CN1172084A - Non-chamotte burning-free flyash cement - Google Patents

Non-chamotte burning-free flyash cement Download PDF

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Publication number
CN1172084A
CN1172084A CN96118276A CN96118276A CN1172084A CN 1172084 A CN1172084 A CN 1172084A CN 96118276 A CN96118276 A CN 96118276A CN 96118276 A CN96118276 A CN 96118276A CN 1172084 A CN1172084 A CN 1172084A
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Prior art keywords
flyash
slag
burning
cement
chamotte
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CN96118276A
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Chinese (zh)
Inventor
李建军
张耀伦
陈丹
周惠君
蔡啡琳
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KELUN NEW AND HIGH TECHNOLOGY DEVELOPMENT INST CHANGSHA
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KELUN NEW AND HIGH TECHNOLOGY DEVELOPMENT INST CHANGSHA
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Priority to CN96118276A priority Critical patent/CN1172084A/en
Publication of CN1172084A publication Critical patent/CN1172084A/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/24Cements from oil shales, residues or waste other than slag
    • C04B7/243Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/08Slag cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/24Cements from oil shales, residues or waste other than slag
    • C04B7/26Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding

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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)
  • Processing Of Solid Wastes (AREA)

Abstract

The present invention relates to a clinker-free burning-free fly ash cement. Its raw material composition is composed of (wt%) 30-50% of fly ash, 20-36% of blast furnace slag, 14-22% of steel dregs, 5.2-7.5% of lime and gypsum, 1.5-2.5% of additive and 4.5-6% of compound hardening agent. Its preparation method includes the following steps: oven-drying fly ash and blast furnace slag: crushing and oven-drying steel dregs; crushing lime and gypsum; mixing all raw materials; and grinding so as to obtain the invented fly ash cement whose grade mark can be up to above 425.

Description

Non-chamotte burning-free flyash cement
The invention belongs to waste material and produce the cement technology field, relate to a kind of non-chamotte burning-free flyash cement.
Flyash is the waste material that modern coal-fired power plant discharges, and quantity is very big, ranks preceding lance in various industrial residues.Along with developing rapidly of power industry, the quantity discharged of flyash grows with each passing day.China is from 83 years, with 4,000,000 tons speed increment every year on average.The flyash annual emissions in the whole nation has approached 100,000,000 tons at present.The particle of flyash is thin, and is in light weight, is the source of pollution that generally acknowledge countries in the world.So a large amount of flyash is as actively not administering, very serious to the pollution of environment.If can make full use of, the renewable resource that are easy to get greatly of the amount of being then, therefore countries in the world are all in the research of actively developing the flyash regeneration, China is to the about 20-30% of the average utilization of flyash, annual about 70% the flyash in addition in the whole nation fails to utilize at present, promptly about 7,000 ten thousand tons/year, this numeral is quite surprising.Utilizing flyash to produce cement is the wide effective technical way of the big use of on record a kind of utilization, but the utilization ratio of flyash in cement is still very low at present, general volume is 20-30%, the more masonry cement that utilizes flyash of energy, its label is low, generally only be cement of low index such as 124,175,225, the market acceptance level is very low, is difficult to mass production.Chinese invention patent application publication number CN1105344A (open day: on July 19th, 95), a kind of " method for making non-clinker cement by wet-milling flyash and goods thereof " patent application is disclosed, this patent application discloses a kind of with wet fly-ash system clinker-free cement, this cement be with wet-discharged coal ash through levigate, store, dewater naturally, carry out a kind of cement of low index (275#) of obtaining behind the thorough mixing with the mixture of levigated lime, gypsum and calcium lignin sulphonate again.This cement, because label is low, purposes is very limited, production process more complicated, levigated flyash again need be passed through and store, be dewatered naturally, so the production time is long, is difficult to promote the use of.
The objective of the invention is to provide a kind of use flyash amount large percentage, production process is simple, cost is low, intensity height, unburned, pulverized fuel ash cement and the manufacture method that need not mix grog.
The objective of the invention is to realize with the following methods.
Non-chamotte burning-free flyash cement of the present invention contains flyash, slag, lime, gypsum, also contain slag, admixture auxiliary agent, composite curing agent, more than the content of each component thing in cement be respectively (weight percent): flyash 30-50%, slag 20-36%, slag 14-22%, lime+gypsum 5.2-7.5%, admixture auxiliary agent 1.5-2.5%, composite curing agent 4.5-6%.The admixture auxiliary agent that is adopted is the mixture that contains naphthalene sulfonic salt water reducer 10-25%, alum 20-40%, sodium sulfate and yellow soda ash 40-70% (weight percent).The composite curing agent that is adopted is the mixture of urea (weight percent) of calcined gypsum, the 10-20% of the water glass of the calcium sulphoaluminate that contains 30-40%, 30-40% or potassium silicate, 10-20%.Non-chamotte burning-free flyash cement of the present invention is different with conventional Portland fly ash cement, and it excites the activity of flyash without Portland clinker, does not also rely on Portland clinker to gain in strength, and does not also need to calcine again and improves performance.But adopt metallurgical industry slag (as slag, slag, manganese slag, phosphorus slag etc.) and flyash collocation, constitute cement matrix, and use the composite curing technology, be aided with lime, gypsum, admixture, auxiliary agent etc. and unite the activity that excites flyash and metallurgical industry slag, make pulverized fuel ash cement, its product strength height, but the cement of stably manufactured 425 labels by the technology of simplifying, the flyash consumption is big, and saving energy, cost are low, less investment, remarkable economic and social benefits.
The present invention makes the method for non-chamotte burning-free flyash cement, be that flyash is dried, lime and gypsum fragmentation, press flyash 30-50% then, slag 20-36%, slag 14-22%, lime+gypsum 5.2-7.5%, admixture auxiliary agent 1.5-2.5%, the ratio batching of composite curing agent 4.5-6% (weight percent), mixed grinding afterwards, grind arrival regulation fineness and get final product test package, moisture<1.5% after the flyash oven dry, moisture behind the slag drying<1%, granularity<5mm behind the slag crushing, moisture after the oven dry<1%, the granularity<10MM after lime and the anhydrite fragmentation.When the mixture after will preparing burden ground, its mesh-of-grind was controlled between the 0.08MM screen over-size 3-4%.
Raw material used in the present invention adopts lime to excite the principle of laying equal stress on gypsum activation.Free calcium oxide (fcao) content is higher in the slag, should make full use of the Ca (OH) after the fcao aquation 2, both with flyash in active SiO 2And Al 2O 3Effect excites the activity of flyash, again with slag in the vitreum effect, the activity of activated slag is eliminated the too high disadvantage of fcao in the slag simultaneously.In addition, also can add lime in right amount, to strengthen to flyash and slag according to the prescription situation, the slag alkaline excitation, CaO that adds and the fcao different in kind in the slag, the former hydration rate is fast, can participate in the early response of cement, latter's calcining temperature height, compact structure, hydration rate is slow, participates in reaction in the middle and later periods.Adopt combination gypsum that flyash and metallurgical slag are carried out the gypsum sulphate activation simultaneously, very fast because of different types of gypsum has different dissolution raties as dihydrate gypsum and semi-hydrated gypsum dissolving, to favourable in early days.The anhydrite dissolution rate is slower, to mid-term mineral form favourable.The calcined gypsum dissolving slowly, and is favourable to later strength.According to flyash, steel, slag strength development situation, adopting rational combination gypsum is effective means.The composite curing agent that adopts among the present invention participates in exciting the lateral reactivity of flyash and metallurgical slag, and promotes the stimulation effect of lime, gypsum.Can replace Portland clinker therefrom, and more effective than exciting of cement clinker with reinforced effects, under the less situation of consumption, obtain higher intensity.The composition of admixture auxiliary agent is mainly efficient additive and microchemistry auxiliary agent, be for satisfying various technical requirementss such as production technique, prescription, wood property, can promote the reaction between each component of prescription, make that proportioned material is easy to grind to disperse, time of coagulation rationally, the early strength development is very fast etc., in order to producing and using.
Be the embodiment that do not limit of the present invention below.Flyash adopts the waste residue of Huaneng Group, Yueyang power plant, belongs to II level ash, and slag and slag are the metallurgical slag of Hunan, Hunan steel and ripples steel.
1, chemical ingredients (seeing Table 1)
2, batching (seeing Table 2)
3, the technological process of production (seeing accompanying drawing 1)
Table 2 column data by the embodiment of the invention is analyzed as can be known:
One, when the flyash consumption is respectively 30%, 35%, 40%, ore deposit, slag content add up to and be respectively 58%, 53%, 48%, other adds the composition resultant and is 12%, when adopting composite curing agent, can make 425 pulverized fuel ash cements.Along with the increase of flyash consumption, label more than needed reduces, but all reaches 425 strength of cement indexs (seeing three groups of C4, C5, C6).
Two, when the flyash consumption be 45%, ore deposit, slag resultant are 42%, other adds composition is 13%, when adopting composite curing agent, can make 325 pulverized fuel ash cements, its resistance to compression, folding strength surplus capacity be big (seeing two groups of C13, C27).
Three, when the flyash consumption be 42%, ore deposit, slag resultant are 45%, other adds composition is 13%, when adopting composite curing agent, can make 425 pulverized fuel ash cements, but label more than needed is less, illustrates that the flyash consumption to this quality reaches the 425 cement limit (seeing the C28 group).
Four, when the flyash consumption is 50%, ore deposit, slag resultant are 34%, other adds composition is 16%, when adopting composite curing agent, also can make 325 pulverized fuel ash cements, but label more than needed is less, and to the flyash of this kind quality, consumption has reached the 325 cement limit (seeing the C30 group).
According to above analysis, can draw to draw a conclusion:
Under situation without Portland clinker, only adopt flyash to cooperate with metallurgical slag, when its total amount reaches 84-88%, add the suitable various composition 12-16% that add of character, can make non-chamotte burning-free flyash mud, different according to the flyash quality with consumption, can produce the pulverized fuel ash cement of different labels.When adopting II level flyash, consumption can be produced pulverized fuel ash cement No. 425 in 42%, and consumption can be produced pulverized fuel ash cement No. 325 at 42-50%.
Table 1
Table 2
Test number Prescription (%) The anti-intensity Mpa that analyses Ultimate compression strength Mpa
Flyash Slag Slag Lime stone-gypsum The admixture auxiliary agent Composite curing agent
??3d ??7d ??28d ??3d ??7d ??28d
?C4 ????30 ???36 ????22 ????6 ????1.5 ????4.5 ??5.16 ??6.82 ??7.48 ??22.58 ??34.54 ?45.26
?C5 ????35 ???33 ????20 ????5.2 ????1.8 ????5.8 ??4.52 ??5.67 ??6.87 ??18.85 ??30.43 ?43.58
?C6 ????40 ???30 ????18 ????5.2 ????1.8 ????5.0 ??3.86 ??5.06 ??6.65 ??17.64 ??27.66 ?42.83
?C13 ????45 ???26.6 ????15.6 ????5.7 ????1.8 ????5.3 ??3.86 ??5.07 ??6.36 ??15.82 ??24.56 ?37.64
?C27 ????45 ???26 ????16 ????5.5 ????2.0 ????5.5 ??3.43 ??4.98 ??6.42 ??16.25 ??25.47 ?38.86
?C28 ????42 ???27 ????18 ????5.5 ????2.0 ????5.5 ??3.33 ??5.22 ??6.53 ??16.74 ??26.78 ?42.65
?C30 ????50 ???20 ????14 ????7.5 ????2.5 ????6.0 ??1.86 ??3.94 ??5.64 ??11.34 ??18.46 ?32.82

Claims (6)

1, a kind of non-chamotte burning-free flyash cement, contain flyash, slag, lime, gypsum, it is characterized in that also containing slag, admixture auxiliary agent, composite curing agent, more than the content of each component thing in cement be respectively (weight percent): flyash 30-50%, slag 20-36%, slag 14-22%, lime+gypsum 5.2-7.5%, admixture auxiliary agent 1.5-2.5%, composite curing agent 4.5-6%.
2, non-chamotte burning-free flyash cement according to claim 1 is characterized in that the admixture auxiliary agent is the mixture that contains naphthalene sulfonic salt water reducer 10-25%, alum 20-40%, sodium sulfate and yellow soda ash 40-70% (weight percent).
3, non-chamotte burning-free flyash cement according to claim 1 and 2 is characterized in that composite curing agent is the mixture of the urea (weight percent) of the calcined gypsum that contains the water glass of 30-40% or potassium silicate, 10-20,10-20%.
4, a kind of method of making non-chamotte burning-free flyash cement, be that flyash and slag drying, slag are dried after fragmentation, lime and gypsum fragmentation, prepare burden in the ratio of flyash 30-50%, slag 20-36%, slag 14-22%, lime+gypsum 5.2%-7.5%, admixture auxiliary agent 1.5-2.5%, composite curing agent 4.5-6% (weight percent) then, mixed grinding grinds arrival regulation fineness and gets final product test package afterwards.
5, the method for manufacturing non-chamotte burning-free flyash cement according to claim 4, it is characterized in that moisture<1.5% after flyash is dried, moisture behind the slag drying<1%, moisture<1% after granularity<5mm behind the slag crushing, the oven dry, the granularity<10mm after lime and the anhydrite fragmentation.
6,, it is characterized in that with the mixture after the batching its mesh-of-grind is controlled between the 0.08mm screen over-size 3-4% when grinding according to the method for claim 4 or 5 described manufacturing non-chamotte burning-free flyash cements.
CN96118276A 1996-07-25 1996-07-25 Non-chamotte burning-free flyash cement Pending CN1172084A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1102543C (en) * 1998-10-09 2003-03-05 株洲市台联企业总公司 High-performance non-clinker powdered coal ash-slags cement
US6749679B2 (en) 2002-01-23 2004-06-15 Advanced Materials Technologies, Llc Composition of materials for production of acid resistant cement and concrete and methods thereof
CN103717547A (en) * 2011-04-14 2014-04-09 格林班德科技公司 Cementitious binder containing pozzolanic material
CN104261705A (en) * 2014-08-27 2015-01-07 成浩 Fly ash synthesized cement and production method thereof
CN105236781A (en) * 2015-10-16 2016-01-13 广西巨邦科技有限公司 Building cement
CN105481278A (en) * 2014-09-15 2016-04-13 武汉鸿信通科技有限公司 Green environmental-protection cement
CN106116189A (en) * 2016-06-28 2016-11-16 东南大学 A kind of no first-hand datum lithium slag composite gelled material
CN106145721A (en) * 2016-08-22 2016-11-23 安徽省高迪环保股份有限公司 A kind of pulverized fuel ash cement processing method
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
CN107056099A (en) * 2017-04-28 2017-08-18 河北科技大学 A kind of preparation method of low-intensity binder materials
CN111302683A (en) * 2019-12-30 2020-06-19 申新民 Masonry cement and production process thereof
CN111646720A (en) * 2020-06-29 2020-09-11 常熟理工学院 Dry process for preparing non-sintered cement and its product
CN113056443A (en) * 2018-11-03 2021-06-29 塞玛特有限责任公司 Additive for inorganic polymer cement

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1102543C (en) * 1998-10-09 2003-03-05 株洲市台联企业总公司 High-performance non-clinker powdered coal ash-slags cement
US6749679B2 (en) 2002-01-23 2004-06-15 Advanced Materials Technologies, Llc Composition of materials for production of acid resistant cement and concrete and methods thereof
US9890079B2 (en) 2011-04-14 2018-02-13 Green Binder Technologies Ltd. Cementitious binders containing pozzolanic materials
CN103717547A (en) * 2011-04-14 2014-04-09 格林班德科技公司 Cementitious binder containing pozzolanic material
CN104261705A (en) * 2014-08-27 2015-01-07 成浩 Fly ash synthesized cement and production method thereof
CN105481278A (en) * 2014-09-15 2016-04-13 武汉鸿信通科技有限公司 Green environmental-protection cement
CN105236781A (en) * 2015-10-16 2016-01-13 广西巨邦科技有限公司 Building cement
CN106116189A (en) * 2016-06-28 2016-11-16 东南大学 A kind of no first-hand datum lithium slag composite gelled material
CN106116189B (en) * 2016-06-28 2018-03-20 东南大学 A kind of no first-hand datum lithium slag composite gelled material
CN106145721A (en) * 2016-08-22 2016-11-23 安徽省高迪环保股份有限公司 A kind of pulverized fuel ash cement processing method
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
CN107056099A (en) * 2017-04-28 2017-08-18 河北科技大学 A kind of preparation method of low-intensity binder materials
CN107056099B (en) * 2017-04-28 2019-04-05 河北科技大学 A kind of preparation method of low-intensity cementitious material
CN113056443A (en) * 2018-11-03 2021-06-29 塞玛特有限责任公司 Additive for inorganic polymer cement
CN111302683A (en) * 2019-12-30 2020-06-19 申新民 Masonry cement and production process thereof
CN111646720A (en) * 2020-06-29 2020-09-11 常熟理工学院 Dry process for preparing non-sintered cement and its product

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