择水泥熟料重量百分比，在小磨实验数据基础上、在步骤②划定的范围内调整硬石膏、矿渣的配比、并经研磨而成的水泥控制技术指标达到：
    初凝时间：9-30分钟、终凝时间：11-40分钟、2小时抗折强度：1.8-4.6Mpa、2小时抗压强度：4.9-25.6Mpa、28天抗折强度：6.3-11.8Mpa、28天抗压强度：45.1-92.7Mpa、28天自由膨胀率：0.012％-0.078％，限制膨胀率：21天空气中0.01％-0.033％、水中28天膨胀率0.009％-0.055％。
  13. 根据权利要求12所述的快凝快硬高贝利特硫铝酸盐水泥，其特征在于所述硬石膏组分可全部或部分用脱硫石膏、或天然二水石膏、或半水石膏、或磷石膏、或氟石膏替代，或者用上述石膏的两种或两种以上混合物替代，替代的原则是替代物中三氧化二硫的当量相同。
  14. 根据权利要求12所述的快凝快硬高贝利特硫铝酸盐水泥，其特征在于所述矿渣可用粉煤灰、或钢渣、或铁尾矿砂、或石灰石、或白云石、或砂岩、或他们的混合物全部或部分替代，替代的原则是替代物中的硅酸二钙和三氧化二铝的对应当量相同。
  15. 一种快凝快硬高贝利特硫铝酸盐水泥的生产工艺，其特征在于具体包括以下步骤：
    ①生料的制备：称取质量百分比为33～62％的石灰石在生料磨粉磨，然后与10.5～28％粉煤灰和19～45％脱硫石膏经风选、均化，得入窑生料；
    ②熟料的制备：将步骤①所得入窑生料在回转窑中经1300±50℃煅烧，得到水泥熟料，所含矿物组份中包括0.5～4.6％f-CaO；
    ③水泥的制备：参照权利要求12之步骤②中的配比，结合水泥标号设计要求选取熟料、并根据混配料化验单、预拟小磨适配方案，进行配比和小磨实验后，根据经验数据决定硬石膏、矿渣以及水泥熟料的具体比例，再混合粉磨至比表面积≥450m2/Kg，制成水泥。
  16. 根据权利要求15所述的一种快凝快硬高贝利特硫铝酸盐水泥的生产工艺，其特征在于所述的步骤③的水泥的制备中、混合粉磨前，加入0.1-0.3％的碳酸锂以缩短凝结时间，提高早期强度。
  17. 根据权利要求15所述的一种快凝快硬高贝利特硫铝酸盐水泥的生产工艺，其特征在于所述的水泥，加入0.2-0.5％柠檬酸以延长凝结时间，提高晚期强度。
  18. 根据权利要求16所述的一种快凝快硬高贝利特硫铝酸盐水泥，其特征在于所述的水泥中加入的碳酸锂可以用氢氧化锂、氯化锂全部或部分替代。
  19. 根据权利要求17所述的一种快凝快硬高贝利特硫铝酸盐水泥，其特征在于所述的水泥中加入的柠檬酸，可用柠檬酸钠、葡萄糖酸钠全部或部分替代。
  20. 基于权利要求12所说的高贝利特硫铝酸盐水泥，包括水泥熟料，调凝、促强组分，填料所配制、并均混研磨而成，其特征在于：
    混配、研磨中所选择的快凝快硬高贝利特硫铝酸盐水泥熟料为5％-12％、硬石膏17％-18％、矿渣71％-78％；
    按设计标号在5％-12％范围内选择水泥熟料重量百分比，在小磨实验数据基础上、在上述划定的范围内调整硬石膏、矿渣的配比，经研磨而成的水泥控制技术指标达到：
    初凝时间不大于43分钟、终凝时间不大于53分钟，28天抗折强度：11.9-12.8Mpa、28天抗压强度：79-82.5Mpa、28天自由膨胀率：0.10％-0.12％、空气中21天膨胀率：0.001％-0.002％、水中28天膨胀率0.017％-0.022％。
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