CN1190385C - Method for making high performance cement mixed material from flyash - Google Patents
Method for making high performance cement mixed material from flyash Download PDFInfo
- Publication number
- CN1190385C CN1190385C CNB021390452A CN02139045A CN1190385C CN 1190385 C CN1190385 C CN 1190385C CN B021390452 A CNB021390452 A CN B021390452A CN 02139045 A CN02139045 A CN 02139045A CN 1190385 C CN1190385 C CN 1190385C
- Authority
- CN
- China
- Prior art keywords
- flyash
- cement
- lime
- high performance
- performance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali 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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a method for manufacturing a high-performance cement mixed material by using fly ash, which belongs to the building material technology and the technical field of environmental protection. The present invention primarily solves the problems of low mixed quantity, poor early strength performance, poor high strength performance, etc., of the existing method of activating treatment of the fly ash. The present invention has the process and the following steps that 4 % to 20% of lime alkali material, 0.5 % to 5% of gypsum material, 67 % to 92% of fly ash, 0.2% to 5% of sodium sulfate, 0.5 % to 7% of calcium carbonate, 0.03 % to 0.07% of triethanolamine, 0 to 2% of calcium chloride, 0 to 0.6% of calcium lignosulfonate, 0 to 3% of sodium nitrite, 0 to 3% of ferrous sulfate and 0 to 5% of water glass are added into a mill according to the weight percentage, are added with water to be milled into slurry with less than 16% of 45 mu m sieve residue and are sprayed with fog for drying, or dehydrated for drying with less than 1% of moisture. The present invention is used for producing fly ash silicate cement, composite silicate cement, high-performance cement and concrete, and the mixing quantity reaches 30 % to 70%. The present invention has the characteristics of high activity, multiple functions, low cost and high performance and is mainly used for manufacturing the cement mixed material or concrete admixture.
Description
Technical field
What the present invention relates to is to make high-performance cement blended material method with flyash, according to said method the cement mixture of Sheng Chaning have high reactivity, contain a large amount of ultrafine powders, characteristic such as multi-functional, can be used for Portland fly ash cement, composite Portland cement, ordinary Portland cement, high performance silicon acid salt cement blended material and levigate after be used for concrete batching, high performance concrete, masonry mortar.It belongs to building material technical field and environmental technology field.
Background technology
Flyash is as the useless assorted slag of large industry, and its processing and comprehensive utilization extremely countries in the world are paid close attention to.In China's method commonly used is that original state flyash or levigated flyash are done the blended material of cement and concrete adulterant, brick, building block.Flyash is as the blended material and the concrete adulterant of cement, and China standardizes, and formulates the corresponding techniques standard.But use dried row's top grade ash, the one-level ash that is preferably sorting at present, a large amount of wet ash discharges and the utilization ratio of inferior grade ash are still lower.Exciting with the method for Study of Activation of flyash is more, mainly is that mechanical grinding method, lime alkali excite method, steam-cured method.At present, use more complex excitation, promptly lime, gypsum, sodium sulfate mix dry grinding with flyash, though early strength increases, activity is not high, and volume is low, is not higher than 30%, and effect is undesirable, and poor stability often will be joined and be mixed slag, zeolite.Adding lime alkali high temperature excites with steam-cured and excites because cost height, big, the complex process of investment fail to be used widely.
Summary of the invention
The objective of the invention is to propose a kind of flyash particularly the activation treatment of inferior grade flyash make volume height, early strengthening and high strengthening, cement mixture and concrete adulterant method that good, the freeze proof impermeability of workability is good.The present invention does not produce secondary pollution, and finished product can improve the stability of cement cementitious performance and cement stone effectively, can also quicken the early hydration speed of cement, and guarantees the later strength development; Can be used as the blended material of high-performance cement and the super fine powder additives of high performance concrete.
Technical solution of the present invention is: make high performance cement mixture method with flyash, its technology and step the following is: (1) is by weight percentage lime alkali material 4～20%; Gypsum material 0.5～5%; Flyash 67～92%; Sodium sulfate 0.2～5%; Lime carbonate 0.5～7%; Trolamine 0.03～0.07%; Calcium chloride 0～2%; Calcium lignin sulphonate 0～0.6%; Sodium Nitrite 0～3%; Ferrous sulfate 0～3%; Water glass 0～5%; Add grinding machine, (2) add water and go into grinding machine then, levigate to slip 45 μ m screeningss less than 16%; (3) carry out spraying drying or dewatered drying to moisture less than 1%.
Lime alkali material described in the technology of the present invention solution can be unslaked lime, white lime, milk of lime or acetylene gas slag.
Gypsum material described in the technology of the present invention solution can be plaster stone, phosphogypsum or citric acid gypsum.
Flyash described in the technology of the present invention solution can be wet row of heat power plant or dry discharge fly ash, and its solid carbon is less than 15%.
Grinding machine described in the technology of the present invention solution can be for water being ball mill, vibrating mill, the tuber grinder of dispersion medium.
A significant advantage of the present invention is that the activation treatment manufacturing that is fit to all flyash has high performance, multi-functional cement mixture and concrete adulterant, be particularly suitable for inferior grade flyash as wet ash discharge be lower than the one-level dry discharge fly ash, avoided that general dry grinding or sorting flyash early activity are low, few as cement mixture or concrete adulterant consumption, strength development waits shortcoming slowly, the very low situation of China's inferior grade utilization of fly ash rate is significant for solving.
Flyash belongs to sillico aluminate glass attitude meal, and main chemical compositions is SiO
2, Al
2O
3, form is by ultrafine particle (＜1 μ m) and a small amount of cenosphere aggregate that links mutually of sintering at high temperature.Surface tissue is very stable, the chemical stability height, so the chemical action of the acid that ability is general, alkali, salt, water at low temperatures is the surface tissue that impossible destroy flyash at short notice, and more can not be with the active SiO of inside
2, Al
2O
3Discharge; So the flyash that does not excite in advance can only be made fine aggregate in early days, and its chemically reactive in cement stone generally just slowly ejects later at first quarter moon, and the following of curing water existence must be arranged, could realize.And the manufacture of cement ball milling can only be broken up the big sintering aggregate that links together and is little sintering aggregate, spheric flyash primary particle still seldom, the dispersity of flyash increases, the flowability of cement slurry makes moderate progress, but generally can not destroy inert flyash surface structure, therefore, the early activity of common machinery dry grinding raising flyash is not obvious, and water-reducing rate is not high.
Characteristics of the present invention are to remove the main exciting agent Ca (OH) that adopts
2, CaSO
4, also add compound activator outward, adopted unique technology simultaneously.The present invention carries out these production processes in two steps, promptly levigate-chemi-excitation and hydro-thermal-chemi-excitation.Its technology is simple, and is easy to operate, and mechanical grinding, chemi-excitation, the many-sided acting in conjunction of hydro-thermal reaction are integrated in one, and what multi-faceted synergy made flyash excites that treatment effect is good, high efficiency.For grinding technics, wet-milling is than the efficient height of dry grinding, with exciting agent with flyash wet-milling together, mechanical grinding and chemi-excitation acting in conjunction, chemical activator is more effective in water and in the levigated process, and particularly excited ion can penetrate into the internal action of flyash sintering aggregate, can effectively destroy the sintering aggregate, accelerate levigate with excite, make slurry behind the mill have a large amount of ultrafine powder (＜1 μ m) and the sphere pearl of wafing.Drying process and chemi-excitation unite two into one, and not only speed of response is fast, and be active high, and solved the shortcoming of flyash oven dry difficulty; Carry out the hydro-thermal provocative reaction in the exsiccant process, because Heating temperature is more much higher than normal temperature, speed of response improves more than tens times, particularly under the condition that has water to exist, gives full play to the most effective exciting agent OH of flyash
-The ionic effect, SO
4 -Ionic exists, and helps Ca (OH)
2Dissolving and OH
-Ionic concentration improves, and the generation that promotes hydrated calcium aluminite in the cement stone, quickens the aquation of cement, improves cement stone early strength.Particularly under the condition of higher temperature, alkalescence, hydro-thermal, finish fast, destroy the surface tissue of flyash, discharge inner active SiO
2, Al
2O
3, hydro-thermal reaction synthetic hydrated silicon calcium aluminate actives.And under the condition that compound activator exists, speed of response is accelerated, and helps improving the aquation of the active of flyash and quickening cement, improves the internal crystal structure of concrete, increases concrete density and weather resistance.
One of feature of the present invention is that flyash manufacturing high-performance cement blended material method has adopted compound activator, removes the main exciting agent Ca (OH) that adopts
2, CaSO
4, also added Wingdale and cement early strength agent, antifreezing agent, water reducer etc. outward, quickened to excite process, improved and excite degree, given simultaneously that it is multi-functional.Except having good excitating performance, make concrete have the early-strength anti-freezing performance as sodium sulfate simultaneously; Lime carbonate has the acceleration aquation, generates new mineral---hydration carbon calcium aluminate, improves early strength, improves microtexture and interface structure, prevents the function of " cement bacillus " several respects; Trolamine has grinding aid and improves the early strength function; Calcium chloride, Sodium Nitrite excitating performance are better, also have freeze proof and early strong function; Calcium lignin sulphonate is wet-milling slip and concrete dispersion agent, water reducer, has the intermiscibility that improves flyash and cement simultaneously, improves concrete strength, weather resistance and workability; Ferrous sulfate, water glass improve concrete strength, impermeability, frost resistance and weather resistance.It is to be noted: although contain a spot of sodium ion in the compound activator, experiment finds that technical recipe of the present invention can not make concrete produce alkali, can not influence concrete weather resistance yet.Reason is that the flyash fine powder has than the higher chemically reactive of gathering materials, and preferential and a spot of sodium ion reacts mineral such as generating feldspar and protects silica to gather materials, and " eating the alkali mineralising " is that flyash is as ultra-fine one of the reason of gathering materials of high performance concrete.
The product of making the production of high-performance cement blended material method through this flyash is a kind of dried mud shape thing, is the not high coacervate of strength of joint that contains a large amount of ultrafine powders and cenosphere, and general dry grinding is easy to it is broken up.Therefore, when grinding as cement mixture or levigate back as concrete adulterant together, more superfine spherical powder, microballon are just arranged in cement or the concrete mortar, have the characteristic of silica flour with grog.Then the flyash of grain effect, micro aggregate effect, closely knit effect, the general dry grinding of pozzolanic activity ratio is strong, and the advantage of being brought is early strengthening and high strengthening, high compact, height is even, height is impervious, high durable and good workability.Thereby the product of producing by the present invention is high reactivity, multi-functional, high performance cement mixture and concrete admixture.
Formed tiny moisture and anhydrous mineral in the flyash product after the processing, it in cement can and the interaction of calcium ion speed up, produce gelling preferably, and dispersity is high more good more.Therefore, the flyash after the processing can improve cement cementitious performance.
Flyash product after the activation treatment contains the mineral that the dewatered aquation of part is crossed, because Heating temperature is low, these mineral and the new crystallizable mineral degree that forms are lower, active high, run into the very fast recovery of water, form the aquation small-crystalline, and become the brilliant base of hydrated cementitious crystalline, promote hydrated cementitious, the glue or the indefiniteness thing that do not lose the aquation mineral of crystal water in the flyash after the processing in addition and do not dewater fully, grinding is distributed to and also forms small-crystalline in the cement easily, and the calcium ion that can absorb in the cement slurry forms hydrated calcium silicate colloid or ca aluminosilicate gelling thing, thereby induce cement clinker ionic aquation,, and can quicken the aquation of cement so the flyash after handling not only self has certain activity.
Embodiment
Embodiment 1
Adopt prescription by weight percentage: unslaked lime 15%; Plaster stone 3%; Wet-discharged coal ash (in solid) 76%; Sodium sulfate 1.0%; Lime carbonate 1.7%; Trolamine 0.05%; Calcium chloride 1%; Calcium lignin sulphonate 0.45%; Sodium Nitrite 1.0%; Ferrous sulfate 0.8%.Adding that water tails at grinding in ball grinder to 45 μ m is 15%, emits slip, and spraying drying is little of 1% to moisture, is early strong, high-strength, freeze proof, impervious high-performance multifunctional water cement mixture.High-performance flyash equivalent with 40%, 50% replaces the 52.5R silicate cement, press GB/T1767T1-1999 " Test method for strength of hydraulic cement mortar detection ", its intensity index reaches 42.5,32.5 grades respectively, and other index all reaches GB GB12958-1999 " composite Portland cement ".Have early strong, freeze proof, impervious, low hydration heat, good workability.Be used for concrete admixture, it is 30～60% that equivalent replaces cement weight per-cent volume.
Embodiment 2
With embodiment 1, different is to use acetylene gas slag or milk of lime by butt equivalent replacement unslaked lime; Phosphogypsum is pressed butt equivalent replacement plaster stone, adopts three grades of flyash of carbon content 12%.It comes to the same thing.
Embodiment 3
With embodiment 1, the fineness of different is slip is that 45 μ m tail over is 9%, replace the 525R silicate cement with 55%, 70% equivalent, press GB/T1767T1-1999 " Test method for strength of hydraulic cement mortar detection ", its intensity index reaches 42.5,32.5 grades respectively, and other index all reaches GB GB12958-1999 " composite Portland cement ".Workability is good, the water-reducing rate height.
Embodiment 4
Adopt prescription by weight percentage: white lime 8%; Citric acid gypsum 2%; Dry discharge fly ash 80%; Sodium sulfate 0.4%; Lime carbonate 4.75%; Trolamine 0.05%; Water glass 3%; Sodium Nitrite 1.8%.Adding that water tails at grinding in ball grinder to 45 μ m is 5%, emits slip, the ageing dehydration, the roller-way kiln dry to moisture less than 1%, be early strong, high-strength, freeze proof, impervious high-performance multifunctional water cement mixture.Replace 62.5 grades of silicate cements with 35%, 55%, 70% equivalent, press GB/T1767T1-1999 " Test method for strength of hydraulic cement mortar detection ", its intensity index reaches 52.5,42.5,32.5 grades respectively, and other index all reaches GB GB12958-1999 " composite Portland cement ".Workability is good.Because of it contains a large amount of ultra-fine micropowders, microballon, be used for high-performance concrete additive, equivalent replaces or excess replacement volume is 30～70%.
Claims (5)
1, make high performance cement mixture method with flyash, its technology and step the following is:
(1) by weight percentage lime alkali material 4～20%; Gypsum material 0.5～5%; Flyash 67～92%; Sodium sulfate 0.2～5%; Lime carbonate 0.5～7%; Trolamine 0.03～0.07%; Calcium chloride 0～2%; Calcium lignin sulphonate 0～0.6%; Sodium Nitrite 0～3%; Ferrous sulfate 0～3%; Water glass 0～5%; Add grinding machine, then
(2) add water and go into grinding machine, levigate to slip 45 μ m screeningss less than 16%;
(3) carry out spraying drying or dewatered drying to moisture less than 1%.
2, make high performance cement mixture method according to claims 1 described flyash, described lime alkali material is unslaked lime, white lime, milk of lime or acetylene gas slag.
3, make high performance cement mixture method according to claims 1 are described with flyash, described gypsum material is plaster stone, phosphogypsum or citric acid gypsum.
4, make high performance cement mixture method according to claims 1 are described with flyash, described flyash is wet row of heat power plant or dry discharge fly ash, and its solid carbon is less than 15%.
5, make high performance cement mixture method according to claims 1 are described with flyash, described grinding machine is for being ball mill, vibrating mill, the tuber grinder of dispersion medium with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021390452A CN1190385C (en) | 2002-09-11 | 2002-09-11 | Method for making high performance cement mixed material from flyash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021390452A CN1190385C (en) | 2002-09-11 | 2002-09-11 | Method for making high performance cement mixed material from flyash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1401606A CN1401606A (en) | 2003-03-12 |
| CN1190385C true CN1190385C (en) | 2005-02-23 |
Family
ID=4749864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021390452A Expired - Fee Related CN1190385C (en) | 2002-09-11 | 2002-09-11 | Method for making high performance cement mixed material from flyash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1190385C (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329336C (en) * | 2005-09-06 | 2007-08-01 | 梅县五彩涂料厂 | Cement early strength agent and its prepn |
| CN1325419C (en) * | 2005-12-19 | 2007-07-11 | 北京朗新明环保科技有限公司 | Dehydration method and apparatus of flue gas desulfurization gypsum slurry |
| CN100369852C (en) * | 2006-08-09 | 2008-02-20 | 姜博 | Calcium enriched grout admixture and its preparation method and use method |
| CN102633458B (en) * | 2012-03-13 | 2013-12-11 | 池州市新科建材有限公司 | Cement mixed material containing coal ash and method for preparing cement mixed material |
| EP2746237B1 (en) * | 2012-12-19 | 2020-02-12 | HeidelbergCement AG | Activator for cement |
| CN103342496A (en) * | 2013-07-23 | 2013-10-09 | 中国石油大学(华东) | Low-temperature early-strength composite exciting agent for lime and fly ash stabilized aggregate based on seawater flushed fly ash and application of exciting agent |
| CN105481279A (en) * | 2014-09-15 | 2016-04-13 | 武汉鸿信通科技有限公司 | Preparation method of green environmental-protection cement |
| CN104326686A (en) * | 2014-09-30 | 2015-02-04 | 鄂尔多斯市蒙西建材有限责任公司 | Silicon waste stone cement mixed material |
| CN106746795A (en) * | 2016-11-21 | 2017-05-31 | 郑州诚合信息技术有限公司 | A kind of inorganic cement material and preparation method thereof |
| CN107311498B (en) * | 2017-07-12 | 2019-10-25 | 武汉理工大学 | A kind of entringite stabilizer and preparation method thereof |
| CN112264183B (en) * | 2020-09-22 | 2022-04-29 | 铜陵有色金属集团股份有限公司 | Resource treatment method of high-sulfur copper tailings, product and application thereof |
| CN112537920B (en) * | 2020-12-04 | 2022-03-01 | 武汉理工大学 | Nano reinforcing agent for sodium sulfate and sodium carbonate alkali-activated cementing material and preparation method and application thereof |
| CN113277805A (en) * | 2021-05-28 | 2021-08-20 | 贵州盘江煤电集团有限责任公司 | High-strength mixed guniting material based on high-content fly ash and application method thereof |
| CN115140966A (en) * | 2022-03-31 | 2022-10-04 | 湖北工业大学 | Concrete composition free of steam curing and concrete member |
-
2002
- 2002-09-11 CN CNB021390452A patent/CN1190385C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1401606A (en) | 2003-03-12 |
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